Mobilizing Chemistry Expertise To Solve Humanitarian Problems. [1] 9780841232655, 0841232652, 9780841232679, 9780841232662, 9780841232686

Table of contents :
Content: Mobilizing Chemistry Expertise To Solve Humanitarian Problems: Introduction / Grosse, Ronda / The History and Mission of Chemists Without Borders / Chambreau, Steven D.
Gerber, Bego / Arsenic Education and Remediation in Bangladesh / Kronquist, Ray
Begum, Shahena / “Penny per Test” --
Low Cost Arsenic Test Kits / Lizardi, Christopher Lee, Clear Waters Testing, 3708 W. Bearss Ave., Suite B3422, Tampa, Florida 33618, United States, Chemists Without Borders / Development of a Test-Kit Method for the Determination of Inorganic Arsenic in Rice / Tyson, Julian
Rafiyu, Ishtiaque
Fragola, Nicholas / Arsenic in Food and Water: Promoting Awareness through Formal and Informal Learning / Tyson, Julian / Lessons from the Field: Humanitarian Work in Latin America / Leigh, Nathan D. / Distributed Pharmaceutical Analysis Laboratory (DPAL): Citizen Scientists Tackle a Global Problem / Bliese, Sarah L.
Berta, Margaret
Myers, Nicholas M.
Lieberman, Marya / Addressing the 3A’s (Availability, Accountability, Adherence) of Supply Chain Systems in Western Kenya / Karwa, Rakhi, Purdue University College of Pharmacy, West Lafayette, Indiana, 47907, United States, Moi University, School of Medicine, Department of Pharmacology, Eldoret, Kenya
Tran, Dan N., Purdue University College of Pharmacy, West Lafayette, Indiana, 47907, United States, Moi University, School of Medicine, Department of Pharmacology, Eldoret, Kenya
Maina, Mercy, Moi Teaching and Referral Hospital, Eldoret, Kenya
Njuguna, Benson, Moi Teaching and Referral Hospital, Eldoret, Kenya
Manji, Imran, Moi Teaching and Referral Hospital, Eldoret, Kenya
Wasike, Paul, Moi University, School of Medicine, Department of Pharmacology, Eldoret, Kenya
Tonui, Edith, Moi Teaching and Referral Hospital, Eldoret, Kenya
Kigen, Gabriel, Moi University, School of Medicine, Department of Pharmacology, Eldoret, Kenya, Moi Teaching and Referral Hospital, Eldoret, Kenya
Pastakia, Sonak D., Purdue University College of Pharmacy, West Lafayette, Indiana, 47907, United States, Moi University, School of Medicine, Department of Pharmacology, Eldoret, Kenya / Acknowledgments / Editor’s Biography /

Citation preview

Mobilizing Chemistry Expertise To Solve Humanitarian Problems Volume 1

ACS SYMPOSIUM SERIES 1267

Mobilizing Chemistry Expertise To Solve Humanitarian Problems Volume 1 Ronda L. Grosse, Editor Chemists Without Borders

Sponsored by the ACS Division of Analytical Chemistry

American Chemical Society, Washington, DC Distributed in print by Oxford University Press

Library of Congress Cataloging-in-Publication Data Names: Grosse, Ronda L., 1965- editor. | American Chemical Society. Division of Analytical Chemistry. Title: Mobilizing chemistry expertise to solve humanitarian problems / Ronda L. Grosse (Chemists Without Borders), editor ; sponsored by the ACS Division of Analytical Chemistry. Description: Washington, DC : American Chemical Society, [2017]- | Series: ACS symposium series ; 1267, 1268 | Includes bibliographical references and index. Identifiers: LCCN 2017046881 (print) | LCCN 2017049595 (ebook) | ISBN 9780841232655 (ebook, v. 1) | ISBN 9780841232679 (ebook, v. 2) |ISBN 9780841232662 (v. 1) | ISBN 9780841232686 (v. 2) Subjects: LCSH: Chemistry--Social aspects. Classification: LCC QD39.7 (ebook) | LCC QD39.7 .M63 2017 (print) | DDC 363.738/49--dc23 LC record available at https://lccn.loc.gov/2017046881

The paper used in this publication meets the minimum requirements of American National Standard for Information Sciences—Permanence of Paper for Printed Library Materials, ANSI Z39.48n1984. Copyright © 2017 American Chemical Society Distributed in print by Oxford University Press All Rights Reserved. Reprographic copying beyond that permitted by Sections 107 or 108 of the U.S. Copyright Act is allowed for internal use only, provided that a per-chapter fee of $40.25 plus $0.75 per page is paid to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, USA. Republication or reproduction for sale of pages in this book is permitted only under license from ACS. Direct these and other permission requests to ACS Copyright Office, Publications Division, 1155 16th Street, N.W., Washington, DC 20036. The citation of trade names and/or names of manufacturers in this publication is not to be construed as an endorsement or as approval by ACS of the commercial products or services referenced herein; nor should the mere reference herein to any drawing, specification, chemical process, or other data be regarded as a license or as a conveyance of any right or permission to the holder, reader, or any other person or corporation, to manufacture, reproduce, use, or sell any patented invention or copyrighted work that may in any way be related thereto. Registered names, trademarks, etc., used in this publication, even without specific indication thereof, are not to be considered unprotected by law. PRINTED IN THE UNITED STATES OF AMERICA

Foreword The ACS Symposium Series was first published in 1974 to provide a mechanism for publishing symposia quickly in book form. The purpose of the series is to publish timely, comprehensive books developed from the ACS sponsored symposia based on current scientific research. Occasionally, books are developed from symposia sponsored by other organizations when the topic is of keen interest to the chemistry audience. Before agreeing to publish a book, the proposed table of contents is reviewed for appropriate and comprehensive coverage and for interest to the audience. Some papers may be excluded to better focus the book; others may be added to provide comprehensiveness. When appropriate, overview or introductory chapters are added. Drafts of chapters are peer-reviewed prior to final acceptance or rejection, and manuscripts are prepared in camera-ready format. As a rule, only original research papers and original review papers are included in the volumes. Verbatim reproductions of previous published papers are not accepted.

ACS Books Department

Contents 1.

Mobilizing Chemistry Expertise To Solve Humanitarian Problems: Introduction .............................................................................................................. 1 Ronda Grosse

2.

The History and Mission of Chemists Without Borders .................................... 11 Steven D. Chambreau and Bego Gerber

3.

Arsenic Education and Remediation in Bangladesh ........................................... 29 Ray Kronquist and Shahena Begum

4.

“Penny per Test” - Low Cost Arsenic Test Kits .................................................. 51 Christopher Lee Lizardi

5.

Development of a Test-Kit Method for the Determination of Inorganic Arsenic in Rice ........................................................................................................ 63 Julian Tyson, Ishtiaque Rafiyu, and Nicholas Fragola

6.

Arsenic in Food and Water: Promoting Awareness through Formal and Informal Learning ................................................................................................. 83 Julian Tyson

7.

Lessons from the Field: Humanitarian Work in Latin America ....................... 99 Nathan D. Leigh

8.

Distributed Pharmaceutical Analysis Laboratory (DPAL): Citizen Scientists Tackle a Global Problem ..................................................................................... 117 Sarah L. Bliese, Margaret Berta, Nicholas M. Myers, and Marya Lieberman

9.

Addressing the 3A’s (Availability, Accountability, Adherence) of Supply Chain Systems in Western Kenya ....................................................................... 129 Rakhi Karwa, Dan N. Tran, Mercy Maina, Benson Njuguna, Imran Manji, Paul Wasike, Edith Tonui, Gabriel Kigen, and Sonak D. Pastakia

Acknowledgments ........................................................................................................ 159 Editor’s Biography ....................................................................................................... 165

Indexes Author Index ................................................................................................................ 169

vii

Subject Index ................................................................................................................ 171

viii

Chapter 1

Mobilizing Chemistry Expertise To Solve Humanitarian Problems: Introduction Ronda Grosse* Chemists Without Borders

http://www.chemistswithoutborders.org/ *E-mail:

[email protected].

This chapter introduces the motivation for the American Chemical Society symposium held, and provides an overview of multiple humanitarian projects that require scientific expertise. The purpose of this book series is to expand on conference discussions and inform readers of ongoing work using chemistry to benefit underrepresented communities. Topics include clean water initiatives, access to quality medicines, science education, and advancements in inexpensive analytical methodologies that can be applied in developing countries. In most cases, utilization of local resources in country is key. Volume 1 covers targeted humanitarian aid work in South Asia, South America, and Africa.

World statistics on top humanitarian issues today include refugees of war, political instability, natural disasters resulting in famine and homelessness, lack of education, poor infrastructure, disease, and scarcity of medicines and clean water (1–4). Around 75% of people living in poverty are located in environmentally vulnerable or politically fragile countries (5). This human suffering has accelerated the search for new practices to allow finite resources to help people affected by various crises. In particular, shortage of clean water has far-reaching negative impact. Improving water quality and availability would bring about real change in the critical areas of hygiene and sanitation, reducing diseases and premature deaths. It would also decrease conflicts and pollution, and increase gender equality, healthy food production, and strengthen communities (6). © 2017 American Chemical Society

Across the globe, a considerable number of humanitarian problems remain unresolved. Many non-profit and non-government organizations (NGOs) work diligently to contribute ideas and resources toward solving these problems. In addition to altruistic aid provided by such charities, as well as what is given by government and other social agencies, creative solutions from chemists are greatly needed. This book focuses on the humanitarian issues that may benefit from applying science, exploring ways in which chemists can uniquely contribute to providing potential solutions to these problems. Analytical chemistry can afford specific benefits in this type of international humanitarian work, as trace measurement of contaminants is often pivotal to confronting problems – whether they involve pure water, food or medicines. This volume (and Volume 2) includes multiple examples from laboratories worldwide where chemistry is being utilized to address humanitarian problems such as water, food and pharmaceutical quality. Several of the authors also volunteer their time at Chemists Without Borders. Chemists Without Borders is a public benefit, non-profit, international humanitarian volunteer network designed to alleviate human suffering through the use of proven chemical technologies and related skills. Its primary goals include, but are not limited to, providing affordable medicines, vaccines and medical devices to those who need them most, suplying environmental solutions (e.g., water purification, green energy and chemistry) in developing countries, supporting self-reliance education, and providing disaster relief. Chemists Without Borders fosters collaborations with other organizations for the mutual benefit of their various missions (7). Chemists Without Borders seeks to mobilize the resources and expertise of the global chemistry community and its networks. Chemists and others have united to work toward solutions to longstanding humanitarian issues. An invited symposium at the 2016 Fall National American Chemical Society meeting, sponsored by the Analytical Chemistry Division, addressed this topic. Given below are abstracts of the ten papers presented at the symposium. 1.

Chemists Without Borders: Providing Humanitarian Solutions by Mobilizing the Chemistry Community and its Networks by Bego Gerber, Chemists Without Borders Imagine a future time when chemists are as renowned for their humanitarian work as doctors are today. Chemists Without Borders is a vehicle that allows chemists and their networks to make that future come true. We will briefly review the history of Chemists Without Borders and its extraordinary team of volunteers, and discuss some of the lessons learned.

2.

Distributed Pharmaceutical Analysis Lab: Citizen Scientists Tackle a Global Problem by Marya Lieberman, Dept. of Chemistry and Biochemistry, University of Notre Dame 2

Falsified and substandard medications harm patients, damage trust in the medical system, and contribute to development of “superbugs”. The analytical procedures needed to assay pharmaceuticals are well established and match the types of experiments often carried out in instrumental analysis courses. The Distributed Pharmaceutical Analysis Lab connects analytical laboratories at academic institutions in the US with medical regulatory agencies in the developing world. Students get the opportunity to analyze samples that really matter, and their results help to ensure that people everywhere have access to high quality medicines. 3.

Solving Problems of Humanity with Separation Chemistry by Satinder Ahuja, Ahuja Consulting Chemists can help solve various problems facing humanity, with their expertise in chromatography and separation chemistry. Adverse effects from chemicals can be encountered even when human beings are not responsible for them. Arsenic contamination of groundwater from Mother Earth is one such example, where about 200 million people have been affected worldwide, including the United States. In response to my worldwide appeal in 2003 in C&EN, a large number of chemists offered to help. With the help of small grants from ACS and IUPAC in 2005, we held a workshop in Bangladesh where this problem was affecting 100 million people. This was followed by symposia at the Atlanta ACS meeting. Following these discussions, potential solutions to the problem were published in Science. Unfortunately, the problem still plagues 20 million to 30 million people in Bangladesh. A study was designed for Chemists Without Borders to help educate students and, through them, the community, on the hazards of arsenic contamination. We found that water drunk by children at 2 out of 6 schools had high arsenic contents. We are in the process of remediating this situation and are looking for volunteers with innovative ideas who can help improve the current water purification systems. This can lead to profitable businesses and more employment. Some examples of our work will be discussed.

4.

Arsenic in Food and Water: Promoting Awareness Through Formal and Informal Learning on and off the Campus by Julian Tyson, Dept. of Chemistry, University of Massachusetts, Amherst Several programs, organized by Chemists without Borders or the University of Massachusetts Amherst, in which secondary school or college students are introduced to the impact of arsenic contamination of the environment, and in particular of groundwater in Bangladesh, are described. A common feature is that students are recruited as members of a research group or investigative team and take ownership of the work by making relevant chemical measurements and participating in discussion of the implications of their findings. Leadership is provided 3

in a hierarchical model in which, very often, more experienced students acting as near-peer mentors guide the activities of the newly recruited members of the groups. In some of the programs, the students work with teachers who have been trained by researchers on the university campus. Both in-school and out-of-school programs are described. Another common feature is that chemical measurements are provided by low-cost field test kits based on the Gutzeit-Marsh reaction, the modification of which has provided a driving force for a considerable number of research projects. Currently, researchers affiliated with Chemists without Borders are critically evaluating several possible strategies for making the test more cost effective. Many hundreds of students have been impacted, and the programs, particularly that in Bangladesh, have considerable potential for empowering the students as agents of change in their communities as they not only take specific action as a result of their engagement but also educate other members of their families and communities about the potential hazards of consuming arsenic-contaminated water and rice and how these can be mitigated. Raising student awareness has also been achieved by incorporating relevant arsenic-related topics into undergraduate courses on the UMass campus, including the junior-year writing class, a large-enrollment, physical sciences general education class for non-scientists (taught in both face-to-face and online modes), a faculty first-year seminar, and a course-based research experience. 5.

“Penny per Test” – Low Cost Arsenic Test Kits by Christopher Lizardi, ChemTel, Inc. Arsenic contamination of drinking waters is a major health and environmental issue, and poor rural communities are often disproportionately affected. This is especially the case in Bangladesh, where most rural water supplies come from tubewells that are contaminated with arsenic from mineral sources and leaching of agricultural and industrial arsenic-containing compounds. In spite of this, testing wells and water supplies contaminated by arsenic remains a challenge for most rural Bangladeshis due to the high cost of arsenic test kits available on the market. Chemists Without Borders (CWB) has recently discovered a possible solution for the people of Bangladesh, by developing a “Penny per Test” arsenic test kit. CWB plans to manufacture test kits based on the established Gutzeit method in Bangladesh, with pilot-scale studies performed at the Asian University for Women. This could lead to the start-up of a manufacturing facility for arsenic test kits in Bangladesh. We envision this will provide the lowest cost option to Bangladeshi laboratories and public health departments, in addition to employing Bangladeshi citizens. This will serve to empower the people of these rural communities, and give them greater chances to protect their families with accurate and precise knowledge about the chemistry and purity of their water supplies. 4

6.

Chemistry Education in Sierra Leone by A Bakarr Kanu, Department of Chemistry, Winston-Salem State University Sierra Leone suffered a civil war from 1991-2002 from which much of the country’s infrastructure and educational system was devastated. To address the urgent need of chemistry education in Sierra Leone, Chemists Without Borders volunteers have partnered with other organizations to provide greatly-needed chemistry materials to resume science coursework and enhance student learning. Our plan is to assemble inexpensive lab kits focusing on experiments relevant to Sierra Leone and other developing countries. In addition to standard labs that will help students understand basic chemical concepts, the laboratory exercises are unique in that they also focus on the application of chemistry towards practical knowledge relevant to the lives of ordinary Sierra Leoneans. Our plan is to assemble 12-15 lab activity kits ready for use in Sierra Leone by September 2017. We anticipate upon implementation of this project, the kits will service between 200-500 teachers and students covering approximately 50 schools in the region annually.

7.

Electrically Controlled Drug Delivery by Richard Zare and Devleena Samanta, Dept. of Chemistry, Stanford University One of the main challenges in drug delivery is to develop less invasive, localized, and precisely controllable drug release methods to minimize side effects and increase drug efficacy. We report the development of a drug delivery system based on electric-stimuli-responsive polymers that can provide spatially and temporally controlled drug release. This could have significant medical applications, particularly in the treatment of chronic diseases that require repeated doses of drugs, such as, cancer therapy, diabetes, and chronic pain management.

8.

A Major Impediment to the Effectiveness of Chemists’ Role in Improving Lives in Developing Countries by Ephraim Govere, Dept. of Crop and Soil Sciences, Pennsylvania State University In virtually all developing countries, people’s main concern is to meet the first level of Abraham Harold Maslow’s hierarchy of needs: water, food, clothing, and shelter. These needs are actually chemical products in which chemists play a superior role. Thus, chemists are essential to human existence. However, compared to other professionals, chemists are not as involved in development projects in developing countries. The general notion of a chemist is someone who works in the laboratory and this is true to a great extent. Our University curriculums also testify to this – a lot of chemistry lectures and laboratory practicums. This mode of education and work style has created one major impediment to the effectiveness of a chemist, as a global team member, to improve the lives of those living in developing countries. My experience as a project 5

manager and project evaluator of international development projects has led me to believe that the major impediment to the effectiveness of a chemist is the lack of cultural competence. Being culturally competent means possessing the values, knowledge, skills, attitudes, and attributes that will allow the chemist to work appropriately, respectfully, effectively, and efficiently with colleagues and clients from different ethnic, racial, religious, geographic, or social groups. This presentation will highlight soil-testing programs for fertilizer application in Africa that failed due to chemists’ lack of cultural competence. The lessons learned will contribute to the understanding of the logistical challenges involved in improving the lives of those throughout the globe. 9.

Extensively Low-cost 3D Printed Biochemical Instrumentation With a Novel Zero-dollar Interface and Distributed Firmware by Matthew Champion, Dept. of Chemistry and Biochemistry, University of Notre Dame Commercial lab equipment remains a challenge in resource-limited areas. Building capacity is critical to developing independent research infrastructures. The high-precision equipment necessary to perform basic molecular biology techniques remains financially and logistically out of reach of many environments. Efforts to design low-cost instrumentation do not factor assay cost. The choice of liquid volume and throughput increases consumable costs eliminating savings from reduced cost-devices. Inexpensive controllers enable complex firmware; however interfaces, screens, and input devices become a substantial portion of costs. Repairing and replacing parts on devices is also problematic and has significant cost. Here we introduce our design framework to ameliorate these barriers by offering nearly fully 3D printed molecular instrumentation which are controlled by a novel firmware which is interface-free. Complex logic to directly control lab equipment and robots is readily encoded in the audio and video signals from online and social media sites like YouTube. Access to mp3 files in the form of video/ipods or even phone calls enables us to perform movement and control tasks to run biochemical equipment without programming, editing or control inputs. We have focused implementation on two major instrumentation areas; Polymerase Chain Reaction with thermal cyclers and liquid chromatography separations. We have built a 3D printed thermal cycler, which is programmed via a social-media interface and is capable of amplifying DNA and RNA in 96-well format. PCR is an essential process for molecular diagnostics and any healthy life-science infrastructure. Parts can be made in situ using the most inexpensive 3D printers currently on the market, and reagent tubes can be scaled to any volume-reducing the operating costs to those of high-throughput instruments. Liquid chromatography is the most dominant form of separation used to purify and separate compounds. We have designed a separate firmware-free FPLC to 6

perform gradient liquid chromatography at biochemical scales using 3D printed pumps valves, and columns. 3D printed materials suffer rapid fatigue and failure under stress; the availability of printable wear-tolerant nylon has made the pumps more durable than peristaltic tubing. Our distributed firmware and on-site part creation raise the distinct possibility that fully-functioning lab equipment will be e-mailed or downloaded at the convenience of a researcher. 10. Physiochemical Changes of Prussian Blue by Adil Mohammad, Division of Product Quality Research, Food and Drug Administration Prussian Blue (PB) or ferric hexacyanoferrate is an FDA approved oral dosage form for the treatment of internal radioactive contamination of cesium or thallium. PB is one of the oldest known and most stable inorganic compounds and is a critical medical countermeasure drug stored in the Strategic National Stockpiles. Previous work conducted in our labs shows that PB is thermodynamically stable, but physiochemical changes in PB crystals occur due to the loss of bound water. This loss of water decreases the binding capacity of thallium and cesium. The current study is focused on evaluating the loss of iron over the human gastrointestinal pH profile, to further investigate the physiochemical stability of PB crystal. Loss of water from PB was determined using thermogravimetric analysis (TGA). PB was incubated in situ at pH 1.0, 5.0 and 7.5 @ 37°C for 1-24 hours. Iron metal was measured using a validated inductively coupled plasma-mass spectrometry (ICP-MS) method. Results show that leaching of Fe from PB crystal is pH dependent, with negligible leaching of Fe at gastric pH 1.0 and upper GI pH of 5.0, but the amount of Fe increased to 50 ppm from PB drug product at pH 7.5. Analytical method development/validation for Fe using ICP-MS and in detail Fe leaching experiments, along with results, will be discussed. The purpose of this book (Volumes 1 and 2) is to expand upon symposium discussions and inform readers of ongoing work applying chemistry to benefit underrepresented communities. Topics include clean water initiatives, expanding access to quality medicines, science education, and advancements in inexpensive analytical methodologies that can be readily applied in developing countries. Projects in progress or completed are summarized, and assessment of the comprehensive benefits of these efforts is provided. In addition, logistical, cultural and technical challenges are explained. Subjects beyond what was covered at the ACS meeting symposium include addressing the heavy metal contamination problem in Bangladesh through education, water testing and well remediation, and development of a test-kit method for the determination of inorganic arsenic in rice. Additionally, the history and mission of AIDSfreeAFRICA in Cameroon is explained, as is the Foundation for Analytical Science in Africa. Specific supply chain issues in Kenya related to availability, accountability, and adherence are discussed. Chapters covering 7

projects in Latin America include science education in Guatemala and engineering work in Bolivia. Topics vary from specific green chemistry using softwood lignon to a general overview of analytical chemists easing world poverty. In Volume 1, the Chapter 2 provides an introduction to the nonprofit organization, Chemists Without Borders, including its inception, organization, and ongoing humanitarian work. Chapter 3 outlines the most significant project of Chemists Without Borders to date: Arsenic Education in Bangladesh. Through a combination of educating high schools and communities about the dangers of arsenic in drinking water, providing test kits and instruction on how to test water, and remediation of contaminated water sources with new wells, CWB has made considerable strides in addressing the arsenic problem in Bangladesh. Chapter 4 describes efforts toward developing an inexpensive test kit for measuring arsenic in water using locally supplied materials. In Chapter 5 and Chapter 6, research into a new method for analyzing inorganic arsenic content in rice is reviewed, and the authors discuss how awareness of the arsenic issue in food and water is promoted in an educational environment. Chapter 7 provides a thorough description of conducting technical humanitarian aid in South America, including challenges and practical suggestions. In Chapter 8, cooperative efforts between institutions to detect substandard and falsified pharmaceuticals using HPLC and paper analytical devices (PAD) are reviewed, and in Chapter 9, the issues of availability, accountability and adherence that prevent broad access to needed medicines are discussed, both with focus in Kenya. Authors recommend ways that chemists can apply their efforts to create straightforward chemical techniques, such as PAD, with the potential to significantly improve quality of medicines and patient outcomes, and to facilitate the delivery of care to patients. The objective of this symposium series volume is to share best practices to date in mobilizing chemistry expertise to solve humanitarian problems, and engage a broader audience of scientists who desire to apply their knowledge and skills to benefit others. The editor and authors hope many more chemists will be encouraged to utilize their time and talents toward humanitarian efforts as we work together to improve the quality of life for many across the globe.

References 1.

2. 3.

4.

Mercy Corps. Nine Humanitarian Crises We Can’t Ignore this Year, 2015. https://www.mercycorps.org/articles/9-humanitarian-crises-we-cant-ignoreyear (accessed February 6, 2017). The Water Project. Water Scarcity and the Importance of Water, 2017. https:/ /thewaterproject.org/water-scarcity/ (accessed February 6, 2017). Marshall, S. Poor Quality Medicines Pose a Danger to Patients. The Pharmaceutical Journal, September 26, 2014. http://www.pharmaceuticaljournal.com/news-and-analysis/event/poor-quality-medicines-pose-adanger-to-patients/20066604.article (accessed March 23, 2017). Newton, P.; Green, M.; Fernandez, F. Impact of Poor Quality Medicines on the Developing World. Trends Pharmacol. Sci. 2010, 31, 99–101. 8

5.

6.

7.

Global Humanitarian Assistance Report, 2016. http:// www.globalhumanitarianassistance.org/wp-content/uploads/2016/07/GHAreport-2016-full-report.pdf (accessed February 26, 2017). The Water Project, 2017. Ten Ways Clean Water Can Change the World. https://thewaterproject.org/why-water/10-ways-clean-water-changes-theworld (accessed February 26, 2017). Chemists Without Borders. https://www.chemistswithoutborders.org (accessed March 23, 2017).

9

Chapter 2

The History and Mission of Chemists Without Borders Steven D. Chambreau and Bego Gerber* Chemists Without Borders http://www.chemistswithoutborders.org/ *E-mail: [email protected].

This is the story of how Chemists Without Borders was created, how we clarified our purpose, what philosophies and thinking are our foundations, how people figure in the picture, what resources and skills are required, and what lessons we have learned – so far. The inception of the organization came about from a letter to the editor of Chemical and Engineering News, and was originally modeled after the global humanitarian organization Doctors Without Borders. The incorporation (2005) and the establishment of the non-profit status (2008) of Chemists Without Borders led to the development of the mission and vision of the organization, which have evolved over the last twelve years to allow us to pursue chemistry-related humanitarian projects and other initiatives. The importance of maintaining an all-volunteer workforce and the complications that arose from cultural differences in our volunteer base will be discussed. Also, the necessity of recruiting non-chemists into the organization is addressed here. Some of the major challenges to the success of Chemists Without Borders include development of a sound organizational infrastructure, project development, fundraising, and volunteer retention. Approaches we are taking to address these challenges are included in this chapter as well. The joy of working for a good cause alongside so many dedicated volunteers is indescribable.

© 2017 American Chemical Society

History “Never doubt that a small group of thoughtful, committed citizens can change the world; indeed, it’s the only thing that ever has.” - Margaret Meade (1).

Thin Threads The original concept of Chemists Without Borders came about in response to an article in Chemical and Engineering News in 2005. Dr. Bego Gerber had read the article “Carbohydrate Vaccines (2)” and suggested that the world perhaps needed a humanitarian organization for chemists similar to Médecins Sans Frontières for doctors. In this letter to the Editor of C&E News, Dr. Gerber translated Médecins Sans Frontières literally as “Chemists Without Frontiers.” Upon reading this letter, Dr. Steven Chambreau responded to Dr. Gerber, explaining that perhaps “Chemists Without Borders” would be a better translation of Médecins Sans Frontières, as Chemists Without Frontiers seemed to indicate a chemist who was not pushing the boundaries of science or was not interested in being on the frontier of their field. Although Dr. Chambreau was the only person who responded to Dr. Gerber, the pair, who had never met prior, decided to pursue the development of Chemists Without Borders as a global humanitarian organization to utilize chemistry and mobilize chemists to solve humanitarian challenges. It is worth emphasizing that roughly 160,000 people receive this news magazine every week, yet only one person responded. Not only that, if the letter to the editor had not contained poor wording, Steve says he would not have responded. How many times have you taken on a challenge with odds of 1:160,000 against? If Bego had known the odds, he may not have written the letter in the first place! For an organization to be successful, it is necessary to have the funding to carry out its mission. Therein lies a dilemma similar to the “chicken and egg” conundrum, where in order to carry out the proposed projects, the organization requires funding, and in order to raise funds, the organization needs to have accomplishments with which to demonstrate effective use of funds. In the first ten years of Chemists Without Borders, most of the funding came from volunteers and Board Members within the organization. Currently, fundraising remains a continuing process, but with several projects underway and the current success of the Arsenic Education in Bangladesh project, these accomplishments can be used to promote donations and apply for grants. We also continually look for ways to make projects themselves be sources of revenue. In addition, as more and more people participate, more and more sources of revenue appear. First, it was necessary to research if Chemists Without Borders already existed. A Google search yielded an article on the UNICEF website called the Tajikistan Diaries (3) and written by Lynn Geldof, the sister of Bob Geldof, the renowned humanitarian of the Boomtown Rats rock band. A chemist in Great Britain is what the United States calls a pharmacist, so Lynn was referring to Pharmaciens Sans Frontières. Since no other instances of Chemists Without Borders was found in the research, Chambreau and Gerber applied for incorporation as a nonprofit entity in California in 2005. Incorporation requires a 12

minimum of three directors to be on the Board., Dr. Rolande Hodel, the founder of AIDSfreeAFRICA, who was very active in the first year of the organization, was asked to fill the seat of the third director along with Dr. Gerber and Dr. Chambreau. By the time we were up and running, the vaccine whose dormancy had originally motivated us, was being manufactured in India for distribution. The first project that Chemists Without Borders sought to implement instead was related to arsenic contamination in the groundwater in places such as Bangladesh (see Chapter 3 on the Arsenic Project for more details). This project was proposed by Steve, one of the co-founders of Chemists Without Borders, and continues today under the auspices of Dr. Ray Kronquist, our current president. As more people became aware of Chemists Without Borders, many project ideas were proposed. Initially, the organization sought simple projects with a high probability of success. Currently, project ideas are submitted to the organization for review on a simple one-page proposal form (available on our website (4)) which asks for information about the potential project and for possible sources of funding. Proposals are reviewed periodically and projects with a high probability of success and good funding possibilities are assigned a project leader to implement them. Other times, project ideas stem from a current project where additional needs are identified by the project leader while carrying out the project. Ideally, the project ideas will come from people on the ground in developing regions where their needs can be best understood. It was important in the application for incorporation to include any potential projects we could imagine Chemists Without Borders overseeing so that we would not subsequently be limited by our role defined in the 501(c)(3) application. This was actually more difficult than it would seem, and many long discussions ensued in the drafting of the 501(c)(3) application. One of the major sticking points was to decide whether or not to organize as a “membership” nonprofit, where members of the organization would pay annual dues and have voting rights on decisions made by the organization. Ultimately, Chemists Without Borders decided to form as a non-membership organization so that no dues were required and anyone could join the organization. The organization’s original mission and vision were finalized, the application was submitted in late 2007, and Chemists Without Borders’ 501(c)(3) application was approved in 2008. In order to maintain 501(c)(3) status for organizations with an annual income of $10,000 or less, the organization is required to file with the IRS annually. This was not initially apparent to us, and in 2011, the IRS revoked our 501(c)(3) status until we applied again. The reapplication process was another major effort, but Chemists Without Borders successfully had its 501(c)(3) status reinstated by the IRS in 2012 and donations from 2011 were retroactively designated as nonprofit donations. Chemists Without Borders has been successfully operating since its inception. A timeline of early milestones is listed in Figure 1.

13

Figure 1. Early chronology of Chemists Without Borders.

14

Purpose Mission Statement “Chemists Without Borders Solves Humanitarian Problems by Mobilizing the Resources and Expertise of the Global Chemistry Community and Its Networks.” In other words, we seek to convert the potential energy of the chemistry world into the kinetic energy of humanitarian solutions. Of course, many of us are already making humanitarian contributions in our daily lives, especially as chemists, but there remain many things which never quite get the energy and resources they need. Those things are our domain of opportunity. How big is the pool of people into which Chemists Without Borders wishes to tap for resources, human and otherwise? According to the International Labour Organization (ILO), “The chemical industry is of strategic importance to the sustainable development of national economies. The ILO estimates that there are up to 20 million people employed in the global chemical, pharmaceutical and rubber and tyre [sic] industries today (5).” Not only that, each of these 20 million people has a circle of contacts, sometimes in the hundreds, in all sorts of occupations from graphic designers to geologists, plumbers to programmers, artists to architects, etc. If there were 100 unique contacts in each person’s circle, that would be a community of 2 billion people! Of course, for whatever reason, not everyone is available to volunteer. According to the US Bureau of Labor Statistics, “The volunteer rate was little changed at 25.3 percent for the year ending in September 2014. About 62.8 million people volunteered through or for an organization at least once between September 2013 and September 2014 (6).” As mentioned earlier, one single step in the thread of Chemists Without Borders’ creation turned out to be a 1 in 160,000 chance. What if, instead of a 25% chance, a mere 1 in 160,000 people volunteered (0.0006%)? Out of 2 billion people, that’s 2×109/160,000 = 12,500. That is a significant number of potential volunteers, if we can find them. This presents a large opportunity to identify people who might be willing to volunteer for a worthy cause to which they could relate, if only they knew the cause existed. What are the magnets that will find the needles in the haystack? What are the best practices of today for recruiting people to a cause in large numbers through social media, and how can we do that? As our slogan says: The Power is in the Network!

Vision Statement Drafting the organization’s mission and vision statements was a lengthy process, and much effort was put into having the right wording to best convey what Chemists Without Borders intends to accomplish. Our mission is “Chemists Without Borders solves humanitarian problems by mobilizing the resources and expertise of the global chemistry community and its networks.” 15

Our vision is: A global support network of volunteers providing mentoring, information and advice to ensure every person, everywhere, has affordable, consistent and persistent access to: -

Safe processes in work environments where chemical hazards exist Education in green chemistry and business, which people can apply in their daily lives and teach to others Sufficient safe water Essential medicines and vaccines A sustainable energy supply Emergency support, including essential supplies and technology

What’s in a Name?

Figure 2. Chemists Without Borders logo. (Reproduced with permission from Chemists Without Borders. Copyright 2017.) Our logo (see Figure 2) symbolizes our name in that it is intended to reflect the idea that we have no borders, that we are limitless. The hexagon (reminiscent of so many chemical structures) has no defined edges. The word Chemists is inside the hexagon, the word Without crosses the no man’s land of the border, and Borders is well outside the border. The name also implies thinking without borders, i.e.., thinking broadly, seeing things through other people’s eyes, imagining what’s possible, working with other people outside our profession, letting go of ownership, and so on. We have the capacity to mold our thoughts and our philosophies to achieve better the ends we wish to accomplish. In the context of Chemists Without Borders, that means focusing on those whom we are serving and looking at things from a totally different perspective so that our personal limitations diminish in importance. It is worth every minute to take a small amount of time each day to read material that will accelerate the work, whether it is about the work itself or 16

about how to become personally more effective. At 10 pages a day, roughly 10 - 20 minutes, one can read most books in a month. That’s 12 books a year and 60 books in 5 years, by which time you are pretty much an expert - all from 10 pages a day! This is known as “the slight edge (7)”. We have found that just one more person reading Dale Carnegie’s “How to Win Friends and Influence People (8)” can change the dynamics of conversations for the better, because there is a fresh perspective and a reminder of what is sometimes forgotten in the heat of the moment. In the words of leadership coach Blair Singer, “When emotion goes up, intelligence goes down.” If other people have been working for decades on a problem, does the problem still remain serious, and what can we at Chemists Without Borders bring to the table that might improve things? We’ve all heard the expression, “Think outside the box.” This has been such a useful metaphor that it’s now become a cliché; but how we describe it is not really the issue. What matters is what we do about it. One challenge often is that the instructions for getting out of the box are written on the outside of the box! How then do we get out of the box? One way is to have somebody who is already outside tell us what the instructions are for getting outside the box, or even tell us what it’s like to be outside the box. Thinking we are outside the box is being outside the box. (Is there something reminiscent of quantum mechanical tunneling about this?) Nobel laureate Albert Szent-Györgyi said, “Discovery consists of looking at the same thing as everyone else and thinking something different.” Here’s an analogy. We ask young Johnny what he wants for dinner, and he says, “I don’t know.” We then say, ”Johnny, if you did know, what would you want for dinner?” Johnny thinks, then says, “Fish sticks.” “Johnny, would you like fish sticks for dinner?” Johnny responds, “Yes, please.” The fundamental point is that the box is an artificial creation of the mind, and the mind has the capacity to change its artificial creations almost all the time. It may take work, but none of us is afraid of work, or it is doubtful you’d be reading this at all. As you will read in the chapters on arsenic, our current approach to addressing the problem of arsenic in drinking water in Bangladesh is very different from our original approaches. First we had to make room for new ideas by accepting that our earlier ideas were not as good as we had thought. Even after decades of work by many people to address this problem, Steve, Peter Ravenscroft and Satinder Ahuja proposed a new strategy which, under the direction of Ray Kronquist and Shahena Begum, is already providing water safe from arsenic in high schools in Bangladesh. How do we come to have these seemingly but not in practice immutable beliefs? There is a strong connection between our beliefs and our associations: family, teachers, friends, books, newspapers, colleagues, journals, the Internet, gossip, social media, TV, radio, movies, etc. When we surround ourselves with different people and ideas, our own ideas tend to shift. Each of us, both inside and outside Chemists Without Borders, has limiting beliefs; collectively, however, where one person has limitations another person has the necessary strengths. At Chemists Without Borders, we focus on people’s strengths. We keep in mind that there is a huge pool of people and resources to tap into if we remember the power of the network. 17

Where Should Chemists Without Borders Put Its Energy? Chemists Without Borders is opportunistic. We go where we can go, where something needs to be done and we have the capacity to do it or to find other resources who will do it. It is tempting to do the obvious. Should we be doing what chemists obviously are capable of doing? We think we should be doing what those in need require most. According to “How the Other Half Dies” (9), severe poverty is the root cause of the high mortality rates in the developing world. Therefore, our principal goal should be to eliminate severe poverty. Poverty results in malnutrition, overcrowded living conditions, inadequate sanitation, and contaminated water. Routine vaccination is often unavailable for both children and adults, and basic clinical care for the acutely ill is in short supply. Thus, poverty creates a fertile environment for infectious and parasitic diseases. Poverty also leads to illiteracy and inadequate education. Deficient education, especially of females, is closely correlated with poor health in developing countries. In many places, people work in very hazardous conditions without any knowledge of what those hazards are. That is why Chemists Without Borders looks at every project in economic terms: Does the money flow into or out of the village? Is the village empowered or disempowered by what we do? Some people ask why we emphasize working in developing countries, for no doubt there are plenty of inadequacies in developed countries too. There are indeed plenty of things to do in developed countries, but by definition, developed countries have resources to deal with their inadequacies, if they choose to use them. Developing countries, on the other hand, lack these resources. That’s where Chemists Without Borders comes in. Many scientists are frustrated in their work because they are allowed to contribute only to the science of an organization and not to its management. One reason this may frustrate scientists is that we are trained to think about problems and solve them, and we feel we have a contribution to make to all kinds of problems because of that training. Therefore, Chemists Without Borders focuses on the big problems, regardless of the chemistry involved. We should, however, apply chemistry to the solutions wherever and whenever chemistry can make a significant contribution. It is true that others may already be addressing some of these problems, yet in many instances, it remains that these problems have yet to be solved. To the extent that Chemists Without Borders can support, catalyze, and promote those other people in their efforts, we should make a point of doing so. To the extent that there are gaps, where problems are not being addressed, we should address them. Determining the priority of these efforts should depend on the magnitude of the needs and the magnitude of the impact we are likely to have. We also keep in mind that, in practical terms, a major factor in solving many of the most critical problems is the distribution of goods, services, and information. How do these get from the source to the users? How does the money flow in the process? Where are the assets and liabilities; i.e., do the processes put money in the pockets of villagers, or take money out of their pockets? One of our goals, therefore, is to promote methods that push or pull money towards the village. 18

Consider that in many places, people live on two or three dollars a day. Consider too that there are many wealthy people in these same countries. There are many people, therefore, who are living on much less than one or two dollars a day. It is hard to imagine as an outsider what that must be like. Why Arsenic? Some people ask, “Why arsenic? That’s old hat. There are so many other people working on the arsenic problem.” To which we reply, “Why address the largest mass poisoning in human history?” See the chapters on Arsenic, and watch this brief video to get a sense of the issue: “People are dying, people are dying” –Dr. A.K.M. Munir, physician-inventor, Bangladesh (10) (See Figure 3.)

Figure 3. Dr. Munir in Bangladesh.

Philosophy Cultural Humility Standing in other people’s shoes is a valuable concept, but is easily misconstrued. It’s all very well for us chemists to express opinions about those living in foreign places; while we may have been around the world and seen much, we have only our own limited experience. For instance, there is no imagining I could do that would give me any realistic sense of what it is like to grow up in a rural village in Sierra Leone during or after a dreadful civil war. We can be misled into thinking we understand things we still do not. Standing in others’ shoes is as fictional as a map is to the territory it represents or a menu is to the meal itself. That does not mean, however, that this thought experiment of standing in others’ shoes has no value. It does get me out of my own shoes, which is a small but significant step in the right direction. 19

Since Chemists Without Borders was founded to be a global organization, it is very important to us that we understand how cultural differences might affect the implementation of a project in another country. Some projects might not be feasible due to cultural differences, or changes to the project plan might be necessary to avoid offending the intended recipients of the project. More importantly, we find the opportunity to solve problems in practical and fruitful ways can only come from listening to the people whom we are aiming to help. “When I went to the village, everything changed.” So said Prof. Bernard Amadei, the founder of Engineers Without Borders. He was talking about his own perceptions of what needed to be done. When he actually got to the village, things looked very different. Sometimes, the problem is not the problem. Consider a hypothetical case where the village water system isn’t working. The engineer in charge knows how to fix it; the mayor knows how to fund it. The real problem: the engineer’s family and the mayor’s family haven’t spoken to each other in five generations, and it is not likely to change soon. The problem is not the problem. Relationships are the problem more often than not. That is why acquiring people skills is so crucial to success in real life problems. How does the job get done even though there seem to be insurmountable barriers? As chemists, we are familiar with energy barriers, how to surmount them or better still, circumvent them. At Chemists Without Borders, we have an opportunity to transfer these skills from the lab to human relationships. Having an expectant attitude, too, makes a big difference at Chemists Without Borders. That is, we make a point of expecting things to go well, expecting that each of us will excel. These kinds of attitudes lead us indeed to perform better than we might otherwise do. Also, if we keep our eyes on our goals, obstacles become mere stepping stones towards those goals. As we chemists know, failure is temporary in science as in life - as long as we persist. People are almost always doing their best. Some days their best is better than other days, sometimes sufficient, sometimes not. Baseball legend Ty Cobb holds the record batting average of 366, which means he missed the ball almost 2/3 of the time. (Nowadays people are paid millions of dollars for such performance!) Every day, he gave it his very best. Some days he was better than average, other days below average, yet they were all the best he had on any given day. So too with us. How often have our chemistry experiments failed en route to success (11)? Regardless of the circumstances, the attitude at Chemists Without Borders is “Keep moving forward,” “I will, until,” as so beautifully described in DH Groberg’s The Race (12). Also, there is a common expression in Glasgow, Scotland: “You never know the minute.” Things can change in an instant and the unexpected can be fraught with challenges and rich with opportunities at the same time. Fortunately, in our kind of team environment, others have the strengths when we happen to lack them. We embrace change, whether expected or not, for none of our aspirations is inside our comfort zone. It is essential to ensure that we do have all the necessary strengths at hand. In Chemists Without Borders, an all-volunteer organization, it is similarly essential that all key positions are supported by a deputy competent to take over if necessary. 20

Errors of the Third Kind Statisticians also have important things to teach us at Chemists Without Borders. They refer to two types of errors (13). With errors of the first kind, or false positives, one concludes something is true when in fact it is false. With errors of the second kind, or false negatives, one concludes something is false when in fact it is true. In 1957, Allyn W. Kimball, a statistician with the Oak Ridge National Laboratory, proposed a different kind of error to stand beside “the first and second types of error in the theory of testing hypotheses”. Kimball defined this new “error of the third kind” as being “the error committed by giving the right answer to the wrong problem” (14). At Chemists Without Borders, we must constantly beware of errors of the third kind, i.e., getting the right answer to the wrong question. In hindsight, the problem of arsenic in drinking water in Bangladesh is partly a result of people’s having asked, “How can we provide water that lacks cholera and typhoid, diseases that are transmitted on surface water?” instead of, “How can we provide water that is safe to drink?” No one seemed to have analyzed the underground water enough to see what else might be there. Analysis of water has become an important component of Chemists Without Borders’ work, and we are always seeking cheaper, easier and more reliable ways to do that. Other questions we ask at Chemists Without Borders include: Is there a bigger question that would subsume this one? What and where are the big humanitarian problems to be solved? How can we, as an intelligent, educated group of people, make the biggest contributions to solving these problems? What have we forgotten to address? Who, outside of our own circle, can see our efforts with new eyes? Again, Szent-Györgyi’s words apply: Discovery consists of looking at the same thing as everyone else and thinking something different. It is as easy to be distracted by the interesting at Chemists Without Borders as anywhere else. Sometimes, when an experiment yields poor results, we focus too much on what went wrong instead of on the original question, which was, “How do we get from here to there?“ Another useful approach, is to imagine that the goal has been reached, to stand there and then to look back at how you might have gotten there. That path is often different from the path looking forward. Maslow’s Hammer This idea is attributed to Abraham Maslow (The Psychology of Science, 1966, page 15 and his earlier book Abraham H. Maslow (1962), Toward a Psychology of Being): “I suppose it is tempting, if the only tool you have is a hammer, to treat everything as if it were a nail (15).” The risk is that we may treat everything as a chemistry problem because we’re chemists. We are more than chemists, however, and that’s where opportunity lies. We are chemists with many interests. We are indeed Chemists Without Borders. We have networks of family, friends and associates in the hundreds. These people cover a huge number of diverse occupations, so we can potentially bring any resource that a problem might require. What an opportunity! 21

Collaborative, Not Competitive Chemists Without Borders is a collaborative organization, not a competitive one. If somebody else goes before us and solves a problem before we get to it, we celebrate! We seek to complement and catalyze the work of others, and sometimes to be an umbrella for them. Our focus is on the village. This perspective has an impact on conflict resolution. There are always conflicts. Some are for the better, some are not. When objects rub against one another, physics and chemistry are involved; so too, with people. In Chemists Without Borders, we assume that everyone is working for the best interests firstly of the people “in the village,” and secondly of Chemists Without Borders and its participants. We assume, therefore, that there is no ill intent in anyone’s behavior. We do care about everyone’s feelings, although sometimes people’s feelings are in conflict. Sometimes it seems fair to one and all, and sometimes, not so much. The more we can learn about building relationships and understanding social styles, the more productive and calm things become (16). Jazz versus Symphony Chemists Without Borders operates in small, flexible teams, with redundancy built in as much as possible to compensate for volunteers’ uncertain schedules and availability. In a former occupation of Bego’s, there was a special corporate event where the president was outlining the direction in which they were going and the mechanisms by which they would get there. In the process, he showed a short film of an orchestra with a conductor, implying that was how the operation would run, as it always had done. Bego relates, “I had a small team of coworkers around me at the meeting. We looked at each other with disbelief. To us, successful projects were not managed like an orchestra, but played like a jazz ensemble.” Everybody is on the same team, all going in the same direction, with a very clear end in sight. There are rules of procedure, there are moments of special contact where things must align, and people have the freedom to accomplish the goal whichever way works best within the rules. Sometimes they are collaborating with one another and sometimes not, nevertheless focusing on the goal. Chemists Without Borders is indeed run as a jazz ensemble.

People Volunteers “There is nothing stronger than the heart of a volunteer.” - Lt Col James Doolittle, USAAF Chemists Without Borders was formed with the intent of being an all-volunteer organization. It seems impossible to do justice to the applause our many volunteers, past and present, deserve. The commitment and heart our volunteers have shown is summa cum laude, of the highest distinction. Finding willing volunteers was initially difficult because the organization was still developing potential projects. Much of the work early on was infrastructure 22

building, so that as the organization grew, there would be processes and procedures that could scale with the growth of the organization. Many chemists were interested in volunteering and were looking for a project that they could carry out “in the field”. Prior to having a working project in place, however, it was very difficult to ask volunteers to perform duties other than chemistry such as fundraising or clerical tasks. Currently, with several projects in place, it is much easier to pair a willing volunteer with a project that can utilize the volunteer’s chemistry skills. It is essential to understand that volunteers cannot be treated the same as paid employees, and without support from the organization, volunteer turnover can be high. The opportunities for leverage, for instance, are different; no one is relying on you for their livelihood. Most volunteers are working in their spare time, and may not have as much time to devote to a project as a paid employee or a retired person. Obviously, there are countless projects in which Chemists Without Borders could become involved. We lack all the resources necessary for all these potential projects, so our approach is simple: for any idea to become a project, it must have a project leader. Therefore, we look for project leaders. We then support the project leader in building the necessary team or teams to fulfill the project goals. This is a human resources function, illustrating our need for a diverse set of skills. It is exciting to have a huge pool of potential volunteers for any and all aspects of a project. The possibilities seem endless. The bottom line is this: All the many volunteers past and present who have been part of Chemists Without Borders have done an extraordinary job of collaboration and accomplishment. From those in the early days, as shown in the chronology above (see Figure 1), to the present, the dedication and commitment of all these wonderful volunteers has been very humbling. All measure of thanks is owed them. (See Acknowledgments.) Promote, Promote, Promote In a recent piece in C&EN, “Chemjobber” addressed the challenges of moving between academia and industry: “Crossing the great divide: As tempting as it is, moving between industry and academia requires a shift in perspective (17).” There is a similar shift in thinking required in moving from industry, academia or government into public benefit work like Chemists Without Borders’. There are necessary shifts in mindset for each and every one of us. Fundamental to that mindset is that we keep our eyes on the goal, on “the village “. Here is an example. Despite its actual spelling, some people think the word “sales” is a four letter word. Yet whatever we may call it, most of us are promoting or selling something some of the time every day. We advertise our own ideas, and those of other people. “Have you seen the latest movie with…” “Let’s meet at the Poisoned Pigeon for lunch.” “Eat your carrots, Mary!” We may, in fact, be good at it, as long as it’s not called “sales”. See also Chemistry Voices: Bego Gerber (18). In Chemists Without Borders, promotion is a key part of the job. As mentioned above, our power is in the network. Tapping the network involves promoting, enlightening, enticing, inviting, referring, begging, leading other people to join 23

the team and make a difference. How? Find out what the volunteer wants, then show them how participating with us can fulfill that want. We are in the Information Age, the new Millennium. We have seen entrenched dictatorships toppled owing to the capabilities of social media. How shall Chemists Without Borders capitalize best on these ever-changing resources? Skills At some point just about every skill you can think of will be valuable, but not all will be needed at the same time. Hence the need to build the network now so that people are on call when the need for them arises. Although the name Chemists Without Borders indicates our focus is on humanitarian chemistry, it is important to involve other fields of expertise to make the organization run smoothly. Such issues as fundraising and accounting, legal matters, recruiting, promoting, and running the nonprofit organization require much more than chemistry. Chemists Without Borders recognizes this and includes volunteers with all sorts of expertise that can be essential in running a nonprofit organization successfully. It is especially gratifying that volunteers do take on so many tasks, and even when they don’t know how to do something, they go and learn of their own volition. Many an enterprise has failed owing to its having poor foundations. The foundations may seem more than adequate at the beginning, but as things grow, the foundations may no longer be up to the task. Instead of becoming more efficient as the organization grows, it becomes progressively less efficient until it is too big for the necessary improvements to be made. To avoid this, Chemists Without Borders employs certain tools that can be utilized effectively at any level in the network. An example is the use of RACI matrices (19). Nobel laureate Melvin Calvin emphasized using the right tools for the job; better to design and create the right tool than to use the wrong one. “Just Give Me a Lab and Let Me Do My Work.” As scientists, we may not be in the “people business”, per se, but if we wish to have any impact at all, we must communicate effectively with others. This is especially true for Chemists Without Borders, which is really as much of a marketing organization as it is a scientific organization - our business is in mobilizing chemists and their networks to achieve humanitarian goals. Though chemists are the base of our operations, we can only accomplish our mission once our volunteers’ networks are mobilized. Within each chemist’s network there are people who fill the gaps that we may lack as analytical scientists. There are salespeople, artists, social workers, teachers all within our networks, all seeking to make the same positive differences in the lives of those in need. Understanding what some people call Social Styles, can be very helpful in working with such different kinds of people. The verbal and body language we use to communicate with our web designer is different than the language we use to communicate with the developer of an analytical chemistry method. 24

These communication shifts are necessary especially when we move from the inner circle of our base, many of whom are detail-oriented, into the secondary circle of our networks, where we find many more who are relationship-oriented, or bottom-line-oriented. While analytical people find it harder to answer how they feel about something, rather than what they think about something, relationship-oriented people tend to be the very opposite. People with all of these social styles are necessary in reaching our humanitarian goals, yet special effort and knowledge are required for communicating effectively among these social styles. Many scientists may find this topic of social styles to be new, and even fascinating, territory. A grasp of social styles has had a favorable impact on both the professional and personal relationships of our members, and certainly on achieving the kind of humanitarian impact we are seeking. These relationships remain keys to success in many areas including ours in Chemists Without Borders. “The Meaning of a Communication Is the Response It Gets.” Here is another enlightening way of looking at how we communicate effectively: “The meaning of a communication is the response it gets.” It seems obvious in retrospect. If I say something to somebody and I get a reaction from them that is quite unexpected, it probably means that what I meant wasn’t what the other person understood. There is an old expression: “I know that you believe you understand what you think I said, but I’m not sure you realize that what you heard is not what I meant.” At Chemists Without Borders, we aim to put the onus not on the listener to understand, but the on the speaker who is trying to relay a message. There is not much point in my speaking in Klingon if you’re listening in Na′vi, or to be more realistic, for me to speak English when you listen in Bangla. If I want you to understand, I had better start communicating in a way that produces understanding. Behavior In our meetings at Chemists Without Borders, whether face-to-face or online, we strive to ensure a safe environment by: Respecting Confidentiality Participating Fully Listening Actively Taking Turns Speaking Respecting All Points of View Showing Positive Regard Being Open and Constructive Leading by Example We seek to edify and bring out the best in one another. These practices have allowed us to engage in productive dialogue with a minimum of conflict. Of course, that doesn’t mean that we do it all perfectly well. We aim to be bold, 25

polite, kind, and to ask for what we want, not what we think we can get. Dream big, then dream bigger! The Casablanca Perspective “…, but it doesn’t take much to see that the problems of three little people don’t amount to a hill of beans in this crazy world.” - Rick Blaine to Ilsa Lund This famous line can be reused by us. Compared to the circumstances in which the people we aim to help are living, the kinds of interpersonal issues that can arise for us in Chemists Without Borders are typically trivial. Sometimes we lose perspective. Information Management Chemists Without Borders has found it imperative to ensure that all information and intellectual property of the organization is stored in a secure central repository with excellent backup protection. Everything goes here, even what seem like trivial ideas. If work is done at, say, one’s home computer, the work is immediately transferred to the central repository for protection, and so that it can be accessed by others. The risk is that when volunteers are no longer active, for whatever reason, the information on their computers and cell phones becomes inaccessible, sometimes permanently. We sadly lost two senior members of the team to illnesses, and discovered how crucial it is to have all data secured. It has been essential for us to look at where we want our organization to be in 10-, 5-, and 2-years’ time, and to use tools which can survive the growth. The decisions made early on tend to have long-term impacts, and are often hard to change. Consider that our railroads have the same gauge as the Roman chariots of 2,000 years ago (20) Delegate, Delegate, Delegate! To achieve Chemists Without Borders’ vision, very clearly there are not enough hours in the day for a handful of people to handle everything. It is essential, therefore, that processes be in place and the culture be in place that catalyze delegation. You may have heard stories of people who were so overwhelmed with “fires” they had to extinguish, that they didn’t have the time to learn fire prevention. If some fires are going to be left unattended owing to a lack of time to attend to them, we at Chemists Without Borders have found value in choosing a couple more to let burn uncontrolled. This yields the time to learn how to prevent so many fires in the first place. If anybody says they don’t have time, they may make time available by delegating some of their work. Remember, there are some 20 million people to tap into! There is a tendency to think that the training of delegates is too time-consuming. If it takes too long to train someone, delegate some of the training. The Chemists Without Borders view is that there are already innumerable issues to address which we are not addressing. Our strategy is to develop 26

processes and systems that can be easily replicated. At the beginning, it is true that all work and teaching must be done by the small group, but as they delegate, more and more teachers come online, freeing the initial group to devote time for another round of delegating. Duplication With delegation comes duplication. To build sustainable networks, the information and methods that are shared need to be applicable to everybody. We may have a special way of doing something with special equipment we have, but if you can’t do it too, it’s not sustainable in our network. To build the network, we teach teachers to teach teachers to teach. For example, getting clean water to the people of Bangladesh has always been a distribution issue in addition to a chemistry issue. In teaching school teachers and high school students about the hazards of arsenic in drinking water, and how to test for arsenic, we empower them to teach others, and have a broader impact. There is a direct line between the person in the field and all the other members of a team connecting them to the same sources of information. For example, in many parts of the developing world, the latest software is not available. Some people may be using software that can handle .doc documents but not .docx documents. Therefore, we create documents with .doc extensions to ensure their compatibility. When everyone can use .docx, we will advance to .docx. If it can’t be duplicated, don’t do it.

Conclusion Working with Chemists Without Borders is a way for chemists to make a unique contribution despite the sometimes perceived gap between their day-to-day chemistry and the needs of the underprivileged. To the extent that chemistry is involved, good, but that’s a very limited vision. Where are the biggest humanitarian needs, where can we have the largest impact, and what particular assets might we have to achieve that? To accomplish our ends, chemistry is only one of the valuable skills. We need a flexible mindset. We are more in the people business than we originally imagined. Fortunately, all the skills necessary are readily acquired with a little steady effort, the slight edge. Just about anyone and everyone is welcome at Chemists Without Borders as long as they are committed to the mission of solving humanitarian problems. This is a wonderful team of people. Do come and join us!

References 1. 2. 3.

BrainyQuote. https://www.brainyquote.com/quotes/quotes/m/ margaretme100502.html (accessed January 15, 2017). Borman, S. Chem. Eng. News 2004, 82, 31–35. UNICEF. https://www.unicef.org/ceecis/reallives_1344.html (accessed January 15, 2017). 27

4. 5. 6. 7. 8. 9. 10. 11. 12. 13.

14. 15. 16.

17. 18. 19.

20.

Chemists Without Borders. http://www.chemistswithoutborders.org/ index.php/projects/submit-a-project-idea (accessed January 15, 2017). International Labor Organization. http://www.ilo.org/global/industries-andsectors/chemical-industries/lang--en/index.htm (accessed May 12, 2017). US Bureau of Labor Statistics. http://www.bls.gov/news.release/ volun.nr0.htm (accessed May 12, 2017). Olson, J. In The Slight Edge; Greenleaf Book Group Press: Austin, TX, 2013. Carnegie, D. How To Win Friends and Influence People; Gallery: New York, 1998. International Medical Volunteers Association. http://www.imva.org/Pages/ deadtxt.htm (accessed May 12, 2017). Munir, A. K. M., physician-inventor, Bangladesh. http://youtu.be/ cBX6V8FsFfg (accessed May 12, 2017). BaseBall Reference. http://www.baseball-reference.com/leaders/ batting_avg_career.shtml (accessed May 12, 2017). Groberg, D., The Race. https://youtu.be/hSQ2R53Ss_g (accessed May 12, 2017). Natrella, M. G. Experimental Statistics, NBS Handbook 91; Washington, DC: U.S. Department of Commerce, National Bureau of Standards, 1963; p 1−17; reprinted 1966. See also NIST/SEMATECH e-Handbook of Statistical Methods, 2006. http://www.itl.nist.gov/div898/handbook/ (accessed September 2017). Kimball, A. W. Errors of the third kind in statistical consulting. J. Am. Statist. Assoc. 1957, 57, 133. Maslow, A. H. The Psychology of Science: A Reconnaissance; Harper & Row: New York, 1966, pp 15 – 16. Gerber, B. in Chemists Without Borders Blog. https:// chemistswithoutborders.blogspot.com/2008/09/on-wings-of-eagles.html (accessed May 12, 2017). Chemjobber. Chem. Eng. News 2017, 95, 31. Gerber, B. Chemistry Voices. https://youtu.be/exMwjpWduiY (accessed May 12, 2017). A Guide to the Project Management Body of Knowledge (PMBOK® Guide), 5th ed.; Project Management Institute, 2013. See also Wikipedia, Responsibility Assignment Matrix. https://en.wikipedia.org/wiki/ Responsibility_assignment_matrix (accessed May 12, 2017). Snopes. Railroad Gauges and Roman Chariots. http://www.snopes.com/ history/american/gauge.asp (accessed May 12, 2017).

28

Chapter 3

Arsenic Education and Remediation in Bangladesh Ray Kronquist* and Shahena Begum* Chemists Without Borders

http://www.chemistswithoutborders.org/ *E-mails:

[email protected] (R.K.); [email protected] (S.B.).

This chapter describes a project of Chemists Without Borders (CWB) to combat the arsenic contamination problem in Bangladesh. The project was a number of years in the planning stage as mentioned in the Chapter 2. This chapter describes the work that started in September 2014 carried out by five interns in Bangladesh working under the direction of Dr. Ray Kronquist, living in California. The goal of the initial project was to educate high school students on the hazards of arsenic in drinking water, to train the students on how to measure arsenic concentration in water from community wells near the schools, and the collection of data from schools by the interns. This first phase of the project lasted 16 weeks, and of all the schools visited, two were found to have very high (250 ppb) concentrations of arsenic in the water from their school wells. The second phase of the project was an attempt to remediate these two wells, and this involved discussions with many individuals and organizations inside and outside Bangladesh. It culminated with the commitment for funding the construction of two ring wells by two Rotary Clubs to replace the contaminated wells. The third phase of the project was the actual construction of the wells. We are now in the fourth phase of the project which is a strategy to provide clean drinking water to all the 400,000 residents of one upazila (county) in Bangladesh by the end of 2018. The strategy involves getting clean water to all 38 high schools and colleges in the upazila and then using the high schools as distribution hubs to deliver clean water to homes in each high school district. We will test all the community © 2017 American Chemical Society

wells and identify the ones that are contaminated with arsenic. Home delivery of drinking water from the high school will be offered to the residents who have been using the arsenic contaminated community wells. Our hope is that we will do this successfully and that this strategy can serve as a model for solving the arsenic contamination health problem nationwide in Bangladesh.

1. Introduction While the subject of this book is on mobilizing chemistry expertise to solve a variety of humanitarian problems, this chapter focuses specifically on resolution of the problem in Bangladesh of arsenic contamination of drinking water. However, since the team has developed a strategy of working through the high schools to address the arsenic problem, it believes that over the coming years, it will also be able to utilize its relationships with the high schools and their students to work on many other humanitarian problems in this developing country. Further, it is believed that Chemists Without Borders will be able to utilize many of the operating models developed for Bangladesh in other countries as well. This chapter describes the work done from 2014 through the first part of 2017 by Chemists Without Borders on the problem of arsenic contamination in drinking water in Bangladesh. Dr. Ray Kroniquist is the CWB project leader based in the United States and Shahena Begum, who started as an intern, is now the Program Manager for Bangladesh. Ray learned of Chemists Without Borders by then Executive Director, Ladan Artusy, in May of 2013. Ladan introduced Ray to Bego Gerber and Steve Chambreau, the co-founders of Chemists Without Borders. He was intrigued by their project to work on the problem of arsenic contamination of drinking water in Bangladesh, which had been in the planning stage at CWB for a number of years. Groundwater arsenic contamination in Bangladesh is reported to be the biggest arsenic calamity in the world in terms of the affected population (Talukdar, et al. 1998) (1). The government of Bangladesh has addressed it as a national disaster. The contamination has been termed as the greatest mass poisoning in human history (Smith, et al., 2000) (2). In the spring of 2014, Amber Wise, a chemistry professor at Chicago State University and a member of CWB, was planning a trip to Bangladesh. Amber had previously spent a year at the Asian University for Women (AUW) in Chittagong, Bangladesh teaching chemistry and setting up a chemistry department. Steve arranged with Amber for her to visit a couple of high schools near Chittagong and to investigate the possibility of recruiting interns from AUW to work on the project. Amber did this, and she asked the Career Development Center at AUW to publish a job description for an internship and to circulate it among their students and graduates. As a result, we received seven applications. Ray began leading the project at this point and he interviewed the applicants via Skype videoconferencing. The objective was to create a team in Bangladesh which would give presentations at high schools, educate the students on the hazards of 30

arsenic in drinking water, and train them on using a test kit to measure the arsenic concentration at community wells near the school. Then, after carrying out this part of the project to evaluate how helpful our efforts were, we decided that this phase of the project should last 16 weeks. Appendix 1 provides information about the project leaders and a description of each intern originally hired. Among the five interns, few had knowledge about arsenic in water. They needed to learn how to test for arsenic in water with the Hach test kit. The Hach Test Kit is manufactured by the Hach Company in Loveland, Colorado, USA. The Model EZ Arsenic High Range Test Kit was used in all measurements. The addition of chemicals to a water sample containing arsenic causes arsenic to be released in a gas form. The gas contacts the test strip, which undergoes a color change. The concentration of arsenic in the sample is related to the extent of the color change, so observation of the color constitutes a measurement of the arsenic concentration. The interns were also sent a video on using the Hach Test Kit prepared by groups of college students and their teachers in the U.S. Through Ray’s guidance and materials provided from the U.S. Chemists Without Borders organization, the interns were trained sufficiently to give their presentations to the Bangladesh high school students. Figure 1 shows the interns in Bangladesh who started in September of 2014 working on the project:

Figure 1. CWB Arsenic Education Project Interns, Monira, Taslima, Nishat, Ano and Shahena (L-R), Sept. 2014. 31

2. Beginning the Project Including Challenges Faced This section describes how the project started, including the obstacles that the interns encountered. The authors consider it instructive to cover what may seem like mundane issues, but the handling of these obstacles in a project such as this often makes the difference between a successful project and a failed project. Here are the interns’ experiences as they started the project:

2.1. Learning about the Arsenic Issue At beginning of the project, local knowledge about arsenic was limited. The five AUW graduates were from different major backgrounds. However, Ray sent many documents on arsenic and explained the project very clearly. During the first 6 weeks of the internship, all were trained on arsenic contamination history, testing and remediation methods and the organization of the project.

2.2. Preparing for Presentations to Schools With input from the AUW IT department, a projector was purchased. During the first few weeks, additional equipment was acquired for communicating and for the high school visits. A projector is one of the most important pieces of equipment needed because the interns expected large groups of students to attend the presentations on the health hazards of arsenic. The projector enabled them to present the slides to a large audience.

2.3. Initiating Contact with Area High Schools At the beginning of the project the interns had a list of hundreds of high schools in the Chittagong area that was downloaded from a government website. The interns were referred to that website by Professor Amber Wise (Former AUW professor). There were a number of errors of headmasters’ names and phone numbers, and the interns had to make a number of calls to reach the right persons. At first it was difficult to establish CWB’s credibility, since it was a new organization in Bangladesh. However, over time the interns were successful in persuading the headmasters that they had something valuable to present to the students, and appointments were made to give presentations to the high school students on the health hazards of arsenic. Logistical problems: Most of the schools do not have any projectors or computers. Some schools do not even have electricity. In addition, the interns took local motor vehicles called CNGs, rickshaws and sometimes local buses for transportation. Directions from each school headmaster over the phone were generally not enough to find the location in an unknown town. For example, even though communicating directly with the Panthichila School, Sitakunda headmaster, it took significant effort to reach the school. 32

2.4. Presentations, Demonstration of the Hach Tests, and Volunteers The five interns visited the schools and delivered a PowerPoint presentation introducing CWB, the goal of the project and then discussed the hazards of having excess amounts of arsenic in the drinking water with the students (most in grades 8 to 10). The interns asked questions of the participating students about their knowledge of arsenic. The presentations were given in the native language (Bangla). The background of the arsenic problem in Bangladesh, symptoms and possible mitigation information were explained in detail to the students and teachers. It took around 45 to 60 minutes to explain all the information in the presentation. During the presentation the interns ensured a friendly environment in the classroom so that students felt comfortable to ask any question. Presentation slides are given in reference (7)

2.5. Demonstration on Measuring Arsenic Concentration The presenters taught the students how to measure arsenic concentration in water by showing them a hands-on demonstration using Hach Test Kits. Then, student who volunteered repeated the test procedure using the arsenic test kits. It was easy to get students to volunteer to make the arsenic measurements at wells in their communities. After the training of the high school students, the interns followed up with them on a weekly basis for 2 weeks as they made arsenic measurements of the local water sources.

2.6. Follow Up To Get Test Data on Neighboring Wells Test kits were given along with a sign-up sheet for the volunteers who wanted to measure the arsenic in their or their neighbors’ water source and a data sheet to enter the measured arsenic in those wells in ppb (parts per billion). Also, an instruction manual in Bangla which included the interns’ contact number was provided to assist the students. One teacher or volunteer student was assigned to keep the data and test kits with him or her. After 1 week the interns went back to the schools and collected both items from them.

2.7. Political Instability: Unsafe To Travel at Times During the first few months of 2015, Bangladesh suffered a political crisis. The two main parties held a controversial general election, and, during the aftermath, there were countrywide protests, traffic blockades, and petrol bombs were thrown at vehicles. Consequently, travel was not safe, and school visitations were delayed during this time period.

33

3. Visit Results A summary of the results of these high school visits by the interns follows: 1. 2. 3. 4. 5.

High attendance (50 to 150 students) Lots of questions A dozen volunteers to test wells near each school 20-30 community wells tested at each school Two schools had high arsenic concentrations in their wells

The Indiegogo site in reference (8) contains details about the arsenic education project in Bangladesh. There are school visit reports since September 2014.

4. Cost of First Phase of Project Money was spent on Arsenic Education Project as follows: CWB money for the Bangladesh project has been used for interns’ stipends, expenses including transportation cost to schools, mobile bill, and internet bills. Total cost for the arsenic education project was $6500 during September to December, 2014. The interns visited six high schools in different areas of Chittagong including Chittagong Government Girl’s High School, UCEP High School, Kumira Residential School and College, Sitakunda Model High School, Teriail High School and ModdhomVaterkhil High School. The first high school visit was made on Oct. 16, 2014 and the last one was made on Nov. 13, 2014.

5. Strategy Change: Focus on Remediation of Sitakunda and Teriail Wells Instead of More High School Visits A result of the initial phase of this project was that high school students are enthusiastic participants in the program to educate the community about the health hazards of arsenic in drinking water and in taking measurements of the arsenic concentration. Unfortunately, of the six high schools, we found two high schools with very high arsenic concentrations. Using the Hach Test Kit, the interns measured the arsenic concentration in the water at both schools to be 250 ppb, which is 5 times more than the allowable level in Bangladesh. The schools that had high amounts of arsenic were Sitakunda high school and Teriail high school. In Sitakunda high school around 2500 people and in Teriail schools around 1500 people were drinking water from the arsenic contaminated tube wells. Our team in Bangladesh consulted with the local office of the Department of Public Health Engineering (DPHE), and they suggested a solution that they had used at many contaminated wells in this region. They explained as follows: In this region, there are three aquifers as you can see in Figure 2. 34

Figure 2. Aquifer Structure at Sitakunda and Teriail High Schools. One aquifer is near the surface and is not contaminated with arsenic. Then there is a deeper aquifer that has some arsenic contamination and a deepest aquifer with the highest arsenic contamination. The tube wells that were currently being used were going down to one of the deeper aquifers. However, DPHE explained that a new shallow ring well could be dug at each high school location to get arsenic-free water from the first aquifer. It is important to understand that the arsenic contamination of the deeper aquifers is not in general from any industrial contamination but results from the fact that arsenic is one of the elements that occur naturally in the Earth’s crust. It is also important to understand that this arsenic contamination model is not valid in all geographic regions in Bangladesh or in other countries. There are regions where the aquifer nearest the surface is the one most contaminated with arsenic. The local DPHE engineers, however, drawing on their extensive experience in contracting wells in this region advised that the surface aquifer at our schools would be free of arsenic. At the end of this Stage 1 of the project, there were no funds in the original project budget for these two replacement wells. It was decided to suspend the arsenic awareness presentations, since it was not possible to correct the arsenic contamination problems we uncovered. It was decided instead to spend the time searching for funding and/or partners to resolve the arsenic contamination that was found at the two high schools. Accordingly, the plan was changed to 35

target provision of safe drinking water in both schools by determining the best alternatives and replacing the contaminated tube wells with safe wells.

6. 2015 Work Seeking Partnerships and Funding Chemists Without Borders’ Bangladesh team built relationships with strategic and academic partners such as the Department of Public Health and Engineering (DPHE), Dhaka Community Hospital, Dhaka University, Dhaka Water and Sewer Authority (WASA), BRAC (Formerly Bangladesh Rural Action Committee), UNICEF, Water Aid Bangladesh, Chittagong University of Engineering and Technology (CUET) and Rotary Clubs. Here are some of the partners that were developed:

6.1. DPHE Engineer at Sitakunda DPHE (Department of Public Health Engineering) is one of the organizations that works to provide safe drinking water in Bangladesh. Their main focus of work is to identify arsenic in drinking water and provide mitigation/alternatives at the national level. Almost every upazila has a regional office of the DPHE to coordinate their work. The team was able to build a good relationship with them. Once the team identified an arsenic contaminated tube well, it contacted the regional DPHE office for determining the best solution based on the geographic location. Mr. Shah Alam is an assistant sub Engineer at Sitakunda who advised the team to set up a ring well in most areas. Since the team was not equipped with the mechanism of constructing ring wells, it needed to install the ring well through construction firms. The employees of these firms are trained by DPHE to build the well and they provide all the materials, labor and other logistic support to build the ring well.

6.2. Rotary Clubs The CWB Bangladesh team communicated with several Rotary clubs in Chittagong city, Bangladesh. One of the Rotary Clubs, Rotary Club of Khulshi, agreed to donate funds for replacing the contaminated well at Sitakunda High School with a safe ring well, which would provide arsenic free water. Additionally, Shallotte Rotary Club of North Carolina, USA funded a ring well for Teriail High School.

6.3. Schools Since plans changed for 2015, there were not as many school visits during this time. Presentations were given to the PSD School in Dhaka, Union Krishi School at Patia, Chittagong, and the Joypura School and College in Lakshimpur (9). 36

Additionally, communication continued with Sitakunda High School, Teriail High School as well as follow up with PSD School, Joypura School, and Union Krishi School.

6.4. Asian University for Women (AUW) Interactions The original five interns were graduates of Asian University for Women(AUW) and were recruited through a job posting in its Career Development Center. CWB set up a Memorandum of Understanding to assist with local funds transfer through the AUW Finance and CDC offices. AUW Professor Andrea Phillott was a co-coordinator and Dr. Harunur Rashid also partnered with CWB.

6.5. Collaboration with Arsenic Experts The CWB team consulted with experts from national and international organizations. Dr. Meera Smith (Public Health Specialist at University of California Berkeley) and Dr. Matin (Professor of Geology department, Dhaka University) gave advice on options for replacing the contaminated wells at Sitakunda and Teriail High Schools. Dr. Asif and Dr. Reaz at CUET (Chittagong University of Engineering and Technology, Chittagong, Bangladesh) ran tests for arsenic concentration in water in their laboratory at CUET.

6.6. Project Well Dr. Meera Smith with her husband, Allan Smith, are the founders of the organization named Project Well in India. Reference 10 gives details about Project Well. Project Well has dug around 300 wells in West Bengal, India, largely to replace arsenic contaminated wells. These wells are treated to kill any bacterial contamination in the water. So, Dr. Meera Smith gave the team good advice on the treatment of water sources and others issues related to replacing arsenic contaminated wells.

6.7. DPHE lab in Dhaka Our measurements of arsenic concentration with the Hach test kits were not as accurate as tests done on water samples in a laboratory. So we looked for laboratories where we could get more accurate arsenic measurements done The DPHE central laboratory is situated in Mohakhali, Dhaka. 54 parameters of water test are available at this lab. DPHE shared water quality parameters and costs are available on their website (11, 12).

37

However, there are some formalities to have water tests performed by the DPHE lab in Dhaka, such as:

1. 2. 3. 4. 5. 6. 7.

Come in person to pick up their approved container. Go back to the water source and take the sample in the approved container. Return to Dhaka and submit the sample in person. Get their form for payment and fill it out. Take the form in person to the bank to make payment for the tests. Return to the lab to show proof of payment and to leave the samples. Come back in person to pick up the test results (in 2 to 4 weeks).

There was no CWB team in Dhaka, so it was hard to complete all of these tasks. We were however able to get some tests run by asking some of our other partners in Dhaka for help with the logistics. 6.8. Paper Presentation at the 16th Asian Chemical Congress, Dhaka, by Shahena Begum The 16th Asian Chemical Congress was held at the Bangladesh University of Engineering and Technology (BUET), Dhaka, Bangladesh, and organized by the Bangladesh Chemical Society. The inaugural ceremony held on March 16th, 2015 at Pan Pacific Sonargaon Hotel, Dhaka, Bangladesh. Mr. Amir Hossain Amu, MP, Honorable Minister, Ministry of Industries, Govt. of the Peoples Republic of Bangladesh was the chief guest in the ceremony. On the evening of the 19th, there was closing ceremony at Dhaka University, Dhaka, Bangladesh. Shahena Begum presented a paper entitled “Arsenic in Drinking Water: Promoting Awareness through Remediation and Measurement Projects for Students” The paper was included in the section of Environmental Chemistry and the paper was presented on 19th March, 2016. Many attendees appreciated the CWB project in Bangladesh and requested for us to continue in Bangladesh. 6.9. Chittagong University of Engineering and Technology Chittagong University of Engineering and Technology (CUET) contains the department Bureau of Research, Testing and Consultation (BRTC). They can test for 15 different metal analytes. While the CWB team was conducting the arsenic education program and measurements, it measured 250 ppb arsenic by using a Hach test kit in two wells at Sitakunda High School and Teriail School where 2500 and 1500 people respectively are drinking water from the arsenic contaminated tube wells. In order to confirm the presence of arsenic in those schools, we conducted more accurate lab-based tests on the 2 highest arsenic concentrations at CUET. They used the ASTEM (American Society for Testing and Materials) method for testing water in their lab. 38

6.10. HOPE Foundation As the name suggests - HOPE Foundation for Women and Children of Bangladesh - HOPE's mission is to serve women and children, especially newborns, in Bangladesh (13). The CWB team communicated with Ashley Pugh, representative from HOPE for Bangladesh. Ashley mentioned that the water in the area of the hospital has a high level of fecal matter with resulting water borne illnesses. She also mentioned a health training class for midwives that the hospital conducts. We discussed possible collaboration on Health Education and on remediation of contaminated water, but at this time (July 2017), we haven’t begun any formal project with HOPE.

6.11. Agami, Inc. Agami is a non-governmental organization that provides financial and other assistance to 20 schools in Bangladesh. Besides Agami’s financial help, they have started a number of innovative classes at these schools. CWB was asked by Agami to develop a course on health that goes beyond water quality to cover many other aspects of health for their students. More on this project is in reference (14). The CWB team members prepared a health project with nine lessons. The goal of this health education project is to create awareness about leading a healthy life for students and their family members. The lessons include topics on: Water Seeing the Doctor Nutrition and Food Exercise Hygiene Mental Health Meditation Sleep Conclusion The health courses were developed for both high school and elementary school students. With the collaboration of Agami, the CWB Bangladesh team taught health education courses at BSRM High School, Chittagong, Bangladesh in September 2016. There was significant positive feedback from students and teachers. As a result, Agami team members in Dhaka started teaching these health education courses in an elementary school in February 2017. Later on, these courses will be taught at four other high and elementary schools in Dhaka.

39

7. 2016 Work: Construction of Two Ring Wells 7.1. Construction of Ring Well at Sitakunda High School In the Sitakunda region of Bangladesh, a ring well is a well-known option for safe drinking water free of arsenic. Ring wells, which bring up water from the aquifer nearest the surface, work in hilly, coastal, arsenic affected and declining water table areas. In these regions, this surface aquifer is usually free of arsenic. The well is lined with concrete rings as shown in Figure 3.

Figure 3. Construction of Ring Well at Sitakunda High School. A ring well is constructed by digging a shaft, generally manually and installing concrete rings, which prevent the dirt walls from collapsing. As the shaft is dug deeper, the rings drop down, and the next ring is placed at the top of the stack. Most of these wells are less than 30 feet deep. 40

At Sitakunda High School, the selected a platform location for the ring well was found to be sanitary, far from potential pollutants and was approved by the DPHE. The ring well depth was 28 feet at Sitakunda High School. The ring well construction was completed in February 2016. At that time there was no problem with the well water, but after one month an odor problem was noticed. While many students were taking water from the ring well they noticed that there was a bad smell from the water. The DPHE Engineer at Sitakunda took water from the ring well and drank it. He also experienced the same smell from the water. He understood that it happened because gases evaporating from the water in the well did not have a way to escape into the atmosphere. He suggested that this problem could be solved by creating ventilation at the top of the well. So an escape path was created at the top of the well, and this solved the odor problem. Additionally, a filter must be installed to remove iron contamination from the well.

7.2. Construction of Ring Well at Teriail High School Ring well construction was completed in June 2016 at Teriail High School, Bangladesh with funding from Rotary Club Shallotte in North Carolina, USA. After the ring well was constructed, the water from the well was tested by the local DPHE engineer, and passed the tests. However, shortly after construction, sand was found in the water. Upon inspection, the DPHE engineer instructed that the well be deepened, so the sand could settle out, and the problem was solved. The students now have drinking water free of arsenic from this ring well. As of July, 2017, we are testing for other potential contaminants. Those tests are so far inconclusive, but we may install filters to the well.

8. 2017 Work and Future Plans This section describes a strategy going forward that we think could be expanded to solve the arsenic contamination problem nationwide in Bangladesh. This strategy represents what we plan to do through the end of 2018, modifying it as new information and ideas appear. There are ten components to this strategy as described below.

Strategy Component #1: Concentrate on Getting Clean Water to High Schools There are about 7000 high schools in Bangladesh vs about 1,000,000 community wells. Because the number of high schools is so much less than the total number of community wells, it is much less expensive to concentrate on providing clean water to the high schools.

41

Strategy Component #2: Deliver Clean Water from the High Schools to the Homes Near the Schools This is a business model developed by Drinkwell Systems. Drinkwell has set up water delivery entrepreneurs at dozens of locations in India and at least one in Bangladesh. The entrepreneurs deliver water to the homes using a very simple vehicle as shown in Figure 4.

Figure 4. Delivery of Water to the Homes by Drinkwell Systems. The residents pay a small fee for the service which covers the costs of the delivery person’s salary and the use of the delivery vehicle. We propose to follow this business model to provide clean water eventually to all the residents of each high school district who normally would use water from contaminated community wells. The high schools serve as water distribution hubs.

Strategy Component #3: Focus on Sitakunda Upazila for Next Two Years To Validate the Model Bangladesh is divided into districts (like U.S. states), and the districts are divided in upazilas (like U.S. counties). Sitakunda Upazila is located in Chittagong District to the north of the city of Chittagong. The main road between Chittagong and Dhaka runs through Sitakunda Upazila. A map of Sitakunda Upazila is shown in Figure 5. Here are some key parameters of Sitakunda Upazila: 38 high schools and colleges, 400,000 residents, 175 square miles. With only 38 high schools and colleges, Sitakunda Upazila is small enough that we think our team can visit all the schools, test their wells, replace the contaminated wells and set up delivery services for drinking water to all the homes that need clean water for drinking in the neighborhood of each school by the end of 2018. At the end of March 2017, we had visited over half of the schools and done a lot of the work to evaluate arsenic testing resources and the various remediation options. Also, with 400,000 residents, Sitakunda is big enough to serve as a template for this business model to replicate across the country if our project is successful there. 42

Figure 5. Map of Sitakunda Upazila. Strategy Component #4: Building a Team We’ve put together a team of people with a variety of skills to execute our strategy: -

-

A team of experts to help make technical decisions. These are professional people, most with Ph.D. degrees and with experience with arsenic contamination. University interns who work with the high schools. High school student interns who will educate family members and neighbors about arsenic. We have a Program Manager for Bangladesh to supervise the interns and high school students. Over the next year and a half, the size of the team will grow as the size of the project expands and we provide water service to more people.

Strategy Component #5: Select Water Measurement Method Having accurate measurements of arsenic and other contaminants in water is critical to making the right decisions in the project. Here are some of the test kits and labs that we are evaluating and using: Test kits: − Hach Kit for arsenic (good for a rough test for arsenic) 43

− Aquagenx kit for e-coli − 3M kit for e-coli Laboratories: (They provide more accurate test results for arsenic and other contaminants) − DPHE in Dhaka − Bangladesh Council of Scientific and Industrial Research (BCSIR) in Chittagong We plan to test each of the community wells in Sitakunda Upazila for arsenic, starting with Teriail High School District. We will test first with the Hach Test Kit, since this is the least expensive testing method. If the Hach test shows no arsenic, we will consider the well to be safe and, with the approval of the well owner, we will paint it green. If the Hach test shows some arsenic, we will submit a water sample to one of the laboratories for more accurate testing. If the lab test shows arsenic at or below 50ppb, we will consider it safe and ask that it be painted green. If the lab test for arsenic is above 50ppb, we will consider it to be unsafe and ask permission to paint it red. We will offer the home delivery service, for a small fee to pay expenses, to the residents who have been using unsafe wells.

Strategy Component #6: Decide on the Remediation Method In 2016, we replaced the wells contaminated with arsenic with ring wells, shallow wells that brought up arsenic free water from the first aquifer nearest the surface. However, this method of remediation may not work in all cases, so other solutions will also be considered, selecting the best choice for each school. Here are our options: 1) ring wells (shallow wells) and 2) deep tube wells (going down below the aquifers contaminated with arsenic) The two wells take water from different aquifers but look the same above ground. We will be testing different aquifers to decide the best one as a water source. We are also evaluating two types of arsenic removal equipment (Figures 6 and 7). Figure 6 shows the arsenic removal system manufactured by Drinkwell Systems, and Figure 7 shows the arsenic removal system manufactured by AdEdge Water Technology. AdEdge Water Technologies is a company that is focused on providing water treatment solutions. AdEdge’s most unique offering is the ability to treat more than 20 different contaminants such as arsenic, nitrate, iron, manganese, radionuclides, ammonia and others, by employing more than 20 different treatment approaches (filtration, biological, adsorption, ion exchange, etc.).

44

Figure 6. Drinkwell Systems Arsenic Removal Equipment.

Figure 7. AdEdge Water Technologies Arsenic Removal Equipment.

45

Strategy Component #7: Recruit More Staff and Develop Management Procedures We will need to train students to monitor wells and maintenance people to do repairs. We will also need to organize and manage water delivery personnel. As the project grows and we provide water services to more and more people, we will need to solve management problems, develop procedures, documentation, training and oversight, for example.

Strategy Component #8: Visit the Schools to: -

Describe our project Test the water Decide with the school if their water is safe or not. If it is not, decide what remediation method is best.

We will be visiting all of the 38 high schools and colleges in Sitakunda Upazila to evaluate each of them. Figure 8 shows Shahena meeting with a headmaster. Figure 9 shows Shahena taking water sample for testing.

Figure 8. Shahena Discussing the CWB Project with a Headmaster.

46

Figure 9. Collecting water sample for testing.

Strategy Component #9: Other Complementary CWB Projects We have three other Chemists Without Borders projects that complement the overall project of getting safe water to the residents of Sitakunda Upazila. They are: -

Health Education Courses Developing Low Cost Arsenic Test Kits Developing a method for testing arsenic in rice

As the water remediation project grows, we will also be working on the above projects. We will be teaching the Health Education Course at the high schools that participate in the water delivery program. We will use arsenic test kits manufactured in Bangladesh as soon as we can qualify them and ensure their accuracy. We will also transfer the test procedure for arsenic in rice to the lab at AUW once the process is fully developed at the University of Massachusetts Amherst in the U.S.

Strategy Component #10: Goal Is Clean Drinking Water to All 400,000 Residents of Sitakunda Upazila by End of 2018 -

Clean water to all the high schools. Delivery of drinking water to homes. Planning for replicating the model throughout Bangladesh. 47

Summary of Impacts of This Project in Sitakunda Upazila -

Clean water and arsenic awareness for tens of thousands of high school students. Clean water delivered to tens of thousands of homes. Dozens of entrepreneurs delivering water. Dozens of lives saved each year. A template for all of Bangladesh (impact will be 400 times the impact for Sitakunda Upazila).

Current Status of the Project in July of 2017 We have visited and tested the water at over half of the high schools and colleges in Sitakunda Upazila. We are encountering some problems in getting accurate laboratory measurements of arsenic and other contaminants. We are learning that the way we collect the samples and handle them before submitting them to the laboratory is critical and we are in the process of solving this problem. We are starting a program of presentations to solicit funding for the project. Our members and volunteers are spread around the U.S. and in other countries, so we are recruiting these members and volunteers to present our work to Rotary Clubs, ACS sections and other organizations.

Conclusion Chemists Without Borders started this project in September of 2014 with the goal of educating high school students in Bangladesh about the health hazards of arsenic in drinking water. The assumption was that, if a well was contaminated, the students could just take water from another well. None of us were experts in this field, and the women encountered a number of obstacles in trying to achieve our objective. As we continued to work on the problem, we found that often there were no secondary wells that could be used and that fixing the problem was really more important than just pointing it out through education. That led to a fundraising effort and the contributions of generous Rotary Clubs to fund the construction of two ring wells to replace the contaminated ones. We now are working on a model in which we concentrate on getting clean water to the high schools and then deliver small quantities for drinking and cooking to residents, using the high schools as distribution hubs. We are hopeful that this model will enable us to ensure safe drinking water for all 400,000 residents of Sitakunda Upazila by the end of 2018 and that the model can be used as a template for other regions of Bangladesh.

Contact Information Anyone who would like to support our work financially or as a volunteer can reach us by e-mail: Ray Kronquist: [email protected] Shahena Begum: [email protected] 48

Appendix 1 About the Authors Dr. Ray Kronquist holds a Ph. D. in Physics from the Massachusetts Institute of Technology. He has had a career as an entrepreneur, starting and managing small companies in a variety of industries. He was elected President of Chemists Without Borders at the beginning of 2016. Shahena Begum started working with Chemists Without Borders Bangladesh project in September 2014. She has completed an online degree in International Development from Queen’s University, Canada and studied Management at the National University, Bangladesh. Asian Studies was her undergraduate major at the Asian University for Women (AUW) in Bangladesh. Original interns, in addition to Shahena: 1. Ano Anowara Begum is currently studying for her Masters in Public Health at University of Colorado Anschutz Medical Campus, USA. She accomplished a B.Sc. in Public Health from Asian University for Women (AUW). She is one of the five initial interns involved in the CWB arsenic project in Bangladesh. Please click the link in reference 3 to know more details about Ano. 2. Nishat Nishat Raihana completed her B.Sc. in Computer Science – Information Communication Technology (CS-ICT) at the Asian University for Women. She belongs to a middle class family and her parents are from a small town of Bangladesh. She is one of the five initial interns involved in the CWB arsenic project in Bangladesh. Please click the link in reference 4 to know more details about Nishat. 3. Taslima Taslima Khanam graduated from Asian University for Women (AUW) in 2014. She had majored in Public Health Studies. She worked with "Skills and Training Enhancement Project" (STEP) of the World Bank Bangladesh as an Education Department Intern. She is one of the five initial interns involved in the CWB arsenic project in Bangladesh. Please click the link in reference 5 to know more details about Taslima. 4. Monira Monira Sultana graduated from Asian the University for Women (AUW) in 2014. She was a former student at Humboldt State University in California, USA. She is one of the five initial interns involved in the CWB arsenic project in Bangladesh. Please click the link in reference 6 to know more details about Monira. 49

References 1.

2.

3.

4.

5.

6.

7. 8.

9. 10. 11.

12.

13. 14.

Talukder, S. A., Chatterjee, A., Zheng, J., Kosmus, W. Studies of Drinking Water Quality and Arsenic Calamity in Groundwater of Bangladesh. Proceedings of the International Conference on Arsenic Pollution of Groundwater in Bangladesh: Causes, Effects and Remedies, Dhaka, Bangladesh, February 1998. Smith, A. H.; Lingas, E. O.; Rahman, M. Contamination of drinking-water by arsenic in Bangladesh: a public health emergency. Bulletin of the World Health Organization 2000, 78 (9). Profile of Anowara Begum. https://docs.google.com/document/d/ 1Hc0IcOU-psYMHvr6HHg64PvDZ3WUcJIlTPYxNRLA5f8/edit (accessed August 2, 2017). Chemists Without Borders Arsenic Education Project. https:// www.indiegogo.com/projects/chemists-without-borders-bangladesharsenic-educ-n/#/ (accessed August 2, 2017). Profile of Taslima Khanam. https://docs.google.com/document/d/ 15ryPSEx6cUWfHxSS1qw0obG2tVK2IsC980gHyQj8R6Y/edit (accessed August 2, 2017). Profile of Monira Sultana. https://docs.google.com/document/d/ 1xVP8fyox7K1PIMdo1TxXI_7WcMXOv4k7oAzdwVnfU6E/edit (accessed August 2, 2017). Arsenic Problem. https://drive.google.com/file/d/0B4RhI2zVeKNVm50X3dhMGpXcW8/view?usp=sharing (accessed August 2, 2017). Chemists Without Borders Arsenic Education Project. https:// www.indiegogo.com/projects/chemists-without-borders-bangladesharsenic-educ-n/# (accessed August 2, 2017). Joypura School Arsenic Awareness Visit. http://www.agami.org/node/269 (accessed August 2, 2017). Project Well. http://projectwellusa.org/ (accessed August 2, 2017). Department of Public Health Engineering. http://www.dphe.gov.bd/ index.php?option=com_content&view=article&id=125&Itemid=133 (accessed August 2, 2017). DPHE Water Testing Cost. http://www.dphe.gov.bd/ index.php?option=com_content&view=article&id=127&Itemid=135 (accessed August 2, 2017). Hope Foundation. http://www.hopeforbangladesh.org/ (accessed August 2, 2017). Chemists Without Borders and Agami Collaborate on Health Courses. http:/ /agami.org/node/309 (accessed August 2, 2017).

50

Chapter 4

“Penny per Test” - Low Cost Arsenic Test Kits Christopher Lee Lizardi*,1,2 1Clear

Waters Testing, 3708 W. Bearss Ave., Suite B3422, Tampa, Florida 33618, United States 2Chemists Without Borders http://www.chemistswithoutborders.org/ *E-mails: [email protected], [email protected].

In late 2011, Chemists Without Borders had become concerned with the prevalence of high arsenic concentrations in the groundwaters of Bangladesh. A low cost arsenic abatement technology was implemented, however it required sustained testing to monitor arsenic levels. Also, widespread testing of domestic ring wells is still needed to determine at risk populations. In response to these issues, Chemists Without Borders sought to develop a low cost arsenic test kit, named the “Penny per Test”, describing the idealistic goal of a test that can be manufactured and purchased by a consumer for less than 1 US penny. Several methods were explored by both the Chemists Without Borders team and in collaboration with the company IdeaConnection®, with the best option proving to be a modified version of the Gutzeit test for arsenic. To this end, Chemists Without Borders set out to develop a semi-quantitative test for the Drinking Water Quality standard of 50 ppb that could be manufactured by local Bangladeshis. So far, Chemists Without Borders has begun working with the Asian University for Women, formulated the reagents for the modified Gutzeit test, which foregoes the use of the lead acetate oxidant, sourced reagents for purchase within the country, and have reached a current manufacturing cost of $0.21 US dollars per test.

© 2017 American Chemical Society

Chemists Without Borders’ Ingress in Developing a Low Cost Arsenic Test Kit The development of the low cost arsenic test kit project began with investigations into a completely different public health issue in the country of Bangladesh. Chemists Without Borders (CWB) had been concerned about reports of Typhoid fever in the country in the past two decades, and began discussing humanitarian efforts to mitigate the spread of the disease. Typhoid fever is caused by the bacterium Salmonella enterica typhi, where infection commonly occurs by drinking contaminated water (1). Waters become contaminated with S. Typhi when human waste is discharged into the water body. Unfortunately this is a common practice in the slums and rural areas of the country. Highlighting the incidence of Typhoid fever in Bangladesh, a 5 year study from 2005-2009, measured rates of infection in the Dhaka Metropolitan Area (DMA). Dhaka is the capital and largest city in Bangladesh, and the population measured in the paper included some 8 million residents. In this work, Ongee and coworkers had shown incidence rates in an urban slum of Bangladesh, at 3.9/1000 persons/year (Figure 1 is a graphical representation of infection over the years) (2).

Figure 1. Incidence of Typhoid Fever in the Dhaka Metropolitan Area. Since Typhoid infection generally occurs from drinking contaminated surface waters, the initial solution was for CWB to look into the installation of wells to pull groundwater for domestic supply (see Figure 2 for an image of a ring tubewell in Bangladesh). Although groundwaters have provided people with potable water for millennia, the geology of Bangladesh introduces its own challenges for providing clean drinking water. Groundwater in the aquifers of the Bengal Basin contain high levels of arsenic adsorbed onto iron oxide minerals and clay. Changes in the oxidation-reduction potential (ORP) and pH are the major causes for speciation and release of arsenic from aquifer materials. Seasonal variations, and pumping of the aquifer can also result in the relase of arsenic from the aquifer and dissolution into the groundwater (3). An exemplary mechanism for arsenic release into the groundwater based on changes in oxidation state comes from microbial action. Sorped As on iron oxyhydroxide clays can release As when undergoing microbial reduction in the presence of organic carbon, producing As(III), As(V), and iron hydroxide (4). Equation 1 shows microbial 52

reduction promoting the release of As into the groundwater. As will be seen later, the reverse of this chemistry can be used to adsorb As back onto an iron matrix. Some aquitards are hydrogeologically leaky, and can sustain As transport to the aquifer in concentrations up to 500 ppb (5).

Figure 2. Ring Tubewell in Bangladesh.

A 2009 study by the Bangladesh Bureau of Statics (BBS) and the United Nations International Children’s Fund (UNICEF) illustrates the extent of arsenic contamination in the groundwaters of Bangladesh. In this study, wells were measured to determine if they contained arsenic in concentrations higher than the Bangladesh Department of Environment’s Drinking Water Quality standard (DWQ) of 50 ppb (6). The intent was to map out the degree of contamination in both rural and urban communities. The study chose 15,000 clusters of random geographic locations to measure, at 20 households per cluster, with a total sample size of 300,000 (7). Based on the results of the survey, an estimated 22 million people may have been drinking arsenic contaminated water beyond the 50 ppb DWQ in 2009. Even more astonishing was the estimate that another 5.6 million people were most likely drinking water with >200 ppb As. In response to this surmounting humanitarian issue, the search for an arsenic abatement technique was begun. CWB deployed the “SONO Filter” for arsenic removal of groundwater, developed by Prof. Abul Hussam at George Mason University. The SONO filter was employed in over 30,000 households in Bangladesh. Filter efficacy verification for the SONO filter was performed by both the Bangladesh government (Bangladesh Arsenic Mitigation Water Supply Project, BAMWSP) and third parties such as Grainger. Ten different filters were studied that treated 590,000 L of groundwater from wells in villagers’ homes. The studies found that the SONO filters arsenic removal brought concentrations down to below the Bangladesh DWQ standard of 50 ppb, and even the World Health Organization (WHO) and United States Environmental Protection Agency (USEPA) limit of 10 ppb (8). The primary active material in the SONO filter is a composite iron matrix (CIM) made of cast iron turnings (9). It is believed that the filter works by iron binding arsenates (HAsO42-, H2AsO4-) and arsenite (As2O3) to form bidentate binuclear complexes with solid phase FeOH and Fe(O)OH. The adsorbed arsenic 53

is stable and does not readily desorb, as illustrated by the large equilibrium constant, K = 1029. IR and X-Ray absorption structural studies led Hussam and coworkers to publish a hypothetical mechanism for the adsorbtion of arsenic species by the CIM. First, oxygen is converted to the superoxide radical by iron(II) catalysis in water (Equation 2). Two moles of the superoxide can then react with As(III) species such as arsenite, and convert them to As(V) arsenates. It is believed that the As(III) oxidation to As(V) is catalyzed by ~1-2% w/w Mn impurities in the CIM (Equation 3). Iron hydroxides and iron oxyhydroxides then adsorb this resulting arsenate (Equations 4 and 5).

Although the SONO filters have shown some initial succes in chemical removal of environmental arsenic species, it has still not been possible to install them in all contaminated homes’ and communities’ wells due to the cost of manufacturing. As of 2007, the SONO filter costs ~ $50 (USD) to manufacture. This led CWB to reconsider the strategy of combating arsenic poisoning in the country. Instead of treating all the wells with contaminated groundwater, it was decided that a simpler, more cost effective solution to helping people drink As free waters is to develop a low cost test kit. This low cost test kit could also sustain monitoring of wells undergoing treatment programs, such as those with installed SONO filters. Furthermore, a low cost readily available kit will allow users to switch from highly contaminated wells to wells that are safe according to the DWQ. This is when the genesis of the “Penny per Test” project began. The desired goal of the “Penny per Test” kit is as follows; develop a test kit that is operationally simple (i.e. operable by users with no formal education), the test should be safe (no personal protective equipment required), the test should have a clear endpoint (i.e. red is contaminated, green is safe), and finally, the test should be cheap (costs one US penny to manufacture each test). 54

Finding the Best Method for the “Penny per Test” Arsenic Test Kit Current methods to determine arsenic concentrations may be conducted in the laboratory or in the field. Laboratory based methods include hydride generation-atomic absorption (10) and the silver diethyldithiocarbamate method (11). In the hydride generation-atomic absorption method, a suitable hydride reducing agent such as sodium borohydride (NaBH4) is used to convert arsenic species to their hydrides (i.e. arsine gas, AsH3) and are subsequently decomposed in an argon-hydrogen flame, allowing for atomic absorption measurement. The silver diethyldithiocarbamate method involves generating arsine gas (AsH3) as above with NaBH4, then by use of oxygen as a carrier gas, passing the arsine into first a glass wool or cotton scrubber with adsorbed lead acetate to remove interfering hydrogen sulfide. The arsine gas then proceeds through the apparatus to react in an absorber tube containing silver diethyldithiocarbamate and morpholine dissolved in chloroform. A red colored solution is formed which may be sampled and measured spectrophotometrically at 520 nm to determine the total inorganic arsenic concentration (12, 13). The most common field method is based on the traditional Gutzeit method for arsenic determination (14). The Gutzeit method was first established in 1879 as a means to detect the presence of antimony and arsenic, and is based on the even older Marsh-Berzelius test. Major suppliers of water quality test kits, such as Hach, LaMotte, and Taylor Technologies, manufacture field kits based on the Gutzeit method. CWB began investigation into finding the best method for the “Penny per Test” arsenic test kit with the help of IdeaConnection®. IdeaConnection® is a company that specializes in providing technical solutions and outsourcing research for other companies which lack the adequate technical resources. With consultation from IdeaConnection®, four methods were provided to CWB that best fulfilled the requirements of “Penny per Test”. These four solutions were an iodometric titration (15–17), an acoustic biosensor (18–20), an E. coli assay (21), and the aforementioned Gutzeit method. The iodometric titration uses iodine formed in situ from potassium iodide to quantitatively react with arsenite (Equation 6). The addition of bromine water (Br2 in H2O) then oxidizes the resulting NaI from the previous reaction to form sodium iodate (Equation 7), which can then react quantitatively with arsenates (Equation 8). With a modified starch indicator, the first excess of iodine can be measured as the color changes from green to a clear blue endpoint. The test is sensitive down to a concentration of 2 x 10-5 M I2.

55

Another method was proposed which used a biosensor and acoustic transducer. A bacterium that consumes As(III) and As(V) can be grown on a membrane attached to an input and output transducer, and adhered to a piezoelectric substrate. Changes in current or magnetic field by the consumption of arsenic would produce ultrasound waves that can be measured and directly related to arsenic concentration. A schematic of the device is shown in Figure 3 for representation.

Figure 3. A Biosensor and Acoustic Transducer for Arsenic Detection. The third solution proposed was an E. coli assay which involved growing two strains of the bacteria, one which is sensitive to arsenic, and the other which uses arsenic as a food source. The sensitive strain would die off in the ppb range of arsenic, implicating a concentration of concern. The other strain would thrive in the arsenic environment, informing the user that the pollutant in question is indeed arsenic and not a false positive for another contaminant. Lastly, a modification of the Gutzeit method was proposed as an ideal solution for the “Penny per Test”. As described previously, the Gutzeit method is a widely used field test, and is available in commercial arsenic test kits. The chemistry of this test will be examined in more detail in the next section of this chapter. The four solutions put forth by IdeaConnection® then underwent an analysis by CWB to weigh the pros and cons of each method, and how well they matched with the “Penny per Test” criteria. A metric system was devised with the more ideal solutions receiving a higher numerical value. The iodometric titration received a 50/100, although it was operationally simple and inexpensive, it lacked the sensitivity, and measurements began in the ppm range. The acoustic biosensor received a 61/100. It was a novel idea and was made of inexpensive materials (quartz, cellulose, etc.). However, the materials needed for the device required advanced manufacturing (360 μm silicon wafer). Also, the sensor had an expiration date, and was most accurate when used within 24 hours after manufacturing. 56

The E. coli assay received a 78/100, this test met the requirement of 1 US penny per test, and was operationally simple, but provided no real measurement of concentration. Although the sensitive strain died off in the ppb range, the exact concentration was not specified, and the ppb range is where arsenic is measured and given regulatory limits (i.e. 50 ppb for DPHE, 10 ppb for the WHO and USEPA).

Current Results and Moving Forward with the “Penny per Test” When it was determined that the Gutzeit method would prove to be the best for “Penny per Test”, CWB set out to optimize and modify the method for its eventual application in rural Bangladesh. The first task was to determine the reagents and formulations used in the Gutzeit method, or any modern variants thereof. Through a search of the literature (22, 23), and manufacturers of Gutzeit-based test kits, a test method was developed by CWB. Before listing the reagents in detail, it will be advantageous to describe the chemistry of the test first, so as to provide insight into why CWB chose these formulations. The Gutzeit method uses highly acidic and reducing conditions to both reduce As(V) down to As(III), and to generate arsine gas (AsH3). The arsine gas then travels its way up the reaction vessel to a mercuric bromide impregnated strip held at the top of the container. The strip will then change color as arsenic-mercury halogenides are formed from the reaction of arsine gas with mercuric bromide. The major interferences are antimony and hydrogen sulfide. Antimony reads the same as arsenic in the test, while H2S also reacts with the mercuric bromide producing a very dark color and false positive. Hydrogen sulfide is removed by the use of cotton, glass wool, or other porous support that is moistened with an oxidizing solution, such as lead acetate. Antimony can not be removed and is a known intereference that must be accounted for through other means. CWB’s choice of reagents to carry out this test were as follows: for a 50 mL volume in a 125 mL reaction flask, 1.5 g of sulfamic acid, ACS reagent grade for the acid, 1.0 g of Zn granules, 10-100 mesh, As free, to produce a reducing environment, and 5% w/v HgBr2 in EtOH impregnated on Whatman filter paper for the detection of arsine gas. The proposed reactions are illustrated in Equations 9 and 10 using the traditional sulfuric acid as a model acid.

57

One important feature to note of CWB’s test for arsenic is the lack of an oxidation step to remove interfering hydrogen sulfide. The rationale for this comes from van Geen and workers (2005) who discovered that when testing the waters of Bangladesh, it was possible to remove the oxidation step with little to no change in the outcome of the measurement. They tested 799 wells over five years and showed that using the Hach field kit for arsenic without the oxidation step produced the same results as found from ICP-MS for 88% of the tests (24). CWB decided then to omit the oxidation step to save on the costs of producing the “Penny per Test”. Figure 4 shows a schematic of how the kit is to be made, and a blank test being performed. First, in Figure 4 a) mercuric bromide is dissolved in EtOH while being shielded from light. The strip support portion of the test strip can be made from 110 lbs. paper or an equivalent material that is of low cost and easy to cut. Figure 4 b) show a cut strips of 110 lbs. paper at 3.8 cm x 8.9 cm, Whatman filter paper is then cut at 3.0 cm x 4.5 cm and adhered to the strip. At this time, the HgBr2 solution can now be added via pipet. Both the sulfamic acid and zinc can be measured out and added to heat-sealable Mylar® bags, 2 Mil thickness. Figure 4 c) shows sulfamic acid in a Mylar® bag as it is then impulse sealed in Figure 4 d). In Figure 4 e-g) the general procedure is shown, which operates the same way as the current commercial Gutzeit-based test kits. In Figure 4 e) the strip is fitted into a rubber cap with a bored hole to allow AsH3 to pass to the reagent containing strip. Zinc and sulfamic acid are added to a 50 mL sample taken, and the user then allows the reaction to proceed for 15 minutes with intermittent swirling (Figure 4 f)). Figure 4 g) shows the evolution of hydrogen gas, and in the case of an arsenic containing sample, arsine gas.

Figure 4. Making the “Penny per Test”. Once the formulations were had, CWB needed to build connections in the country of Bangladesh to facilitate the development and deployment of the kit. CWB had worked with the Asian University for Women on projects in the past, and decided that hiring on interns who could work in the lab would be ideal for beginning prototypes of the kits. In late 2015 two interns were hired from the university who spearheaded the Bangladesh portion of the project. The first goal was to find sources for raw 58

materials which could be easily purchased in the country for similar or lower costs than what would be found in the United States. The interns working under CWB sourced all the requisite reagents for the formulations, materials for manufacturing the packaging and cases, and equipment for furnishing the lab. All of this was done to a budget of $2000 US dollars. However, this dollar value equated only to the initial production of ~8-10 test kits which house 50-100 tests each. Further budgeting is required to produce a value that will describe how much it will costs to equip a lab, and purchase the materials required to make enough reagents until a return on investment (ROI) can be seen from a potential start-up company. This is one of CWB’s current milestones for this project, and proper budgeting with a small company in mind are at the fore of the work on “Penny per Test”. Another major goal of the project is the continued research into a test that costs 1 US penny to manufacture. As of September 2016 the current costs per test was ~ $0.89 US dollars to manufacture in the US and $0.48 US dollars to manufacture in Bangladesh. However, this was due to the misconception that 2.0 g of sulfamic acid were needed per test, and that the concentration of the mercuric bromide was 5% w/w. New insight showed that the kits could be manufactured in the US at $0.44 US dollars and at $0.21 US dollars in Bangladesh. Still, these values are far off from the idealized penny per test goal that CWB has envisioned. Continued work goes into optimizing the test kit, and more effectively, finding newer and cheaper suppliers for raw materials. Some reagents and items are actually more expensive purchasing in Bangladesh than the US, such as sulfamic acid which the interns found listed at 2500 BDT (Bangladeshi Taka) for 500 g vs $12.00 USD for 11.33 kg in the US. Ensuring quality control and product uniformity is another challenge for the project. As daily manufacturing of the kits will eventually occur without supervision from CWB team members, proper training of the students and future employees of AUW is imperative. One strategy for maintaining quality assurance is through CWB sponsored training at the university. By sending CWB volunteers to train students and staff at AUW, good manufacturing practices and proper quality control procedures can be passed down to those who will be involved with the daily production of the kits. Chemists Without Borders has already held online training seminars with the students via Skype and distributed electronic files of the manufacturing and quality control of the kits. Laboratory staff at AUW have also volunteered to assist CWB with training students. Chemists Without Borders has tasked themselves with aiding the rural and poor people of Bangladesh who are affected by the surmounting humanitarian issue of arsenic in their drinking water. Many strategies have been employed to mitigate arsenic in drinking water supplies, but as of now Chemists Without Borders has decided to develop low cost test kits for determining which drinking supplies are safe, instead of the gargantuan task of treating the vast number of wells in the country. To this end, the idea of a “Penny per Test” kit was envisioned for determining arsenic in drinking waters in Bangladesh. A kit that was operationally simple, safe to use, easy to understand the results, and above all, affordable to poor villagers (the cost to manufacture and purchase at one US penny per test). So far, Chemists Without Borders has teamed up with industry and academia to tackle this problem, and has come up with a test kit which works, can be used by trained 59

individuals in the country, and is rather inexpensive at $0.25 US dollars per test in Bangladesh. Continued efforts will reveal whether or not a “Penny per Test” kit is feasible, and how best it can be distributed to needing communities in the country of Bangladesh.

References 1. 2. 3. 4. 5. 6.

7.

8. 9. 10. 11. 12. 13. 14. 15. 16.

17. 18.

19. 20.

Watson, H. C.; Edmunds, J. W. Vaccine. 2015, 33, C42–C54. Dewan, M. A.; Corner, R.; Hashizume, M.; Ongee, T. E. PLOS Neg. Trop. Dis. 2013, 7, 1–14. British Geological Survey. Groundwater Quality: Bangladesh; Technical Report, 2001; pp 1−6. Ravenscroft, P.; Burgess, G. W.; Ahmed, M. K.; Burren, M.; Perrin, J. Hydrogeol. J. 2003, 13, 727–751. Hoque, A. M. Models for Managing the Deep Aquifer in Bangladesh; University College London, London, United Kingdom, 2010. Bangladesh Department of Public Health and Engineering. Arsenic Contamination and Mitigation in Bangladesh. https://www.dphe.gov.bd/ index.php?option=com_content&view=article&id=96&Itemid=104 (accessed March 18, 2017). Mollah, A. S.; Bangladesh National Drinking Water Quality Survey of 2009; Bangladesh Bureau of Statistics, MICS, and UNICEF Technical Report, 2011; pp 1−16. Hussam, A.; Munir, M. K. A. Compilation of SONO Filter Validation Third Party Data, 2008. Hussam, A.; Munir, M. K. A. J. Environ. Sci. Health, Part A: Toxic/Hazard. Subst. Environ. Eng. 2007, 42, 1869–1878. Irgolic, K. J. Sci. Total Environ. 1987, 64, 61–73. Agget, J.; Aspell, A. C. Analyst 1976, 101, 912–913. Howard, A. G.; Arbab-Zavar, M. H. Analyst 1980, 105, 338–343. Pande, S. P. J. Inst. Chem. 1980, 52, 256–258. Gutzeit, H. Pharm. Z. 1879, 24, 263. Hildebrand, H. J.; Benesi, A. H.; Mower, M. L. J. Am. Chem. Soc. 1950, 72, 1017–1020. Mendham, J.; Denney, C. D.; Barnes, J. D.; Thomas, K. J. M. Vogel’s Textbook of Quantitative Chemical Analysis, 6th ed.; Pearson Education: London, United Kingdom, 2009. Tobia, K. S. Z. Anal. Chem. 1973, 265, 23–24. Gao, J.; Carlier, J.; Wang, S.; Campistron, P.; Callens, D.; Guo, S.; Zhao, X.; Nongaillard, B. Soci´et´e Fran¸caise d’Acoustique. Acoustics 2012, 3323–3328, paper 000480. Reyes de Corcuera, J.; and Cavalieri, R. Encyclopedia of Agricultural, Food, and Biological Engineering; Boca Raton, FL, 2003; pp 119−123. ForteBio Interactions. Technical Tip: Preserving Biosensors for Long-Term Storage. http://www.fortebio.com/interactions/July_2008/biosensors.html (accessed March 18, 2017). 60

21. Saltikov, W. C.; Olson, H. B. Appl. Environ. Microbiol. 2002, 68, 280–288. 22. Das, J.; Sarkar, P.; Panda, J.; Pal, P. J. Environ. Sci. Health, Part A: Toxic/ Hazard. Subst. Environ. Eng. 2014, 49, 108–115. 23. Cherukuri, J.; Anjaneyulu, Y. Int. J. Environ. Res. Public Health. 2005, 2, 322–327. 24. Van Geen, A.; Cheng, Z.; Seddique, A. A.; Hoque, A. M.; Gelman, A.; Graziano, H. J.; Ahsan, H.; Parvez, F.; Ahmed, M. K. Environ. Sci. Technol. 2005, 39, 299–303.

61

Chapter 5

Development of a Test-Kit Method for the Determination of Inorganic Arsenic in Rice Julian Tyson,* Ishtiaque Rafiyu, and Nicholas Fragola Department of Chemistry, University of Massachusetts Amherst, Amherst, Massachusetts 01003, United States *E-mail: [email protected].

There is compelling evidence that in many countries, certain sectors of the populations are at risk of long-term adverse health effects from the ingestion of arsenic compounds in their diets. Most at risk are those whose diet consists predominantly of rice and rice products, a group that includes young children and infants, and there are calls for the introduction of arsenic-in-food regulations as well as the provision of advice on limiting consumption. For this advice to be meaningful, information about the chemical composition of rice is needed, with particular reference to the concentration of inorganic arsenic, a class 1 carcinogen, which is thus the species for which, at present, the availability of reliable methodology is crucial. In addition, to meet the needs of inhabitants of countries, such as Bangladesh, with limited (or no) capability to conduct high performance liquid chromatography with inductively coupled plasma mass spectrometry detection, simple inexpensive methodology is needed. As the problem is similar to that of measuring the arsenic concentration in ground water, one possible way forward is to adapt the field test kits that are available for water testing. A progress report on the development of a method for the determination of inorganic arsenic in rice in which the measurement is made with the Hach EZ kit is presented. The co-extracted starch and protein material causes a severe depression of the response when arsine is generated by the reaction of zinc with acid and so an alternative chemistry based on the reaction (well known to analytical atomic spectroscopists) with borohydride in acid is being investigated, © 2017 American Chemical Society

for which there is evidence from other researchers that the reaction is interference-free. A major problem is the control of the kinetics in a batch reaction vessel and procedures in which the borohydride is encapsulated prior to addition. A number of such procedures have been investigated and the most promising appears to be dissolution of borohydride in alkaline solution in an agar hydrogel. A number of parameters of these BAG (borohydride agar gels) are being optimized by three groups of students: those pursuing independent studies in the Tyson research group, those in a course-based research experience, and those in two chemistry classes in a local high school. The most promising composition appears to be 2% agar, 0.2% xanthan gum, to the cooling mixture of which is added (a) sodium hydroxide solution such that the final concentration in a 5 mL volume is 0.1 M and (b) 350 mg of solid sodium borohydride. The BAGS react with almost any acid extract of powdered rice grains to release arsine that forms a color on the mercuric bromide test strips that is close to that of standards of the same concentration.

Introduction The growing interest by all sectors of the scientific community in all aspects of the presence of arsenic compounds in rice is readily shown by interrogating the Web of Science database. When the search terms “arsen*” and “rice” are entered into the title field, some 672 items are retrieved from the core collection. Well over 90% of these items are the results of original research in peer-reviewed publications of one sort or another. The number of items published as a function of time is shown in Figure 1, from which it is readily seen that since around the year 2002 there has been a steady increase in output, such that in 2016, the year with the highest number of articles, just over 80 reports were published. The activity is worldwide: 60 countries are home to the 500 institutions at which the 1,830 researchers, whose names are associated with these reports, are (or were) working. The status of our knowledge of the causes, extent, and implications for this contamination of the world’s rice supply was summarized by Meharg and Zhao in a 170-page book published in 2012 (1). There is no doubt that the potential health problems are enormous, as all rice contains inorganic arsenic, a known human carcinogen, and, possibly even higher concentrations of dimethylarsinic acid, which even if not carcinogenic to humans is not harmless. Every recent article of the type mentioned above opens with some summary statement of the extent of rice consumption. For example Bralatei et al. (2) write, “rice is a staple food eaten by more than 50% of the world’s population,” and inform readers that China, Bangladesh, India, and Indonesia, whose populations get 70% of their caloric intake from rice consumption, produce nearly 70% of the world’s rice. Furthermore, we learn that some of these countries use groundwater contaminated with naturally occurring inorganic arsenic to irrigate the rice fields, 64

which compounds the problem as “rice, unlike most grains and cereals, has the ability to take-up and store arsenic [compounds] in the grain.” Those of us living in the USA have no cause for complacency, as rice grown in many parts of the USA has the highest arsenic contamination of any rice on the supermarket shelves. The most likely causes are (a) the past of use of arsenical pesticides, herbicides and desiccants that were widely and liberally applied to growing cotton, so that rice grown in the same parts of the country now takes up the legacy of these compounds (3), and (b) the high concentrations of naturally occurring arsenic in the soil (4). The extent of exposure in the US was summarized by Consumer Reports in a November 2012 article (4) to which a number of experts had contributed, entitled, “Arsenic in your food: our findings show a real need for federal standards for this toxin.” A more fine-grained picture was present two years later (5) when results of the US Food and Drug Administrations (FDA) analysis of 656 rice-containing products (6) were available. Both of these Consumer Reports articles include recommendations for limiting one’s intake, which are based on current information about the inorganic arsenic content of relevant foodstuffs and the resulting excess lifetime risk of getting lung cancer.

Figure 1. Number of papers published each year with the terms “arsen*” and “rice” in the title.

In early 2016, the US FDA issued guidance for industry on an action level of 100 µg kg-1 for inorganic arsenic in infant rice cereal (7), pointing out that this was the same as that introduced by the European Union (EU) in 2015 for rice to be used in the production of infant foods (8). The EU also has a limit of 200 µg kg-1 for inorganic arsenic in polished white rice (9), which is the same as that proposed by the Codex Alimentarius Commission [a joint initiative of the Food and Agriculture Organization (FAO) of the United Nations (UN) and 65

the World Health Organization (WHO)] (10). The Codex adopted a limit of 350 µg kg-1 for inorganic arsrenic in husked (bown) rice (11). The development of arsenic-in-food regulations around the world up to August 2105 was summarized by Petursdottir et. al. (12), who also discussed the implications for chemical measurement, pointing out the development of screening methods would be an important step because when large numbers of samples must be monitored, it is more efficient to determine inorganic arsenic by a rapid, but possibly imprecise, method and then use more precise (and accurate) methods for those samples who arsenic concentrations are possibly above the regulatory limit. For countries, such as Bangladesh, with limited access to facilities with the relevant analytical chemistry instrumentation, but who have a severe arsenic-contamination problem, a simple, low-cost measurement method will be the only way that large numbers of measurements of the arsenic content of rice can be made. On this basis, Chemists Without Borders (CWB) initiated a project in early 2016, whose goal was to devise a method for the determination of inorganic arsenic in rice based on a procedure that has been available for some time (and is widely used) for the determination of inorganic arsenic in ground water. This topic is the basis of an earlier CWB project that is described in Chapter 4 of this book (“Penny per Test” - Low Cost Arsenic Test Kits by Christopher Lizardi). Although a number of variations of the procedure have been described in the literature and are commercially available, CWB has selected the version in which the arsine, generated by the reaction with zinc powder in acid solution, reacts with mercuric bromide impregnated in a test strip exposed to the head-space gases of the reaction vessel to form a yellow/brown product. Although almost any acid (except nitric) is suitable, the kit comes with reagent packages of sulfamic acid. Two versions of a test based on this chemistry are available from the Hach Company of Loveland CO (13). They differ in the way they remove the potential interference from sulfide, which under the conditions of the test produces hydrogen sulfide, which also gives a colored product on the test strip. The more expensive, “5-reagent” version of the kit (product number 2800000) includes reagents to (a) oxidize sulfide to sulfate and then (b) remove the excess oxidant, whereas the lessexpensive “EZ” version (product number 2822800) removes the hydrogen sulfide from the gas phase by scrubbing with lead acetate solution supported on a cotton wool plug held in place immediately below the hole in the vessel lid over which the test strip is mounted. The company refers to the former product as the “low range test kit,” and the latter as the “high range test kit,” but the reality is that the EZ version will detect down to 10 µg L-1 of inorganic arsenic in a groundwater sample. Both test kits come with a chart on which the colors expected to develop on the strip for a limited number of concentrations are printed. The EZ test kit chart contains colors for 10, 25, 50, 100, 250 and 500 µg L-1, which are calibrated for a 50-mL sample volume and a 20-min reaction time. Researchers in our group have extensive experience of the performance of this test going back more than 10 years (14, 15), and we have used the EZ version of the test kit to support many of the research experiences for students (also described in Chapter 6 of this book: Arsenic in Food and Water: Promoting Awareness through Formal and Informal Learning by Julian Tyson). We have also examined the performance of the test itself and made some suggestions for improvement (16), 66

which can be summarized as run the test for longer and calibrate the response with the help of digital image analysis software. The Hach test kit, its basic operation and the basis of digital image analysis are shown in Figure 2.

Figure 2. A. Hach EZ test kit (reproduced with permission from the Hach Company). The carrying box contains two 50-mL reaction vessels with lids, 100 sachets of reagents 1 and 2, and 100 test strips, tipped with mercuric bromide, in a light-tight container. B. Exposed test strip and calibration chart for arsenic concentration in rice extract solution. Visual interpolation is needed. C. Plot of R, G, B values as a function of arsenic concentration in the rice extract solution. Graphical interpolation gives a more precise result. (see color insert)

Adapting the Hach EZ Test Kit for the Determination of Arsenic in Rice When rice is cooked (or extracted with dilute acid), four arsenic compounds appear in the solution: the two so-called inorganic arsenic compounds arsenate and arsenite, and two organic arsenic compounds monomethylarsonate and dimethylarsinate. As all of these compounds are weak acids, the exact forms in solution will depend on the pH. At the time of writing, all interest appears to be on the concentrations of the inorganic species, which range from low double-digit µg kg-1 values to high triple-digit µg kg-1 values. The good news is that (a) the chemistry of the Hach test kit ignores the methylated species: even if the hydrides are formed by reaction at the zinc surface, they do not react with mercuric bromide to form a yellow/brown product, and (b) the test does not distinguish between the two inorganic forms: arsenate and arsenite both react under the conditions of the test to give arsine. The bad news is that it is difficult to get less than a ten-fold dilution during the extraction process and so as the minimum concentration that can be detected by the test is about 10 µg L-1 in the extract, the minimum concentration that can be detected in the rice would be about 100 µg kg-1. If the goal is to screen rice against a statutory limit of 100 µg kg-1, then clearly some significant method development is needed to achieve the desired improvements in detection capability. Either the dilution during the extraction has to be decreased or the detection capability of the test has to be improved, or both. If the decision level is 200 µg kg-1, a method based on the procedure outlined above is clearly feasible and more detailed questions can be asked about, for example, the precision of the measurements as this is the parameter that limits the methods performance when the target analyte concentration is close to the decision-level 67

value in terms of the risks of false positives or false negatives. In addition to uncertainties in the various chemical stages of the method, there is another possible source of imprecision to consider, namely sampling. This is an important topic, which does not get the recognition it deserves in regards to the determination of arsenic compounds in rice, to be discussed later. We have preliminary results showing that sufficient inorganic arsenic can be extracted from rice grains by hot water to give a response with the Hach EZ test kit. Participants (about 30) in a citizen science activity in conjunction with a public lecture-demonstration (How Much Arsenic Do We Eat?) in December 2011 on the UMass campus (sponsored by the American Chemical Society as part of the celebrations of National Year of Chemistry) were given a Hach test kit and set of instructions as to how to make the measurement in their kitchens. About 10 of the participants emailed digital images of test strips clearly showing yellow colorations. Since that time, the development of this “citizen-science” method has been an on-going, but challenging, project because only readily available household chemicals and apparatus can be used. However, for the CWB project, the method developed is to be implemented by students working in a laboratory in the Asian University for Women in Chittagong in Bangladesh, and some of the “kitchen-method” restrictions can be relaxed. Method Development Of course, questions about precision are not the only ones to be asked. Accuracy is also a major concern. There are two stages that might be problematic: (a) the extraction of arsenic species from the rice into solution and (b) the generation of arsine in the presence of the co-extracted matrix components. Fortunately, the first of these is a feature common to all procedures in which the goal is to determine the individual arsenic species in rice, and as several research reports of this determination are published every year, the extraction of arsenic species from rice has been extensively studied by a large number of research groups. Not surprisingly, there is not universal agreement among the findings. Procedures for the determination of total arsenic may or may not be suitable. Some researchers claim that plasma-source instrumentation gives a response that is independent of the chemical form of the analyte, and so (a) it doesn’t matter what forms are produced by the extraction as long as all the arsenic is extracted, and (b) any convenient arsenic compound can be used for calibration. Some methods are clearly designed to convert all the arsenic species to an inorganic species and as much of the matrix as possible to products, such as carbon dioxide and water, that will not interfere in the subsequent measurement. Clearly such a sample preparation method is unsuitable for the determination of just the inorganic forms, but, looking ahead, if a future goal is to determine both inorganic and organic arsenic in rice by a Hach-test-type method, then a second stage in the overall procedure is needed in which all arsenic is converted to forms measurable by the test. The organic arsenic can now be determined from the difference between the total arsenic and the inorganic arsenic. On the other hand, there is almost no information in the peer-reviewed literature about the second stage, the generation of arsine in the presence of the 68

co-extracted matrix components. All of our preliminary work with the Hach test kit indicates that these components interfere. For the kitchen method, we have focused on water as the extractant and have been investigating some possible means of separating the arsenic species from the macromolecular species that we think are present by dialysis (the dialysis bag is placed in the extract with the goal of collecting small ionic arsenic species inside the bag and excluding the rice matrix). Although this is not the only possible procedure that we have in mind, the appearance of a paper in Analytical Chemistry in the fall of 2015 (2) has moved our research in a slightly different direction. It was also the impetus for CWB to raise the whole question of a simple, low-cost method for the determination of inorganic arsenic in Bangladeshi rice that could be implemented in a lab at the Asian University for Women.

The Bralatei et al. Paper The title of the report is “Determination of Inorganic Arsenic in Rice Using a Field Test Kit: A Screening Method,” which at first sight, might suggest that we had been “scooped.” The field test kit in question turns out to be the Arsenator, a system made by Wagtech Ltd in the UK, available from Palintest (17). The test is based on the same color-forming reaction as that of the Hach EZ kit, namely the reaction between arsine gas and mercuric bromide solid immobilized on a paper support. However, the arsine generation reaction is the hydride generation reaction widely used in analytical atomic spectrometry, in which arsenic species in solution react with tetrahydroborate (also known as borohydride). In the Arsenator version of the reaction, the borohydride is added as the sodium salt, which constitutes about 10% of the mass of a tablet that is dropped into the reaction vessel containing the acidified sample before securing the cap in which the test strip is mounted. As with the Hach EZ kit, the acid provided is sulfamic acid, and the color chart shows colors for 20 min-reaction time and 50-mL sample volume. An important difference between the two kits is that the Arsenator comes with a battery-operated, combined timer/reflectance spectrometer (called a DigiPAsS). When the holder containing the mercuric bromide strip is inserted into the spectrometer, not only is the blank reading established but also the timer is initiated. After the development of the color, the strip is reinserted in the device and the reading (µg L-1 of arsenic in solution) noted. The Arsenator also features a second strip to capture any excess arsine (users of the Hach kit are told to open in a well-ventilated space). Like the Hach kit, the Arsenator features an optional sulfide removal procedure: a filter that is placed in the cap of the reaction vessel immediately below the mercuric bromide test strip. The Arsenator may thus be considered the “Cadillac” version of arsenic field test kits, and, of course, is priced accordingly. It therefore, does not meet an important criterion of the CWB project: the costs must be as low as possible.

69

What the Results in the Bralatei et al. Paper Tell Us about the Prospects for a Hach Kit Method To determine inorganic arsenic in rice, the researchers ground 5 g (measured volumetrically) of rice grains in a coffee grinder or with a mortar and pestle, and boiled the powder in 50 mL of 1% nitric acid for 15 min. The solution was cooled (in a water bath) and the entire mixture (of solution and suspended rice matrix) was transferred to an Arsenator reaction vessel, 2 – 3 drops of antifoaming agent were added followed by one sachet of sulfamic acid and finally a borohydride tablet. The vessel was capped with a bung containing all three adsorbers (sulfide removal, mercuric bromide color development, and arsine collector). After 20-min reaction, the strip was read by the DigiPAsS device. The procedure is illustrated in Figure 3. A second sample for analysis by HPLC-ICP-MS was treated identically, followed by centrifugation at 3000 rpm and 100 µL was injected with no further treatment.

Figure 3. Outline of the Arsenator-based method. Adapted with permission from Bralatei, E; Lacan, S; Krupp, E; Feldmann, J. Determination of Inorganic Arsenic in Rice Using a Field Test Kit: A Screening Method. Anal. Chem. 2015, 87 11271–11276. Copyright 2015. American Chemical Society.

The researchers validated the method by the analysis of a very well characterized pseudo-reference material, the rice flour used in the IMEP-107 proficiency test (18), whose inorganic arsenic concentration is 107 ± 14 µg kg-1, where the ± term is the expanded uncertainty with a coverage factor of 2, corresponding to a confidence interval of approximately 95%. They analyzed 30 rice and rice products, purchased in local shops, by the methods described above for inorganic arsenic (Arsenator), for inorganic arsenic and DMA (HPLC-ICP-MS), and also for total arsenic (ICP-MS), for which a 200-mg sample was digested with a mixture of concentrated nitric acid (70%) and concentrated hydrogen peroxide (30%) in a microwave oven. 70

The results presented showed that the total arsenic ranged from 6 µg kg-1 to 477 µg kg-1 and that the inorganic arsenic in the nitric acid extract ranged between 5 and 301 µg kg-1. All results were presented as the mean of three replicates together with the standard deviation as the ± term. A comparison of the results for the inorganic arsenic determined by the Arsenator method and the HPLC method is described, based on a plot of Arsenator results (y-axis) vs HPLC-ICP-MS results (x-axis), as “accurate.” The slope of the plot presented is 0.928, but no ± term is given, nor is a value for the intercept. Comparing the results by a paired t-test (two-tailed) of the differences shows that the Arsenator values are significantly lower than those of the HPLC method, even at 99% confidence. The average difference is about 10%. In terms of the performance one would expect from a screening method, this is perfectly acceptable, given the spread of values likely to be encountered. In the 30-sample date set under discussion only 2 had mean values above 200 µg kg-1, with a further 2 whose 95% confidence intervals about the means included 200. Applying a “correction” of 10% does not change these numbers. For a decision level of 100 µg kg-1, 14 samples had concentrations above this value, with a further 6 whose 95% confidence intervals about the means includes 100. Again, these numbers do not change if a 10% correction is applied. The good news for our proposed Hach test kit method is that the Arsenator results are only in error by about -10% when compared with the results obtained for the same nitric acid extract by HPLC-ICP-MS, meaning that the presence of the rice matrix does not exert a severe depression on the field test kit method, which we interpret as a result the generation of arsine by reaction with borohydride rather than by reaction with zinc. In addition, we conclude that under the conditions of the test, there is no difference between the response for arsenite and arsenate, although such a difference is well-known in continuous-flow and flow-injection hydride generation (HG) with borohydride for detection by atomic spectrometry (19). It is also well known that arsine can be selectively generated from arsenite (by reaction with borohydride) in the presence of arsenate by controlling the acidity. As the acidity is decreased, the efficiency of HG from arsenate decreases, eventually falling to zero. We also deduce that methylated arsines do not cause any intereferene. It is well known that both DMA and MMA react with borohydride in acid solution to form dimethylarsine and monomethylarsine, both of which will be transferred to the headspace of the reaction vessel by the co-evolution of hydrogen from the decomposition of the excess borohydride. However, there is no evidence that samples that had a high concentration of DMA (as measured by HPLC-ICP-MS) gave a higher concentration by the Arsenator method than by the HPLC-ICP-MS method. In fact, for the three samples with the highest concentrations of DMA, the mean of the Arsenator results were lower than those obtained by HPLC-ICP-MS. The same evidence leads us also to conclude that boiling with 1% nitric acid for 15 min does not convert any of the DMA to inorganic arsenic. The evidence for the completeness of the nitric acid extraction is less compelling, as only one sample (the IMEP-107 material) whose inorganic arsenic content is known has been analyzed. Validation of a method that consumes 5 g of sample for each measurement by the analysis of certified reference materials represents a very considerable cost, as certified reference materials are expensive 71

(many hundreds of dollars for a few tens of grams). Furthermore, a fairly crucial aspect of the analysis is not discussed at all, namely accounting for the moisture content of the samples. As foodstuffs contain considerable percentages of water, it is important to know whether the results provided are on a “wet” (as received) or dry basis. Almost universally for rice, researchers report the results on a dry weight basis. In the case of the IMEP-107 material, the 107 ± 14 µg kg-1 mentioned earlier is the concentration of inorganic arsenic on a dry weight basis; on a “wet” weight basis, the inorganic arsenic concentration is 88 ± 15 µg kg-1, where the ± term is the 95% confidence interval (calculated from data in Table 1 is reference (16)). Bralatei et al. reported obtaining 119 ± 14 µg kg-1, where the ± term is not defined. Assuming this is one standard deviation for three replicates, the 95% confidence interval is ± 35 µg kg-1 and so, based on the overlap of the confidence intervals and the likely outcome of t-testing, there is no significant difference between the value measured by the Arsenator method and the “reference” values from the IMEP-107 material, regardless of whether the wet or dry value is considered. As most rice contains relatively low concentrations of MMA, to a first approximation the total arsenic concentration can be accounted for by the sum of the concentrations of DMA and inorganic arsenic, which in turn is the sum of arsenate and arsenite. Most rice contains more arsenite than arenate, but the arsenate concentration is not negligible. When the data presented by Bralatei et al. is examined there are 10 samples for which the sum of the inorganic and DMA arsenic is 85% or less than the total, determined by the more aggressive “nitric acid plus hydrogen peroxide” digestion followed by ICP-MS. This suggests that for some samples, boiling with 1% nitric acid for 15 min is not sufficient to extract all the species. It has been pointed out by Huang et al. that “substantial time length seems to be necessary to break AsIII-thiolate complexes with dilute HNO3” (20). Possible inaccuracies due to incomplete extraction are of less concern, as this step of the method is common to all methods that have been developed for the determination of arsenic species in rice. In addition to the many tens of articles describing such methods, there are several reports of studies in which the focus was on the accuracy of the extraction method.

Development of a Hach Kit Method for Inorganic Arsenic in Rice Our reading of the Bralatei et al. paper and other relevant reports has led to the following strategy for the development of a method in which the quantification is performed by the Hach EZ test kit (or the CWB version of this): step 1, replace the zinc with borohydride; step 2, investigate possible interference by the antifoam agent, step 3, ensure the extraction procedure solubilizes all the arsenic species; step 4, decrease the quantification limit of the Hach EZ test (from 10 µg L-1 to 5 µg L-1); and step 5, validate the method by the analysis of the same rice material by a different method. We also expect that creation of a new calibration relationship will be needed because the colors on the printed chart provided by Hach will no longer apply. 72

We also envisage a step 6: improve the precision demonstrated by the Arsenator method. Clearly, it is not possible to ignore precision as a figure of merit, but our expectation is that once steps 1 and 3 have been devised, the precision will also, to a large extent, have been optimized. We already know from our previous work with the Hach test how we can improve the test performance: longer reaction times and digital image analysis (16). We decided not to try to implement step 4 by increasing the ratio of mass of rice to volume of extractant. Many researchers have indicated that 1 : 10 (mass in g to volume in mL) is the limit, nor did we decide to try (at this stage) to increase the volume of solution. Though this is clearly a possible route, as the volume of the reaction vessel is such that, say, 100 mL could easily be accommodated. It would also seem relatively straightforward to decrease the volume of the solution by evaporation. Our initial experiments have been conducted for the most part on aqueous standards containing 50 µg L-1, made by serial dilution from a stock 1000 mg L-1 arsenite standard from Hach. We have an Arsenator device, purchased about 12 years ago, that was used in some comparative studies of field test kits (14). There were still some reagents available, including the borohydride tablets. As a first step in our investigations, we repeated the procedure described by Bralatei et al. except that the extracted rice suspension was transferred to a Hach reaction vessel, followed by a few drops of the same antifoam agent, one sachet of sulfamic acid from the Hach test kit (about 0.7 g) and one 12-year-old borohydride tablet from our Arsenator. A measurable color was obtained on the test strip. Iodometric titration (21) of the borohydride in a tablet showed that it contained 320 mg of sodium borohydride Step 1. Addition of Sodium Borohydride to the Reaction Vessel Almost all of our experiments to find a suitable way to carry out the hydride generation reaction have been motivated by the need to control the reaction kinetics. The Arsenator borohydride tablets contain about 300 - 400 mg of borohydride, but if a standard arsenic solution is placed in the reaction vessel and acidified with a sachet of sulfamic acid, it is impossible to get the lid of the reaction vessel secured sufficiently quickly after the addition of a few hundred mg of solid sodium borohydride to ensure that the appropriate color develops on the mercuric bromide strip. We think there are three reasons for this: 1) the arsine generated escapes from the reaction vessel before the lid can be screwed on to make a reasonably gas-tight seal, 2) borohydride also reacts sufficiently rapidly with the acid (to form hydrogen) near the surface of the liquid so that there is not enough reagent left to generate arsine from the arsenic in solution near the bottom of the reaction vessel, and 3) the rapid decomposition of borohydride releases too much hydrogen early in the process so that not all of the arsine generated is purged from solution (arsine is soluble in water to the extent of about 700 mg L-1). Quite possibly all three of these mechanisms are in operation simultaneously. That the successful generation and release into the gas phase of arsine produced by the reaction of inorganic arsenic species in acid solution with borohydride depends critically on the reaction kinetics and the use of a purge gas is well-known to the HG atomic spectrometry community (19). Most modern 73

instrumentation is based on a two-line continuous flow (or flow injection) system in which the acidified sample solution is merged with a borohydride solution (stabilized with sodium hydroxide). The hydride is generated downstream of the merging point, together with hydrogen gas, and the vapors are separated in a gas-liquid separator device aided by the merging of a purge gas (usually argon). Typically the sample and reagent are flowing at single-digit mL min-1 values, whereas the purge gas is flowing at many tens of mL min-1. The purge gas delivers the volatile hydride to the atomizer of the spectrometer. In the regular version of the Hach kit, the sulfamic acid is the limiting reagent and the reaction with the powdered zinc is relatively slow so that even well after the 20-min recommended reaction time has elapsed, bubbles of hydrogen are still forming and detaching. As the zinc sits on the bottom of the reaction vessel, the release of bubbles of hydrogen helps both to purge the arsine from solution into the headspace and to stir the solution so as to aid in the mass transfer of arsenic species from the bulk solution to the surface of the zinc. Despite a diligent internet search, we have been unable to find a supplier of borohydride tablets similar to those supplied with the Arsenator, which contain about 450 mg sodium borohydride and about 4 g of an “inert” filler material that disintegrates (and or dissolves) slowly when the tablet is in contact with the solution in the reaction vessel. It is possible to purchase tablets or caplets that are essentially 100% sodium borohydride, but we found that these reacted in much the same way as the powdered material does and low results were obtained. They are also more expensive than the powder. We were able to delay the reaction long enough to get the lid on the vessel by loading powdered sodium borohydride into gelatin capsules of various sizes, which were then dropped into the acidified sample. As might be imagined, there was little activity until the gelatin had dissolved, whereupon a vigorous reaction occured with considerable frothing and splashing. As a general precaution, we insert a small amount of the cotton wool (approximately 0.02 g) provided into the holder on the underside of the vessel lid to prevent liquid droplets from reaching the mercuric bromide strip. If the drops contain borohydride, the strip turns a dark brown/black color, under which circumstances the test has clearly failed. To some extent the transition from inactivity to rapid reaction could be smoothed out by perforating the capsule once or twice (at one or both ends) with a “push pin.” Results with these “holey capsules” were much better, but were still not as precise as nor developed the same extent of color as the regular Hach reaction with zinc. Despite ingenious modifications to the number and positions of the holes, the performance was always poorer than that of the regular Hach reaction. Two other methods of adding borohydride have been investigated. Attempts were made to prepare sodium borohydride in kaolin tablets according to the procedure described by Yamamoto and Kumamaru (22); however, this proved to be a challenge and after several attempts failed to produce usable tablets, this line of investigation was abandoned. It was considered too complicated for use in the Asian University for Women in Bangladesh. As our research group has developed a number of chemical vapor generation procedures in which the borohydride is immobilized on an anion-exchange resin (23), we have also investigated adding the borohydride to the reaction vessel in this form. Amberlite IRA-400 resin was 74

converted to the borohydride form by stirring in a saturated solution of sodium borohydride, washing and drying. Only 1.5 g of this material was needed to produce the same color with the Hach test kit for a 500 µg L-1 solution as was obtained with the regular operation of the test. In addition, slighter darker colors were produced by replacing the sulfamic acid with 0.1 M hydrochloric acid. It was also found that stirring was not necessary and that darker colors could be obtained by running the reaction for 40 minutes (instead of the recommended 20). However, problems were encountered with aerosol deposition on the strips that could not immediately be alleviated by the use of the cotton wool barrier and this line of investigation has been temporarily put aside in favor of the investigation of another promising procedure.

Gum-Based Gels The procedure currently being investigated by us and our student collaborators at Four Rivers Charter School, Greenfield MA, is the encapsulation of the required mass of sodium borohydride in a polysaccharide gel to which sodium hydroxide has been added as a stabilizer. Initial experiments were performed with agar, a hydrophilic colloid extracted from certain red-purple seaweeds of the class Rhodophyceae, and readily available from a number of suppliers. An agar gel may be easily prepared by transferring an appropriate mass of agar and 50 mL of water to a 50-mL centrifuge tube, which is then capped and immersed in boiling water (supported vertically, so that the cap is above the surface of the water) for about 20 minutes with occasional removal and shaking. Masses of agar corresponding to a final concentration of a few percent (m/V) have been used so far. Agar will also gel in sodium hydroxide solutions and up to 0.2 M NaOH solutions have been used to prepare gels. To procedure a borohydride agar gel (BAG), an appropriate mass of powdered sodium borohydride was transferred to an empty well in a 12-well polystyrene tray (Falcon brand, non-tissue culture treated plate, 12 well, flat bottom, Ref 351143). Each well is a cylinder of about 5-mL volume and diameter 23 mm. To this was added an appropriate volume of sodium hydroxide solution and the contents stirred with a glass rod. Finally 5-mL of the cooling molten agar gel was added and the mixture again stirred. The lid was secured with a rubber band and the tray placed in a refrigerator (approx 3 °C) to accelerate the setting process. Typical values for the mass of sodium borohydride and the final sodium hydroxide concentration are about 300 mg and 0.1 M, respectively. When dropped into a Hach reaction vessel containing an acidified inorganic arsenic solution a mild reaction occurs almost immediately with large bubbles of gas (presumably hydrogen) forming rapidly at the surface of the BAG, which floats. The reaction persists for at least 60 minutes, by which time the mercuric bromide strip will typically have been removed and “read.” Swirling the reaction vessel produces the evolution of small bubbles uniformly throughout the solution. This is interpreted as being due to the mixing of borohydride diffusing from the BAG with the acid in the remainder of the solution by the convection currents produced by the swirling action. At this stage, it is not known whether such swirling is necessary or not. 75

In addition to gels made just from agar, we have investigated some other gel compositions involving mixtures of materials. Both locust bean gum and xanthan gum have been added in smaller amounts to agar gels as a possible strategy for improving the mechanical stability and decreasing syneresis (seepage or weeping). Currently the best performance is obtained from a gel consisting of 2% (m/V) agar and 0.2% (m/V) xanthan gum, containing 400 mg of sodium borohydride in about 0.1 M sodium hydroxide, known as an XBAG. Chemical stability is related to the amount of sodium hydroxide, without which the borohydride reacts to liberate hydrogen, presumably because of the acidic nature of agar. Figure 4 shows a Hach test kit with an aqueous sample and an XBAG reagent.

Figure 4. A Hach test vessel containing a borohydride agar gel reagent. The color developed on the strip is shown in Figure 5 together with the color for the same concentration (200 µg L-1) measured by the standard Hach test reaction (zinc and acid). Both tests were run for the same time (40 minutes). Compared with the color on the printed chart, that produced by the XBAG is lighter and that produced by the zinc is darker. In Figure 6, the test in action with some rice extracts is shown, from which the potential problem due to foaming can be clearly seen.

Figure 5. Color developed with XBAG reagent (top) and with zinc (bottom). (see color insert) 76

Figure 6. Hach test in progress for several rice extracts with XBAG reagents. In addition to these gums we are also investigating the possibilities for gels made from a variety of other gums, including various carrageenans. There are a large number of possibilities (24). Other Preliminary Experiments: Acid, Rice Matrix, and Antifoam Agent As both the generation arsine and the extraction of arsenic species from rice depend on the concentration and maybe the type of acid, we have also been investigating the role of the acid. In the simplest version of the overall procedure, we envisage that the same acid concentration that would be used to extract the arsenic species from the rice would also be suitable for the arsine generation reaction. Our initial thoughts were that this might not be a parameter with much effect, in the sense that there would be a wide range of acid types and concentrations that would be suitable for both extraction and the hydride generation. We also considered that it might be possible to control the rate of the hydride generation reaction by adjusting the acidity, and we have results that show that for a perforated gelatin capsule, the reaction is less vigorous with 0.01% (1.2 x 10-3 M) hydrochloric acid than with higher concentrations. Reversing the order of addition of reagents does not offer any benefits. When an alkaline solution containing borohydride and arsenic was acidified by pouring in the contents of a sachet of sulfamic acid, a rapid vigorous reaction ensued and a (very) low result was obtained. We also have results that show there is a possible difference, in terms of the color developed for a given concentration of arsenic, between hydrochloric, nitric, and sulfuric acids, as sulfuric acid (0.1%, 1.8 x 10-2 M) gives results that are darker for a given concentration and reaction time than either nitric or hydrochloric acids. We are currently using 0.1% sulfuric acid to extract the arsenic compounds from rice. We confirmed that the reaction with borohydride tablets works in the presence of the rice matrix by preparing 400 mL of extract from 40 g of rice with 0.1% sulfuric acid (heat for 40 min). The remaining material was then poured into 6 Hach reaction vessels, 3 - 4 drops of antifoam agent were added and spikes of 5, 10, 15, 20, 25, and 30 µg L-1 inorganic arsenic were added and the test run with an Arsenator borohydride tablet with 40-minute reaction time. The results are shown in Figure 7, from which it may be deduced that not only was a measurable 77

concentration of inorganic arsenic extracted from in the rice, also that it might be possible (a) to apply the method of standard additions, and (b) to distinguish between 5 and 10 µg L-1 of arsenic in solution. Experiments in which the antifoam agent was added to standards indicate that there is a slight, but measureable, depression in the extent of color formation when antifoam is present. However, this feature of the method is essential, as without the antifoam agent the foaming overwhelms the reaction vessel and contacts the mercuric bromide strip even when a protective cotton wool plug is present. In these preliminary studies, we did not measure the moisture content, though in a parallel project (is arsenic lost on drying?) we have measured moisture contents of up to 12%. Typically, we grind the rice grains as received (i.e. without drying) in a domestic coffee grinder or food blender and then use the powdered material. We do not have any details of the particle-size distribution, but all the particles pass through a 1-mm sieve.

Figure 7. Colors developed on strips for additions of 5 (bottom), 10, 15, 20, 25 and 30 (top) µg L-1 inorganic arsenic spikes to 6 portions of the same rice extract. (see color insert)

Conclusions and Future Work From our results so far, we are convinced that the reaction between borohydride and inorganic arsenic to generate arsine does not suffer any major interferences from the components of rice that are co-extracted by dilute acids, and that provided the arsine can be purged from solution into the head-space of the reaction vessel, it may be detected by reaction with mercuric bromide. We are confident that by the judicious use of longer reaction times with, possibly, elevated temperatures and addition purge gas generation (for example by reaction between acid and a carbonate), the quantification capability of the Hach EZ kit can be decreased to 5 µg L-1 in the presence of both rice matrix and antifoam agent. We are also confident that a method that ensures complete extraction of 78

all inorganic arsenic species can be developed, though we think it will involve (much) longer heating than the 15 min of the Bralatei et al. method. Times of 90 minutes (20) and 2 hours (25) are reported by other researchers. We think it would be relatively easy to incorporate a pH/acidity adjustment step, if needed, between the extraction and the hydride generation stages. We have some concerns about the sampling of rice grains from the bulk material. A grain of rice weighs about 20 mg and so a 5-g sample contains 250 grains. If all rice grains contained the same concentration of inorganic arsenic there would be no sampling error, but we have evidence from experiments by a doctoral student (26) and more recently by undergraduates in our lab that there are very considerable differences between grains from the same bag, some of which have concentrations of thousands of µg kg-1. Suppose 10% of the grains contain 1000 µg kg-1 inorganic arsenic and the remaining 90% contain 0 µg kg-1. For a sample of 250 grains, the sampling standard deviation for the 25 grains (on average) that contain arsenic is the square root of (250 x 0.1 x 0.9), which is 4.74. So the relative uncertainty is about 19%. And this is the best-case scenario in which the two types of grain are thoroughly mixed. This is a really a problem for all rice analyses that start by taking a relatively small mass of grains. As almost no researchers report how the sample was taken, we have almost no idea of what the current practice is. Most descriptions of procedures simply indicate that the rice was ground and a few hundred mg were taken for the digestion/extraction procedure. Often no information about the particle size of the ground sample is provided. Drying is another important aspect of the method that is often omitted from reports in the peer-reviewed literature, but as has been discussed above is perhaps not of major concern for a screening method. Not correcting for moisture will cause results to be biased low by not more that about 10% or so. Although making tablets is a little more complicated than making agar gels, it is not out of the question even for a simple laboratory. So our future studies will certainly include making borohydride tablets with a variety of filler and excipient materials and evaluating their performance in our Hach EZ kit method.

Acknowledgments We gratefully acknowledge the contributions by UMass Amherst undergraduate students Da (Harry) Lu, Cassandra Martin, Thanh Mai, Jem Sibbick, Paul Sinno, Patrick Tonne, Alex White, and Chloe Zhang to various aspects of this method development. We thank Andrew Patari and his chemistry students at Four Rivers Charter School in Greenfield MA for their work on the polysaccharide gels. We also acknowledge the work of, and helpful discussions with, Richmond Ampiah-Bonney of Amherst College. Financial support, in the form of a Bradspies summer research fellowship for Ishtiaque Rafiyu, is gratefully acknowledged.

79

References 1. 2. 3. 4.

5.

6.

7.

8.

9.

10.

11.

12. 13.

Meharg, A. A.; Zhao, F.-J. Arsenic & Rice; Springer: New York, 2012 Bralatei, E;; Lacan, S.; Krupp, E.; Feldmann, J. Anal. Chem. 2015, 87, 11271–11276. Williams, P. N.; Raab, A.; Feldmann, J.; Meharg, A. A. Environ. Sci. Technol. 2007, 41, 2178–2183. Smith, D. B.; Cannon, W. F.; Woodruff, L. G.; Solano, F.; Ellefsen, K. J. Geochemical and Mineralogical Maps for Soils of the Conterminous United States; Open-File Report 2014-1082; U.S. Geological Survey, 2014; https:// dx.doi.org/10.3133/ofr20141082 (accessed June 6, 2017). Consumer Reports. Arsenic in Your Food: Our Findings Show a Real Need for Federal Standards for This Toxin, November 2012. http://www.consumerreports.org/cro/magazine/2012/11/arsenic-in-yourfood/index.htm (accessed April 5, 2017). Consumer Reports. How Much Arsenic Is in Your Rice? New Data and Guidelines Are Important for Everyone but Especially for Gluten Avoiders. November 18, 2014. http://www.consumerreports.org/cro/magazine/2015/ 01/how-much-arsenic-is-in-your-rice/index.htm (accessed April 6, 2017). U.S. Food and Drug Administration. Analytical Results from Inorganic Arsenic in Rice and Rice Products Sampling, September 2013. https:/ /www.fda.gov/downloads/Food/FoodborneIllnessContaminants/Metals/ UCM352467.pdf (accessed April 5, 2017). U.S. Food and Drug Administration. Draft Guidance for Industry: Inorganic Arsenic in Rice Cereals for Infants: Action Level. https://www.fda.gov/ Food/GuidanceRegulation/GuidanceDocumentsRegulatoryInformation/ ucm486305.htm (accessed April 8, 2017). The European Commission. Commission Regulation (EU) 2015/1006 of 25th June 2015 amending regulation (EC) No. 1881/2006 as regards maximum levels of inorganic arsenic in foodstuffs. Off. J. Eur. Union. 2015, L 161/15. Report of the Eighth Session of the Codex Committee on Contaminants in Foods; The Hague, The Netherlands, 31 March–4 April 2014. http://www.fao.org/news/story/en/item/238558/icode/ (accessed April 8, 2017). Report of the 39th Session of the Joint Fao/Who Food Standards Programme Codex Alimentarius Commission. FAO Headquarters, Rome, Italy 27 June−1 July 2016. http://www.fao.org/faowho-codexalimentarius/sh-proxy/es/?lnk=1&url=https%253A %252F%252Fworkspace.fao.org%252Fsites%252Fcodex%252FMeetings %252FCX-701-39%252FREPORT%252FREP16_CACe.pdf (accessed June 6, 2017). Petursdottir, A. H.; Sloth, J. J.; Feldmann, J. Anal. Bioanal. Chem. 2015, 407, 8385–8396. Hach Arsenic. https://www.hach.com/single-parameter-test-kits/specialtytest-kits/family?productCategoryId=35547009719 (accessed April 9, 2017). 80

14. Ampiah-Bonney, R. Developments in the Analytical Chemistry of Arsenic to Support Teaching and Learning through Research in Environmental topics, Ph.D. Dissertation, University of Massachusetts Amherst, Amherst, MA, 2006. 15. Tyson, J. F. In Arsenic Contamination of Groundwater: Mechanism, Analysis and Remediation; Ahuja, S. Ed.; Wiley: Hoboken, NJ, 2008; pp 147–178. 16. Kearns, J.; Tyson, J. F. Anal. Methods 2012, 4, 1693–1698. 17. Palintest, Digital Arsenic Test Kit. http://www.palintest.com/en/products/ digital-arsenic-test-kit (accessed April 14, 2017). 18. de La Calle, M. B.; Emteborg, H.; Linsinger, T. J. P.; Montoro, R.; Sloth, J. J.; Rubio, R.; Baxter, M. J.; Feldmann, J.; Vermaercke, P.; Raber, G. TrAC. Trends Anal. Chem. 2011, 30, 641–651. 19. Dedina, J.; Tsalev, D. L. Hydride Generation Atomic Absorption Spectrometry; Wiley: New York, 1995; pp 182–245. 20. Huang, J-H.; Ilgen, G.; Fecher, P. J. Anal. At. Spectrom. 2010, 25, 800–802. 21. Lyttle, D. A.; Jensen, E. H.; Struck, W. A. Anal. Chem. 1952, 24, 1843–1844. 22. Yamamoto, Y.; Kumamaru, T. Fresenius Z. Anal. Chem. 1976, 281, 353–359. 23. Wang, N.; Tyson, J. F. J. Anal. At. Spectrom. 2014, 29, 665–673. 24. Industrial Gums: Polysaccharides and Their Derivatives, 3rd ed.; Whistler, R. L.; BeMiller J. N. Eds.; Academic Press: San Diego, CA, 1993. 25. Hamana-Nagaoka, M.; Nishimura, T.; Matsudo, R.; Maitani, T. J. Food Hyg. Soc. Jpn. 2008, 49, 95–99. 26. Wang, N.; Studies in the Atomic Spectrometric Determination and Speciation of Arsenic in Environmental Samples; Ph.D. Dissertation, University of Massachusetts Amherst, Amherst, MA, 2014.

81

Chapter 6

Arsenic in Food and Water: Promoting Awareness through Formal and Informal Learning Julian Tyson* Department of Chemistry, University of Massachusetts Amherst, 710 North Pleasant Street, Amherst, Massachusetts 01002, United States *E-mail: [email protected].

For many years, Professor Julian Tyson has, through a variety of activities and programs, introduced secondary school and college students to the impact of arsenic contamination of the environment. Arsenic-related topics, which include groundwater in Bangladesh and rice around the world, are featured in formal classroom based courses, course-based research experiences, independent studies, and a variety of outreach and public engagement projects. A common feature is that students are recruited as members of a research group or investigative team and take ownership of the work by making relevant chemical measurements and participating in discussion of the implications of their findings. Leadership is provided in a hierarchical model in which, very often, more experienced students, acting as near peer mentors, guide the activities of the newly recruited members of the groups. In some of the programs, the students work with teachers who have been trained by researchers on the university campus. Both in-school and out-of-school programs are described. Many of the chemical measurements are provided by low-cost field test kits based on the Gutzeit-Marsh reaction, the modification of which has provided a driving force for a considerable number of research projects for the college students. Many hundreds of students have been involved and the programs have considerable potential for empowering the students as agents of dissemination and change, as they educate other members of

© 2017 American Chemical Society

their families and communities about the potential hazards of consuming arsenic-contaminated water and rice and how these can be mitigated.

Introduction Much has been written in the scientific literature related to gaining a deeper understanding of the biogeochemistry of arsenic, particularly of those aspects that impact human health. In addition to the articles appearing in the peer-reviewed primary literature, there is a steady output of review articles in the secondary literature, and there are several excellent recent textbooks (the tertiary literature) covering both the global situation (1), as well as the slightly more specialized areas of groundwater (2), and rice contamination (3). Although it is probably the case that interest in global arsenic-contamination issues in the scientific community, as evidenced by publications in scholarly journals, is at an all-time high, the outlook for the inhabitants of rural areas of Bangladesh, to select a subset of the world’s population that are particularly at risk, would appear to be just as grim as it was when the scale of the problem was first brought to the world’s attention some 30 years ago (4). Clearly there are no simple, easily implemented solutions that would provide “arsenic-free” water in sufficient quantities to meet the requirements of communities in rural Bangladesh for drinking, cooking and irrigation of crops (particularly rice). On the other hand, many countries with arsenic-contaminated groundwater do not face the same catastrophic outcomes—probably because the citizens have expectations that in return for their tax contributions to central government, they will receive, among other services, some degree of protection from potentially harmful chemicals in their foods and drink. Should their particular circumstances put them outside the safeguards created by their government, they have the resources to make the necessary changes to their immediate environment and lifestyle. However, even for the most developed nations in the world, public health is not necessarily the highest priority for governments facing other demands on their resources from areas that might be seen as equally, if not more, important, such as education, national security, and defense. The current debate in the United States over the long-term health implications of consuming rice (all of which is contaminated with carcinogenic arsenic compounds) provides an excellent example of the conflicting forces that shape public health policy in a capitalist democracy. From time to time, both scientists (5) and science writers (6) summarize the situation, usually concluding with a call for action. Items appear in the popular media related to some particular discovery, such as fruit juices sold in the United States contain measurable concentrations of arsenic, some of which may be in the form of the carcinogenic inorganic arsenic compounds, or that some wine may contain concentrations of arsenic higher than the maximum contaminant level of 10 µg L-1, set by the US Environmental Protection Agency and the World Health Organization. Relatively recently, for example, the US Food and Drug Administration announced the introduction of an “action level” for the 84

inorganic arsenic content of rice cereal (7) and the American Association for the Advancement of Science organized a well-attended symposium at the February 2017 meeting in Boston entitled “Arsenic in Food: from soil to plate to policy.”

Promoting Dissemination and Engagement However, it is difficult for scientists to engage the public in any sustained way that would create a lasting awareness of any of the various arsenic-contamination situations. They are not constantly on the front page of the major newspapers, as they do not have the characteristics that media journalists use to select topics, such as immediate impact on the lives of individuals with whom many consumers of the media will readily identify. Hence, at the time of writing, the media are focused on (a) the changes to the legislation in the US by the incoming administration, (b) whatever weather-related disaster has befallen some unlucky township, and (c) threats to our national security by both terrorists and/or foreign governments. In this Chapter, I argue that approaches to public engagement that have the potential for long-term impact are (a) to involve students (at all stages of the education processes) in research projects related to arsenic-contamination issues, and (b) embed relevant topics in undergraduate courses and research experiences. Before describing the details of these various activities, I want to address the question of whether students at early stages of their educational careers can meaningfully participate in research. A number of authoritative organizations, such as the American Association of Colleges and Universities (AAC&U), list “undergraduate research” as a high impact practice (8). The AAC&U is the leading association concerned with the quality, vitality and public standing of undergraduate liberal education. Founded in 1915, AAC&U now comprises more than 1200 member institutions—including accredited public and private colleges and universities of every type and style. In 2010, the AAC&U published “Five High-Impact Practices” (9) an account of the findings of research on learning outcomes, completion and quality by Jayne Brownell and Lyn Swaner, who were tasked by George H Kuh (the Chancellor’s Professor of Higher Education at Indiana University Bloomington and Director of the Indian University Center for Postsecondary Research), to “delve more deeply into the research that supports the general pattern of findings associated with the ten high-impact practices indentified in the 2007 AAC&U Liberal Education and America’s Promise (LEAP) report, College Learning for the New Global Century.” The five practices that were the subject of study by Brownell and Swaner were first-year seminars, learning communities, service learning, undergraduate research and capstone experiences. They attempted to separate the findings concerning “underserved” students as well as identify the “general effects.” In summarizing their findings of the research on learning outcomes, Brownell and Swaner write (9), “across the five practices, the most common outcomes . . . include higher grades, higher persistence rates, intellectual gains, greater civic engagement, increased tolerance for and engagement with diversity and increased interaction with faculty and peers.” With regard to underserved students, they conclude that although the numbers of studies examining the experiences of such students is far more limited, 85

outcomes included “higher grades, higher persistence rates, a greater sense of belonging on campus, and higher rates of graduate student enrollment.” As the AAC&U has recently released a report of the preliminary findings of the Valid Assessment of Learning in Undergraduate Education (VALUE) initiative (10) in which evidence is presented for arguing that learning among college students is on solid ground with regard to written communication, critical thinking and quantitative literacy. Almost all of this report is concerned with the methodology by which student learning was assessed (reading student papers, and scoring against a rubric, by experts), but it is not hard to envision that the discussions that are initiated as a result of valid evidence that students are learning will broaden to identify the high impact educational practices. And that many universities and colleges are investigating, and possibly investing in, the practices on their particular campus that lead to these demonstrable gains in student learning, which surely correlate with the success and satisfaction that all institutions of higher education seek to provide for their graduates.

The Nature of Research If research is defined as the generation and dissemination of new knowledge, it is difficult to envision how students can participate: they don’t know enough to contribute at the level commensurate with authorship on a publication. The guidelines for authorship of any published scholarly work by members of the University of Massachusetts Amherst are listed below (11), from which it may be seen that authorship by an undergraduate in a STEM discipline would be relatively rare. Guidelines for authorship of any published scholarly work at UMass Amherst: 1.

2.

3.

4.

5.

If a contribution is of a clearly technical nature (such as performing routine chemical analyses, transcribing interview records, or tabulating raw data), an acknowledgment could be sufficient. The same applies to professional help such as material preparation and instrument construction, drafting, statistical or computer assistance, and so forth. If, however, the central topic of the publication is the presentation or evaluation of a technique (including computer software), then a technical contribution may be of sufficient importance to merit authorship. If an individual suggested an idea that had an impact on the work development but did not actively participate in its implementation, acknowledgment of the contribution will be sufficient. If an individual contributed a key idea or ideas, and/or made other substantial creative contribution to the work in its design, execution, interpretation, and/or summary, then (s)he is entitled to authorship. A graduate student whose thesis work is used as the major source of material for a publication is entitled to authorship. However, (s)he is not automatically entitled to authorship if some material from the thesis is used in a review paper, proposal, progress or final report written by the 86

6.

advisor or project director. In such a case, a reference to the material’s origin is sufficient. And finally, administrative or financial responsibility by itself does not merit authorship.

However, I think it entirely reasonable to explain to students what constitutes research and indicate that they are at the start of their career as professional scientists. My hand-out for students at the initial meetings is given below. What is research? Definition: Systematic investigation with the goals of discovering and communicating new knowledge.

How is research done? By scientists working in industry, government labs, and universities and colleges Most organizations have a large number of research groups, whose members collaborate. Most groups are relatively small (< 10). Groups are dynamic. New members join; older members move on; leadership is stable. New members learn from the more experienced members.

New members need training: Background to problem (big picture) Local picture (what the group is interested in) Techniques to be used. Experimental design. Statistical evaluation of results Hypotheses to be tested. Plan of action Communication skills (written and oral) How to find out (library)

Research involves: Getting up to speed (finding out about relevant previous work) Keeping up to date (staying on top of recent contributions) Leading the field (generating and communicating new knowledge) Critical evaluation at all stages

87

How is new knowledge communicated? Within members of research group at regular group meetings Conference presentations (oral or poster) Scientific literature: journal articles Recent work is reviewed periodically by experts, who write “review articles”. Important stuff eventually finds its way into textbooks.

There is evidence (12) that some professional scientists are employed in (or have experience of) institutions that do not have (or maybe do not apply) such guidelines. John Griffiths writes, in the February 2017 issue of The Analytical Scientist, “I have encountered several situations where authorship expectations have been of a somewhat dubious nature.” For high school students and undergraduates, I provide further information about the publication process, consisting of passing around print copies of single issues of several different analytical chemistry journals and explaining the process by which a report of experimental work gets to be included in one of these “magazines.” By explaining the peer review and revision processes, students are introduced to the “way science works” and for the need to develop the skills necessary (a) to find, (b) to extract information from, (c) to evaluate critically the contents of, and (d) to write reports in the format of journal articles. I usually also take the opportunity to stress the importance of chemical analysis, on the basis that many investigations in a whole range of scientific disciplines need reliable information about the chemical composition of relevant materials, which is often difficult to provide. All researchers, therefore, need to know about the scope and limitations of chemical measurement methods, which are often set by the instruments used. Hence, all chemistry degree programs include courses on analytical chemistry, which everyone should take. I conclude by pointing out that by joining my research group for a semester, new members of my group will experience many of the components of the research process listed above, including the opportunity (a) to become familiar with the relevant big picture, detailed background, and previous work done, (b) to conduct a series of experiments in which the designs of the later ones can be based on the outcomes of earlier ones, (c) to draw conclusions, summarize the findings, make suggestions for further work and (d) create a written document containing the material of interest to the broader community (without necessarily defining exactly who this “broader community might be). I also point out some other features of a research program that will apply, such as (a) that the relatively inexperienced and unskilled workers work alongside the more experienced and knowledgeable workers, from whom they can obtain guidance and information as needed; (b) participants are part of an active community of scholars who regularly come together to discuss their interests, findings, and to examine critically relevant new knowledge in the field; and (c) 88

participants take some responsibility for the design and implementation of the experiments and are allowed a certain degree of autonomy in the direction of the work and the design of the experiments. Thus, I would argue that the only feature of an authentic research experience that I cannot routinely provide for the high school students and undergraduates who participate is authorship of an article in a peer-reviewed primary journal. Nonethe-less, I consider it legitimate to describe these various programs for students as “research,” and to offer students the opportunity to join my research group and contribute to our on-going work related to the analytical and environmental chemistry of arsenic.

The University of Massachusetts Amherst Programs Graduate Students in K-12 Education Many of the activities in which students and their teachers have been engaged have been organized by the universities STEM Education Institute, at whose website (13) further details may be found. In 2002, the University received a grant from the NSF’s Graduate Student in K-12 Education (GK-12) program, and for four years organized a program in which graduate students spent several hours a week in middle-school classrooms working with the teachers to implement inquiry–based learning activities around the research interests and scientific expertise of a number of faculty members. One of the topics was arsenic-in-the environment. At the time, not only was arsenic contamination of drinking water a prominent topic, but also there was considerable debate about the possibilities for arsenic ingestion as a result of contact with wooden structures pressure-treated with chromated copper arsenate (CCA), and of the leaching of arsenic into the soil. As one of the goals of the program was to for students to understand the importance of chemical analysis, it was necessary to find a way to integrate chemical measurement into the classroom activities and not take samples back to the university campus and present the students with results. We chose the Hach 5-reagent kit to start with and then switched to the EZ kit when it became available, as it is less expensive and quicker. We realized that for almost all of the materials we were examining, it was not necessary to deal with a possible interference from sulfide. None-the-less, it was still not possible for students to prepare materials and run a test in one class period, and so the 24-hour version of the test was born, in which the strip was read in class the following day, 24 hours after the reaction was initiated rather than the 20 minutes recommended by the manufacturer. Meeting the in-class needs for chemical measurement stimulated an interest in field test kits, particularly those base on the Gutzeit modification of the Marsh test. The timely arrival of an NSF research grant in 2003 allowed some of these interests to be followed while strengthening active involvement with one of the teachers and her students through the “broader impacts” components of the grant. This program was selected, following a national competition, as an exemplary broader impact component and was showcased at an American Chemical Society National Conference in Washing DC in 2005 (14). 89

Course-Based Research Experience for First-Year Undergraduates In fall 2004, an arsenic-related research experience modeled on the success with the middle school students in the GK-12 project was created for undergraduate students at UMass Amherst taking the first- or second-semester of the general chemistry sequence. This program is now in its 21st semester and over 560 students have participated. The basic format is that students work in small groups, sometimes with a more experienced undergraduate, on a project related to Professor Tyson’s interests in the environmental and analytical chemistry of arsenic compounds. There are several goals for this activity: getting the undergraduate student participants interested in research by creating an “authentic” research experience, raising awareness of the impacts of the transport and transformations of arsenic compounds in the environment, and inculcating an understanding of the critical importance of reliable chemical analysis in underpinning these kinds of studies. The plight of rural communities in Bangladesh is always featured in the background to many of these projects. Participants in the arsenic project write (a) a background paper that includes a description of one measurement technique, and some suggestions for the initial experiment (not exactly a research proposal, but the analogue of one), and (b) a final report in the form of a journal article. For most of the semester, outside of the lab each group works period to its own schedule, set by the members of that group. However, all the groups come together on three occasions, in addition to the very first meeting, at which each group makes a PowerPoint-assisted presentation of their progress. Each member of the group contributes to the oral presentation. Everyone in the program is therefore exposed to the topics that the other groups are working on, which always include a number related to the low-cost, small scale remediation of contaminated ground water. Other projects are concerned with improvements in the Hach test kit, or the development of methods of analysis for materials, such as soils, for which the kit is not originally designed. Recently several projects have been focused on the extraction and determination of arsenic compounds in rice. In the past two years, the projects have been closely linked to the Chemists Without Borders arsenic measurement projects (the low cost arsenicin-water test and the arsenic-in-rice measurement).

Research Academies for Young Scientists In the fall of 2006, the first cohort of teachers started work on after-school programs in an NSF-funded program called Research Academies for Young Scientists, known on the UMass Amherst campus as STEMRAYS (15). In this program teachers ran after-school science clubs on environmental. Arsenic topics formed the basis for activities by five teachers, each of whom led a club of about 10 students (grades 4 – 6). The following year, two teachers were trained to be club leaders. There was an education research component to the project and the results formed the basis of a publication in the science education literature (16).

90

Innovative Technology Experiences for Students and Teachers In the fall of 2010, work started on creating materials for the teacher participants in an NSF-funded Innovative Technology Experiences for Students and Teachers (ITEST) program. The UMass Amherst program was known as STEM DIGITAL (digital images in geoscience investigations: teaching analysis with light) and once again featured several environmentally related themes for which chemical measurement was needed. This time all the measurements were of the interaction of ultraviolet, visible or infrared light with relevant materials captured in digital images that were subsequently analyzed by suitable software. For three summers, 30 teacher participants learned about the problems of arsenic contamination of groundwater and of rice and of the role of spectrochemical analysis (as exemplified, at least for the arsenic-related projects, by the Gutzeit-Marsh reaction augmented by digital image analysis) in supporting such investigations. This theme, of improvement through digital image analysis, formed the basis of part of a doctoral dissertation in, and subsequent publication by, the Tyson group (17). The teacher participants took materials back with them to further develop curricular materials for their students. Projects for High School Students Over the years, one or two high-school students have worked on summer projects in my lab. These “internships” have arisen either through contact with a parent of the students through another program, including some of the ones for teachers described above, or through a “summer school” initiative started a few years ago by our Provost. I only participated for one summer, as this was very time-consuming, requiring my presence in the lab or classroom essentially all day for two weeks. I did not consider it to be a useful diversion for the graduate students in my lab at the time. However, since the fall of 2013, students at Four Rivers Charter School in Greenfield MA have been engaged in small group project work for several weeks of their chemistry classes with teacher Andrew Patari. The activity is modeled on the course-based research experience for first year undergraduates, described above. Each year 20 – 30 students are involved, and so well over 100 high school students have learnt about the relevant topic. In the past two years, the projects have been closely linked to the Chemists Without Borders arsenic measurement projects (the low cost arsenic-in-water test and the arsenic-in-rice measurement). Arsenic Topics in the Chemistry Courses CHEM 101: A General Education Course for Non-Science Majors In spring 2013, I offered a version of CHEM 101 (a 4-credit, physical sciences general education course for non-science majors) with the provocative title “How Much Arsenic Do We Eat?” The course contained material not only to enable students to answer this question, but also to allow them to understand the possible health consequences of the chronic ingestion of small amounts of arsenic 91

compounds (some of which are human carcinogens). Rice, therefore, featured prominently among the foodstuffs that were discussed. I also included information about “how science works” as the course aims to address “fundamental questions, ideas, and methods of analysis in the humanities and fine arts, social sciences, mathematics, and natural and physical sciences,” and to illustrate “the application and integration of these methods of analysis to real world problems and contexts,” to quote from the Universities description of “gen. ed.” courses. Students in the course also read a series of articles (5, 18–23), all but one of which, were taken from the original peer-reviewed scientific literature. To help them engage with the contents, a glossary of terms was provided for each article. Questions about the contents of the articles appeared in the quizzes and exams. I also included material relating to the analytical chemistry needed to provide information on the concentration of arsenic compounds in rice. Some of the articles selected for reading were primarily analytical and these (and the others) allowed me to demonstrate that some articles (a) are not well written, (b) contain mistakes, and (c) contain results that are questionable. I have taught the course in the face-to-face mode on campus each spring semester since then to a total of 600 students, I have also offered an online version of the course (also 4 credits) 14 times since the summer of 2013. The numbers are much smaller, typically 12 – 15 students per course for a total of about 186.

Faculty First-Year Seminar For three fall semesters starting in 2009, I offered a 1-credit faculty first-year seminar (FFYS) entitled “Arsenic Around the World” in which I took a broad brush to the canvas of arsenic-related topics. After a sabbatical break in 2012, I offered the seminar for a further three fall semesters, this time as “How Much Arsenic Do We Eat?” Each class contained about 15 students, for a total of about 90 students.

Junior-Year Writing in Chemistry The University of Massachusetts Amherst has a writing requirement consisting of two, three-credit, writing-intensive courses: Introduction to College Writing, taken in the first year, taught by instructors in the University Writing Program, and junior-year writing in the discipline taught by a discipline-specific instructor working in collaboration with a writing specialist. From 1996, members of the UMass Chemistry program’s junior-year writing class (essentially all chemistry majors) taught by myself (and Professor Holly Davis, a writing specialist at Smith College) were given an exercise in which they were asked to write an article for a non-science readership based on the contents of one original article in the primary peer-reviewed literature. Of the 16 times that this version of the course has been offered over the past 20 years, on 12 occasions the class was asked to explain the technical scientific content of “Arsenic in ground-water in 6 districts of west-Bengal, India - the biggest arsenic calamity in the world: 1. arsenic species in drinking-water and urine of the affected 92

people” in language accessible to a non-scientific readership (24). In recent years, students were asked to write about the contents of either “Anthropogenic influences on groundwater arsenic concentrations in Bangladesh” (25) or “Arsenic levels in rice grain and assessment of daily dietary intake of arsenic from rice in arsenic contaminated regions of Bangladesh—implications to groundwater irrigation" (26). Although the classes contained some students who had been involved in the general chemistry arsenic-related research projects that started in 2004, I estimate that a further 300 chemistry students have learned about the ground-water contamination in SE Asia, and of the importance of chemical analysis in supporting research directed towards an understanding the associated geochemistry and the impact on the local populations. Instructional materials developed for the class formed the basis for a textbook in the Pearson Longman “Short Guide to Writing” series (27). Arsenic-in-theenvironment topics are featured, though not to the exclusion of other topics, when examples of particular types of writing are needed. As nearly 7,500 copies of the book have been sold (as of March 2017), it might be argued that the numbers of students aware of these topics is more than just the numbers of students taking the classes on the UMass Amherst campus.

Undergraduate Research Students pursuing a BS major in chemistry UMass Amherst are required to take a minimum of a one three-credit independent study course. In addition, students pursuing the advanced scholarship portion of the Commonwealth Honors College curriculum are required to undertake a two-semester, six-credit culminating experience that is modeled (at least in the STEM disciplines) on a laboratory-based masters thesis. Thus there is currently considerable interest on the part of students in “getting into a lab.” So although there is no shortage of interest in my research by such students, I have found that the introduction to the relevant issues through the course-based research experience described above has been an effective way of recruiting undergraduate students into my research group. I was also for a few years, a participant in a program run by the Dean of the College of Natural Sciences in which well qualified applicants to UMass were enticed to accept the offer by the promise of a place in a faculty lab in their very first semester. Eventually this program grew to accommodate about 50 students and was taken over and modified by the Provost’s office (broadened to included all disciplines, for example). In total, 89 UMass undergraduate students have worked in my research lab, many for multiple semesters. In addition, supplements to NSF research grants and an Alliance for Graduate Education and the Professoriate, a major NSF initiative aimed at increasing participation in STEM graduate programs by under represented minorities (known as the NE Alliance (28) funded about 16 participants in REUs (research experiences for undergraduates) in my group, almost all of whom worked on arsenic-related topics. Not all of these 89 students worked directly on an arsenic-related project, but as the relevant environmental and analytical chemistry topics have been a major component of my work since 93

about 1993, all students would have been aware of the problems through the regular weekly group meetings, and of course, the informal contacts in the lab. Again, in the last two years, projects have been closely linked to the Chemists Without Borders arsenic measurement projects (the low cost arsenic-in-water test and the arsenic-in-rice measurement). Our results so far are described in another Chapter in this book, and, because of the rather amazing coincidence of having a student from Bangladesh work on the rice measurement project, featured in a short video and press release by the UMass Office of Media Relations (29). Graduate Student Research Since arsenic-related topics became a major, though by no means the only, research theme that formed the basis of dissertation or thesis work, about 31 doctoral and 7 masters students have completed their studies in my group. Even those students whose work was not arsenic-related were not only exposed to the work of other students (who were engaged in an arsenic project), but also acted as mentors for other participants in the various programs described above. The major roles for all graduate students was (a) in the course-based undergraduate research experience and (b) mentoring undergraduates in semester-long independent study or summer REU-type experiences. In addition, some students were involved in the GK-12 project and some in the Research Academies for Young Scientists. Seven of these former students are now working as chemical educators in high schools or colleges, mostly in the USA (one is in SE Asia and one in Africa). Public Engagement and Outreach I first used the title “How Much Arsenic Do We Eat?” in December 2011 for a public lecture demonstration sponsored by the American Chemical Society. This was my first attempt at getting members of the public involved as “citizen scientists” in the arsenic-in-rice project. At the time, the method we had developed (for the ITEST) program was able to detect inorganic arsenic in rice if it was present at a concentration of greater than, say, 200 parts per billion (ppb), and so (as much of the rice in people’s kitchens has concentrations below this value), many of the 20 or so participants failed to detect any arsenic. Refining this method has been an on-going research topic in my group, and has challenged a number of undergraduate students. The boundary conditions of only using reagents and equipment that one would encounter in the average kitchen make this a difficult method to develop. I have talked to general audiences about the arsenic in rice situation several times since then (at the Hitchcock Center, to students and parents at the Science Quest events at UMass, and to Girl Scouts at the Geek is Glam event at WPI). I was selected (along with this topic) to be a member of the first cohort of UMass Public Engagement Fellows, and during the tenure of my fellowship I wrote an article for a general readership that was published by The Conversation (30). According to the statistics available at the website, this article has been read almost 51,500 times. On a somewhat less upbeat note, a proposal to NSF joint with the Museum of Science, Boston for funds to run an “advancing informal science learning” project based on the arsenic-in-rice theme was not reviewed favorably. 94

The same goes for at least one regular single-investigator proposal to the NSF’s Chemical Measurement in Imaging program. Since fall of 2014, I have been helping Chemists Without Borders (CWB) with two of their arsenic-in-Bangladesh projects (31). The most recent of these, the development of a method for inorganic arsenic in rice that can be implemented in a basic lab by interns at the Asian University for Women in Chittagong, has become the focus of much attention. The University featured the work in a recent press release and associated video (29), and my CWB colleagues have convinced me of the urgency of the work and so several undergraduates have been involved since the spring of 2016. Some of the restrictions of our kitchen method can be relaxed, and so the task would appear to be a little less daunting. The SCIX annual conference, organized by the Federation of Analytical Chemistry and Spectroscopy Societies, has for the past several years organized a session on “analytical chemists easing world poverty and/or solving global health challenges.” The Fall 2016 SCIX conference will be the second time I have spoken about our work with CWB.

Concluding Remarks On eight occasions during the regular semester (and another four occasions during the summer) I have taught CHEM III, the first semester of the year-long general chemistry course. The total number of students is probably around 2000. Although I have tried to enliven my classes with material drawn from my own research, the opportunities are somewhat limited (especially when all of the “classical” analytical chemistry is taught via the associated laboratory component), and I have typically confined my self to pointing out that there are some really important practical applications of atomic spectroscopy, such as measuring low concentrations of potential harmful elements in food and drink. So while there is potential to reach large numbers of students in such classes (UMass teaches CHEM III to some 2000+ students each year), the vast majority take the class because it is a requirement for their major and, conversations with students reveal that often they are not putting the mamimum effort into their learning—just enough to get a grade that will allow progress in their major. I think such students are less invested in becoming genuinely engaged with the material than they are when they take an elective course. Thus I think the physical science general education courses for non-science majors have the potential for greatest impact on students as they progress to becoming the citizens of tomorrow.

Acknowledgments The various projects on the UMass Amherst Campus have been supported by funding from the following NSF grants: DGE-0139272, CHE-0316181, DRL103115. Professor Tyson was awarded a National Science Foundation Discovery Corps Senior Fellowship (CHE-0725257) in 2007, which allowed him to travel to several countries in SE Asia, including Bangladesh. Funding from the Camille and Henry Dreyfus Foundation and the US Geological Survey for the development of 95

undergraduate research projects is also gratefully acknowledged. The American Chemical Society is thanked for the sponsorship of a public lecture-demonstration “How much arsenic do we eat?” in December 2011.

References 1. 2. 3. 4. 5. 6. 7.

8. 9.

10.

11.

12. 13. 14. 15.

16. 17. 18. 19.

Ravenscroft, P. R.; Banner, H.; Richards, K. Arsenic Pollution: A Global Synthesis; Wiley Blackwell: Chichester, 2009; pp 588. Arsenic Contamination of Groundwater: Mechanism, Analysis and Remediation; Ahuja, S. Ed.; Wiley: Hoboken, NJ, 2008; pp 387. Meharg, A. A.; Zhao, F.-J. Arsenic & Rice; Springer: Dordrecht, 2012; pp 171. Flanagan, S. V.; Johnston, R. B.; Zheng, Y. Bull. W. H. O. 2012, 90, 839–846. Meharg, A A.; Raab, A. Environ. Sci. Technol. 2010, 44, 4395–4399. Schmidt, C. W. Env. Health Perspec. 2015, 123, A17–A19. US Food and Drug Administration proposes limit for inorganic arsenic in infant rice cereal. https://www.fda.gov/NewsEvents/Newsroom/ PressAnnouncements/ucm493740.htm (accessed April 4, 2017). Kuh, G. D. High-Impact Educational Practices: What Are They, Who Has Access to Them and Why They Matter; AAC&U: Washington, DC, 2008. Brownell, J. E.; Swaner, L. E. Five High-Impact Practices: Research On Learning Outcomes, Completion and Quality; AAC&U: Washington; DC, 2010. The American Association of Colleges and Universities. https://www.aacu.org/sites/default/files/files/ FINALFORPUBLICATIONRELEASEONSOLIDGROUND.pdf (accessed April 1, 2017). Special report of the Graduate Council and the Research Council concerning policy statement on joint authorship at the university of Massachusetts Amherst. http://www.umass.edu/senate/sites/ default/files/Policy%20Statement%20on%20Joint%20AuthorshipSen.%20Doc.%20No.%2006-040A_0.pdf (accessed March 30, 2017). Griffiths, J. Credit where credit’s due. The Analytical Scientist 2017 February, 17–18. STEM Education Institute, University of Massachusetts, Amherst http://umassk12.net/stem/ (accessed April 1, 2017). National Science Foundation. http://www.nsf.gov/pubs/2005/nsf0540/ nsf0540.jsp (accessed April 2015). Research Academies for Young Scientists, http://umassk12.net/rays/ (accessed April 2015). Feldman, A.; Pirog, K. J. Sci. Educ. Technol. 2011, 20, 494–507. Feldman, A.; Pirog, K. J. Sci. Educ. Technol. 2011, 20, 494–507. Kearns, J. K.; Tyson, J. F. Anal. Methods 2012, 4, 1693–1698. Arsenic in Your Food: Our Findings Show a Real Need for Federal Standards for This Toxin. Consumer Reports, November 2012. Francesconi, K. A. Analyst 2007, 132, 17–20. 96

20. Zavala, Y. J.; Gerads, R.; Gurleyuk, H.; Duxbury, J. M. Env. Sci. Technol. 2008, 42, 3861–3866. 21. Gilbert-Diamond, D.; Cottingham, K. L.; Gruber, J. F.; Punshon, T.; Sayarath, V.; Gandolfi, A. J.; Baker, E. R.; Jackson, B. P.; Folt, C. L.; Karagas, M. R. Proc. Natl. Acad. Sci. U. S. A. 2011, 108, 20656–20660. 22. Raber, G.; Stock, N.; Hanel, P.; Murko, M.; Navratilova, J.; Francesconi, K. A. Food Chem. 2012, 134, 524–532. 23. De la Calle, M. B.; Emteborg, H.; Linsinger, T. P. J.; Montoro, R.; Sloth, J. J.; Rubio, R.; Baxter, M. J.; Feldmann, J.; Vermaercke, P.; Raber, G. TrAC, Trends Anal. Chem. 2011, 30, 641–651. 24. Chatterjee, A.; Das, D.; Mandal, B. K.; Chowdhury, T. R.; Samanta, G.; Chakraborti, D. Analyst 1995, 120, 643–650. 25. Neumann, R. B.; Ashfaque, K. N.; Badruzzaman, A. B. M.; Ashraf Ali, M.; Shoemaker, J. K.; Harvey, C. F. Nat. Geosci. 2010, 3, 46–52. 26. Rahman, M. M.; Owens, G.; Naidu, R. Environ. Geochem. Health. 2009, 31, 179–187. 27. Davis, H. B.; Tyson, J. F.; Pechenik, J. A. A Short Guide to Writing about Chemistry; Longman: New York, 2010. 28. North East Alliance for Graduate Education and the Professoriate. http:// www.neagep.org/ (accessed April 2015). 29. UMass News and Media Relations. http://www.umass.edu/newsoffice/ article/measuring-arsenic-bangladesh%E2%80%99s-rice-crops (accessed March 30, 2017). 30. Tyson, J. https://theconversation.com/are-we-eating-too-much-arsenic-weneed-better-tests-to-know-40732 (accessed April 4, 2017). 31. Chemists Without Borders. http://www.chemistswithoutborders.org/ (accessed April 2, 2017).

97

Chapter 7

Lessons from the Field: Humanitarian Work in Latin America Nathan D. Leigh* Department of Chemistry, Missouri University of Science and Technology, Rolla, Missouri 65409-0010, United States *E-mail: [email protected].

The author is a relative newcomer to Chemists Without Borders but not to humanitarian efforts in Latin America, working most recently as a mentor to student members of a large engineering-centric humanitarian organization. This chapter is not a description of research but rather the author’s reflections on his experiences living and working in Latin America, specifically with regard to humanitarian work. Although the focus is on the western hemisphere, much of what is observed and the advice proffered are applicable worldwide. Opinions and suggestions given herein are those of the author, and not necessarily of Chemists Without Borders nor the American Chemical Society.

Fortunately for chemists, not all humanitarian work happens away from the laboratory, and the vision of Chemists Without Borders (1) embraces a plethora of laboratory-based opportunities to better the human condition. There is, however, some work which must take place in the field, and the more unfamiliar the field, the more daunting it may be to step into it. In this chapter I share some of the lessons I’ve learned from fieldwork in Latin America in hopes that it will be that much easier for the reader to take their work to where it is needed.

© 2017 American Chemical Society

Introduction The casual observer might be forgiven for thinking of Latin America (2) as a vast region of poverty, punctuated by archaeological attractions, tourist bars, and sunny beaches full of vacationers. It does seem that most of what enters the public consciousness about Latin America doesn’t stray far from the wonders of Chichen Itza and Machu Picchu and vacation hotspots like Cancún, Mazatlán, and Rio de Janeiro (3). The reality is much more complicated (and Latin America much more expansive) than the general public may readily remember. Between the US-Mexico border in the north and Tierra del Fuego in the south, today’s traveler will find modern airports, well-paved roads, high-rise buildings and familiar fast food in most major cities. However, farther from the capitols, commercial centers, and tourist towns, the affluence abates and the reality is much closer to the historical stereotype (4). Opportunities for improvement in the standard of living abound; many humanitarian organizations are engaged in this work, but there is much more to be done than can be accomplished by those presently working on it. In this chapter I will discuss some of the challenges and needs of Latin America, some general cautions for working there, and some of the lessons learned that hopefully will be of help to others planning to work there. This is not intended to be an all-inclusive instruction manual, particularly with respect to things like culture and etiquette (which are largely omitted here and can/should be studied elsewhere), nor will the advice given here necessarily apply to all projects.

Challenges and Needs in Latin America Before discussing some of the humanitarian needs, it should be observed that one thing the people of Latin America generally have in abundance is happiness. Newcomers to the region, visiting from areas of greater wealth and higher standards of living, are often astounded at the levels of happiness enjoyed by people who have so little and who live under such relatively difficult circumstances. According to the 2017 World Happiness Report, most Latin American countries are among the top one-third of the nations of the world with regard to happiness (5); in nearly all of Latin America happiness is increasing (6). The same report finds that some wealthier countries are not as happy as those in Latin America, while most similarly-impoverished nations are significantly less happy. A discussion of the reasons behind this apparent contradiction could be voluminous; by way of explanation I will simply point to an oft-uttered Spanish phrase: “como Dios quiera”, which is to say “as God wishes”. This is spoken not in a fatalistic or resigned fashion, but rather as an acceptance of their lot in life, and is accompanied by gratitude for what they do have. It appears that this outlook, widespread among the lower socioeconomic strata of Latin America, is a protective against affluenza (7) and the unhappiness it produces. Moving on from that, humanitarian needs in Latin America are much like needs throughout the rest of the world and are mentioned here in no particular order. 100

Poverty Of the challenges Latin America shares with other areas of the world, first and foremost is poverty – not necessarily universal, but widespread. In most Latin American nations, one-fourth to one-third of the population lives below the poverty line; in Chile and Uruguay poverty is less common (approaching the US rate of about 15%) but in the Dominican Republic, Bolivia, Guatemala, and Honduras the situation is significantly worse (8). Rural areas are more impoverished, with nearly two-thirds of the rural population living in poverty (9). Those accustomed to a higher standard of living may think that money is the answer, and too often money has been the proffered solution. Tossing strings-free money at poverty is akin to someone winning a big lottery prize (about 70% of such winners go bankrupt within a few years) (10); the two-part remedy of microfinance and education is promising (11, 12). Clean Water On one visit to Bolivia years ago, I traveled by bus on a mountain road between the cities of Sucre and Potosí. The empty, arid landscape is periodically broken by small homesteads eked out of the hillsides or occupying what little flat ground can be found in that area. Those living in such places are utterly “off-grid” and by and large practice subsistence farming. As I contemplated what modern marvels they might wish to have, and which would be of the most benefit, I concluded that foremost would be access to an adequate supply of clean water. The World Health Organization’s Joint Monitoring Program defines an improved water source as “one that, by the nature of its construction and when properly used, adequately protects the source from outside contamination, particularly faecal matter”. Improved sources include water piped to a residence, plot, or community tap; protected springs and dug wells; bored wells; and rainwater collection. Unimproved sources include surface waters, unprotected springs and dug wells, tanker truck deliveries, and bottled water (13). According to their statistics, most urban Latin American households receive water from an “improved source” (14), such as a community or residential tap, but typically half or more of the water sent into the distribution system is lost due to leaky pipes (15). Rural households are much more likely to receive water from an unimproved supply or non-piped sources. Despite improvements to water supplies, concerns still exist regarding the safety of the water provided, with an “improved source” not necessarily guaranteeing safe drinking water. Water quality varies dramatically from country to country and sometimes from city to city, with microbiological issues being the most common hazard. Other pollutants are possible, with heavy metals contamination a risk in some areas due to mining or improper hazardous waste disposal and natural sources posing problems in other areas (16, 17). Facile and inexpensive testing of water quality (mineral and microbiological) would help with avoidance of bad water regardless of the source, and filtration and purification methods that could be easily implemented even in resource-poor areas would permit use of otherwise unsafe drinking water. Technologies for 101

small-scale as well as community/municipal reuse and recycling of water would benefit areas with limited and/or expensive supplies as well as potentially being useful to improve existing supplies of poor quality. (Given the looming freshwater crisis here in the United States, such technologies might well be employed domestically as well as in developing areas abroad.) Sanitary Facilities Expansion of improved water supplies has also brought into focus the inadequacy of sanitary systems in much of Latin America. Access to improved sanitation (which can range from “simple but protected pit latrines to flush toilets with a sewerage connection”) has improved steadily over the past decade (18) – but as with water supplies, rural areas lag behind urban areas in the presence and sufficiency of their sanitary systems, and increased water usage can overburden sanitary systems with insufficient design capacity. Improved sanitation has health and environmental benefits not just on the “input” end but also on the downstream side, where significant country-to-country variations exist in the extent of sewage treatment (19). Rural areas may benefit from sewage treatment alternatives such as biodigestors, which can potentially convert wastes into fertilizer and fuel (20–22). Housing In Cochabamba, Bolivia I met a family of four living in a lean-to shelter beside the basketball coliseum; they felt fortunate to have a plastic tarp for their roof. In contrast, the family of five in El Alto, Bolivia (23) that lived in a 130 square foot home with unplastered adobe walls and a tin roof (beneath which shone a single, bare light bulb) was comparatively well-off (24). Statistics published by the Inter-American Development Bank indicate that vast swathes of Latin Americans are either homeless or live in poor-quality housing; Costa Rica and Chile fare better (18% and 23% respectively) while Bolivia and Nicaragua (75% and 78%) have the highest percentage of their population housed inadequately (25). The problem is particularly bad in urban areas (which hold four-fifths of the region’s populace) where urban planning is inadequate or absent, congestion is both chronic and acute, and danger due to crime and health risks is high (26). A variety of governmental and private sector efforts attempt to solve the housing shortage but are hampered by lack of funding (27), lack of suitable land, and inadequate infrastructure in places where building is undertaken (28). Transportation and Communication Only once in my adult life have I traveled in a motor vehicle and desperately wondered, “Are we there yet?” We journeyed by truck from La Paz, Bolivia to a small community in the Yungas, and were fortunate to take the “new” road and not the fabled “Death Road”. The trip of about 170 miles (with a net vertical drop of 2 miles, which we may have done several times) took 12 nail-biting hours, part 102

of that in the dark (which, when it fell, mercifully cloaked the steep drop-offs common along that road). Bolivia has fewer miles of roadway per square mile of area than most of Africa, and only a tenth of those roads are paved (29). The rest of Latin America does somewhat better, and Bolivia itself is improving – 140 miles of highway between La Paz and Oruro were recently improved to become the country’s first divided highway (30). With so many of the opportunities for humanitarian work being located in rural areas, the condition (or even existence) of roadways must figure into your plans, not forgetting how weather may impact their passability. Rain will not only muddy or flood the roads but may wash them out entirely; in hilly or mountainous areas, be mindful of the risk of landslides or rockfall (31). Cell phone penetration (loosely defined as the number of cell subscribers divided by the population) in Latin America is quite complete; like most of the rest of the world, it seems that nearly everyone has a cell phone (32). However, cell towers are not ubiquitous, being concentrated near areas with a sufficient subscriber base; thus, don’t count on cell service while traveling on rural roads between populated areas (33).

Some General Cautions Some cautionary material is found in the “Challenges and Needs” section above; here are some additional items that should be taken into account for those planning and carrying out work abroad. Materials Availability It is no surprise that many of the materials that we are accustomed to finding in the hardware store or delivered next-day by an online vendor cannot be found or had in less developed areas. Often, comparable products with which we are unfamiliar are available, and you should be prepared to substitute locally-available materials for whatever you might have planned. This is actually a great opportunity for learning: from time to time, inexperienced students working on project designs will specify a material or fabricated item that is common in the US but unavailable abroad, and the consideration of substitutes fosters innovation in the spirit of “necessity is the mother of invention”. Some things can be found as imports, but at a price point that strays into ludicrous territory; I remember one store where toothpaste imported from the US could be purchased at about 10 times the price as the South American version of the same product. Personal care products are a relatively trivial example; more to the point for chemists, starting materials, solvents, equipment and instrumentation just might not be available (34). A colleague at a semi-rural university campus in Costa Rica once asked for some titanium dioxide, explaining that it was very difficult to obtain chemicals and reagents due to high costs and excessive paperwork. Due to availability and affordability, that same colleague worked with welding gases instead of high purity reagent gases (which is a marvelous “make do” approach as well as a lead-in to the next point). 103

Different Standards and Expectations The standards and expectations in your work country may be dramatically different than what you expect. Countries lacking the same regulatory infrastructure may have what we might view as relatively lax standards with regard to construction techniques, materials quality, testing rigor, etc. Seek ways of adjusting your expectations without sacrificing important and critical aspects of your work (e.g., safety, quality, durability). Hopefully you will be able to laugh at things like pipe with a nominal diameter measured in inches and a length in meters! The mingling of metric with what are considered traditional units in the US will crop up elsewhere (including the kitchen); even though you probably won’t be trying to land a probe on Mars, don’t let confusion over units doom your project (35). Another facet of standards and expectations is the trap of thinking that humanitarian aid means making their lives look like ours. For example, in the US we build our buildings so as to make them nearly airtight; I’ve enjoyed the places I’ve stayed within 20° latitude of the equator that allowed at least some free exchange of air with the outside. We can’t do that in locations where the climate is too cold, and there are ramifications to allowing that air to flow. Sometimes and under some circumstances the differences are consequential, but sometimes they are merely a matter of preference or custom. Government as Impediment Some governments think it best to protect their citizens by tying them up in red tape. A colleague in Central America explained that the government of his country relied on the bureaucracy of paper to reduce corruption. While the prescribed paperwork has reduced the amount of bribery, one can still wonder what other, less impedimentary means might be employed to bring about that desired end. Because governments tend to have monopolies on the services that they provide, the customer service normally expected of a competitive enterprise may be lacking. Civil servants often have no incentive to deal with out-of-the-ordinary requests and formalities that may arise in the course of a project spearheaded by foreign aid workers. Your in-country partner (see below) will probably handle most of the necessary interactions with government officials (other than “meet and greet” sessions and photo opportunities), but be aware that obstacles may arise and solutions may not be rapid. Envy of Neighboring Communities My post-doctoral mentor sagely asserted, “If you don’t ask, you don’t get.” Those who ask and get may be envied by those who failed to ask (or didn’t know they could ask). A Bolivian community requested help improving the water collection and distribution system which they had implemented as private citizens; they worked through an NGO and were delighted to be selected for assistance. When outside help arrived, the community became the target of 104

envy of the neighboring municipality (of which they were a subdivision). This became problematic when legal paperwork required for improvement of their water system had to be approved by a government official residing in the envious area. Calm and careful discussion led by our in-country partner helped defuse the situation. (Stares and scowls from the community that thought itself slighted turned to smiles as we explained the process to anyone who would listen; it helped that we bought ice cream and soft drinks from their shops.)

Some Things I Have Learned The following suggestions are based on my own experiences and are not meant to be an exhaustive list of hints and tips. Although these lessons are based on my experiences in Latin America, most of them will probably apply to any unfamiliar place in which you wish to work.

Importance of a Capable In-Country Partner Ships traveling the Mississippi River from the Gulf of Mexico to New Orleans and Baton Rouge engage the services of a river pilot to help them navigate the difficult waters. The river pilot, expert in his stretch of river, knows the shifting sandbars, fickle currents, and the local winds; understands when to turn a large ship so as to avoid grounding and what speed to travel to prevent damage to docked ships; and how to use the winds, currents, and tugboats to move or stop the big ship as needed. Any time you work in a foreign place, work with someone who can be your “river pilot” - someone who knows the particulars of the location, how to get things done, and how to get help when needed. Ideally, your in-country partner will be able to help with the following: •

•

•

•

Language translation – even if your team speaks the language, your partner should know the local slang and subtle nuances and should be able to talk you through and out of difficult situations; this is especially important if working in an area where multiple languages are prevalent. Avoiding faux pas – your partner organization should be able to act as your cultural attaché, advising you on things you should (and should not) do. Transportation – rely on your in-country partner to get you from place to place, whether by arranging public transportation, private carrier, or by driving you themselves; in many places, the pitfalls of short-term foreign visitors driving are sufficiently numerous as to make it foolhardy to drive yourself. Best times to travel – get advice from your partner organization in order to avoid the rainy season, holidays, strikes and upheavals, or other times that might interfere with your mission. 105

•

•

•

•

•

•

Supplies – whether you need building materials, equipment and tools, books, medicines, food, chemicals, etc., your partner should either know where to acquire needed supplies or where to seek help finding them. People/connections – your in-country partner should have a network of contacts that you can tap for services, advice, and needed expertise that you didn’t bring with you. Government – whether it be legal paperwork required for a project or a courtesy call to help things go smoothly, your partner should know the people to meet, how to find and access them, and the protocols to follow when interfacing with government functionaries. Visas and permits – you can’t always trust a consular website to give you correct information, but your partner organization should be able to convey up-to-date details (and insider tips) on things like visas (36). Any permits needed for work to be done are best handled by them as well. Paying for things – a good in-country partner will have a mechanism to receive payments from your organization and make disbursements on your behalf as they arrange your visit. They probably can get better pricing on lodging, transportation, supplies, etc., than you could by making arrangements yourself; they should also know the best currency exchanges. Phones and other communication – you’ll need to be able to communicate during your travels and your personal cell phone may not be of any use in your target location; you partner organization should be able to either provide cell (and/or satellite) phones or help you buy and set up a suitable phone. For some projects, a team will rely on radios (“walkie-talkies”) for short-range communication; radio communications are governed by national laws and international agreements, and you should check with your partner organization to be sure you do not violate the rules regarding use of radios.

In addition to these capabilities, look for a partner organization that is wellestablished and stable. One of our projects in Central America nearly failed when the NGO with whom we worked went defunct. Learn the Language, Connect with the People Having a partner organization that can provide translation is invaluable, but being able to speak the language yourself takes things to a whole new level; until you speak the language, you will always be an outsider, even if you are appreciated and loved by the people you endeavor to serve. Not everyone in the group needs to learn the language – even if just one member of the group can communicate effectively with the local population, it links the whole group to the people. I first traveled to Costa Rica with a couple of fantastic colleagues who spoke no Spanish and whose English was accented. We were making presentations at a host university where the audience’s level of English language comprehension covered a spectrum from “very little” to “a fair bit”, with whispered translations provided by those with better comprehension. 106

My colleagues presented first and were accepted politely; I spoke next and as I began in Spanish, a young man at the back of the room gasped audibly, and everyone relaxed and listened. At the end the atmosphere had changed and we were no longer just the visitors from elsewhere but colleagues with whom the locals could work. (I relate this not to boast but to illustrate – and to be fair, common language only takes you so far, as evidenced on the same trip by the colleague who had an incredible knowledge of agriculture which he used to great effect in making friends and developing relationships in spite of the difficulties of communicating in a mutually non-native language.) The information age has brought with it additional options for studying a new language. No longer limited to formal classroom instruction or an immersion program requiring foreign residence, the aspiring student has options including free (37) and fee-based on-line (38) as well as off-line (39) courses (40). Note that these are geared toward conversational and business language; acquisition of technical vocabulary beyond cognates (41) is a more difficult proposition. Learning the local language will not only enable better communication and connections with the people where you work, but will also permit a better appreciation of their culture and thinking. Whether or not you speak the language, you can learn about the food, music, weather, and local customs. Of particular importance are holidays – so much so that you should learn about this before traveling. (For example, you might wish to avoid Brazil during Carnaval (42); you might not be able to purchase needed supplies in Paraguay on May 15th, their Independence Day.) Be prepared for surprises as you might not be able to learn about all the local holidays in advance. In Bolivia, local holidays seemed to be all over the calendar, and parades complete with brass bands and marchers from the local schools are frequent (43). Shed Attitudes of Superiority Early in my career, my job required me to work with a broad variety of solvents in a laboratory setting; my wife could always tell when I’d been working in the lab as she could smell it on my breath and clothing. The stench of supposed superiority is no less detectable on the person of someone who believes himself or herself to be working with or for an inferior group of people. This is not meant to be an accusation but rather a caution and an opportunity to examine motives and perspectives. Working abroad with people of different backgrounds can break down stereotypes and preconceived notions, but the traveler must be willing to accept that he or she individually (and, by extension, his or her culture and heritage) holds no monopoly on goodness, on valuable ideas and habits, or on the best way to do things. Just as a visiting scientist will acquire new and important skills and knowledge from a host lab, as visitors to places where we go to share our skills and expertise we return changed by the things we learn while away. Allow yourself the opportunity to improve by keeping the door open to learning from people who are poor or less educated; at a minimum, they can probably teach you something about happiness (as discussed above). 107

Look for Synergistic Opportunities One of the fundamental principles of the UNIX computer operating system is that a program should do one thing, and do it well; this has contributed to the longevity of the operating system (44). On the other hand, our financial advisors tell us to have a diversified portfolio. Personally and professionally we are probably somewhere in between, with broad shallow capabilities and narrow areas of deep expertise. While we can outsource tasks outside our core expertise, the transaction costs may not be worth it – for example, learning how to glue PVC pipe isn’t difficult and doesn’t require the skills (and expense) of a plumber. However, constructing a community-wide water distribution system using PVC pipe requires a more specialized skill set and greater experience, and designing that system requires yet another set of skills and expertise not common among chemists. The trend toward increased interdisciplinary research (and the possibilities it affords) suggests a similar need in fieldwork. An organization that understands its own strengths and weaknesses and is willing and able to partner with another organization having complementary abilities will be able to accomplish more than the organization that attempts to do everything on its own. Unfortunate bureaucratic barriers often prevent such collaborations; seek ways to transcend those barriers and multiply your efforts by partnering with other experts. For example, chemistry expertise in water quality testing and water purification could be partnered with the engineering expertise of organizations like Engineers for a Sustainable World or Engineers Without Borders who are often engaged in water supply projects. There are large numbers of humanitarian organizations with whom you might partner; the challenge is first to find one with complementary interests, and then to overcome the institutional barriers that would otherwise hinder or prevent cooperative efforts. Plan for Sustainability In the context of humanitarian work, sustainability means that the beneficiaries of aid will be able to manage and maintain the deliverables. For example, if a composting toilet is built for community use, the members of the community need to be instructed not only in how to use it but also how to maintain it, what supplies are needed for its replenishment and where to obtain them, and how the compost must be handled in order for it to be safe for use. Such instruction is conveyed not only verbally and by demonstration, but also in the form of an “operations and maintenance manual” (O&M) that provides sufficient information – in an easily understandable form – for users to be able to undertake the needed operational and maintenance tasks. Ideally an O&M would have plenty of pictures, each of which (if well done) will save a thousand words of misinterpretable explanation (45). Sustainability involves not just the ability of aid recipients to maintain improvements but also their willingness to do so. That willingness can be manifested in what they do to better their own condition prior to asking for help: the community that organized a water committee, instituted a funding mechanism, 108

built their own water collection and distribution system, and then went through the formal process of requesting assistance from an NGO will probably take good care of the improved water system built for them. The engineering organization with which I work also requires that the community being served make a token financial contribution to the cost of project materials; we also like to have as much “sweat equity” as possible (46). Guard Your Health One of the first principles of emergency response is to protect yourself, because an injured responder is unable to help others; this also holds true for those traveling abroad in humanitarian efforts. Water tends to be the biggest issue – avoiding tap water will lead to dehydration if sufficient bottled water is not available, and those who gamble with dubious tap water invariably fall ill. (Remember, if it’s not clean enough to drink, it’s not clean enough to use for brushing teeth!) At high elevations it is easy to get sunburned, so sunscreen and a hat are de rigeur; at lower elevations, insects may present a greater hazard, necessitating insect repellent and netting (47). Know the typical hazards of all the places you expect to be, and all the activities in which you will engage, and have a written plan for dealing with them with one or more members of your party prepared to deal with such exigencies (48). Although you hopefully will never need it, you should always have some form of international travel insurance with provisions for medical evacuation. Write Things Down, Take Plenty of Pictures As scientists, we are conditioned to write things down in our laboratory notebooks. That conditioning should extend to fieldwork and associated travels – failure to properly record something the first time may mean a trip of thousands of miles to try to recapture the needed information. Write down not just measurements and observations but also names of places and people, phone numbers and addresses, implementation ideas and possible impediments. When you are out of your familiar surroundings, the plethora of unusual stimuli will make it harder to remember fleeting thoughts, so write things down. We advise the students with whom we travel to keep a journal of their experiences, to write a little something every day about what they’ve accomplished, what has happened to them, the people with whom they’ve worked, and how they feel about the work in which they are engaged. Write about the positive things, but don’t neglect the bad things – your journal should be a place where you can be completely honest in your expression, and eventually you’ll be able to laugh about the negative things that you recorded. The journals I’ve kept have helped to keep the experiences fresh for me and keep the details of stories straight. Good pictures encapsulate a great deal of information and can be used for project documentation as well as serving the usual tourist-type purposes. Pictures of people you meet are useful for helping you remember their faces so that you can greet them properly the next time you are face-to-face. One sometimes forgotten 109

purpose of good pictures is public relations (PR), and time spent learning how to compose good photos for PR purposes is well invested. Bring Small Gifts It is likely that gratitude for your efforts on behalf of others will be expressed in the form of some small token of appreciation (and maybe even a party near the end of your visit) (49). It is good form to have some small gifts to give as well – nothing expensive, but something that shows you were thinking ahead. Check with your in-country partner for suggestions (50). Another nice touch is to bring some candy to give to children (51); they are the ones who will benefit most from the work you do and can teach you words, games, songs, and a thing or two about happiness as a way of life. I recommend candies that are not individually wrapped, unless you want to follow kids around and pick up their discarded candy wrappers (52). If you find yourself bereft of ideas for things to take, choose some non-perishable food items that you enjoy and take enough to share. The novelty of it may be fun for those with whom you share, and if nothing else you’ll have some comfort food to carry you through difficult moments (53).

Last, but Not Least... Humanitarian work – wherever conducted – is a rewarding and life-changing experience. Don’t hesitate to tell others (54) what you’re doing; share pictures and stories, not to boast or induce guilt but rather to illustrate how it has impacted you positively. Invite your listeners to be part of your efforts – there is plenty of work to go around, and no matter what your expertise there is somewhere and some way that you can contribute.

Biography Nathan D. Leigh holds a PhD in Analytical Chemistry from the University of Missouri – Columbia and is currently Assistant Director of Research at the Missouri University of Science and Technology. He lived in Bolivia for two years (half that time above 13,000 feet elevation, and always above 8300 feet) and has traveled elsewhere in South and Central America. In his travels he enjoys meeting people, eating local food, joking with children and contributing to the improvement of their quality of life. He eagerly anticipates his next trip.

References and Notes 1.

To wit: “a global support network of volunteers providing mentoring, information and advice to ensure every person, everywhere, has affordable, consistent and persistent access to: essential medicines and vaccines; sufficient safe water; a sustainable energy supply; education in green chemistry and business which people can apply in their daily lives and 110

teach to others; safe processes in work environments where chemical hazards exist; emergency support, including essential supplies and technology”. See Chemists Without Borders - Mission and Vision, www.chemistswithoutborders.org/index.php/about/mission-and-vision. 2. While Latin America technically is much more encompassing, I will limit my discussion to those countries where Spanish and Portuguese are the principal languages. With all apologies to the other countries of South and Central America and the Caribbean, whose needs I do not mean to minimize: it is just that I do not know you yet, but I do hope to some day visit you and experience your wonders too. 3. Lamentably, much-ignored Ecuador seems best-known for having Wikileaks founder Julian Assange as a long-term couch-surfing asylum seeker at their London embassy. Ecuador should be known for, among other things, its wonderful biological and geographical diversity, its well-preserved historical sites, the Quito-Guayaquil train, and of course the Galapagos Islands. 4. A wealth gradient from the urban areas to the countryside is in no way surprising as the same is generally observed in the United States, where we are likewise not immune to urban decay and crises (of which the recent contaminated drinking water debacle in Flint, Michigan, is prima facie evidence). 5. The World Happiness Report (worldhappiness.report/ed/2017/) has been prepared annually since 2012 by independent experts acting under the auspices of the United Nations’ Sustainable Development Solutions Network. 6. A notable exception to this upward trend is Venezuela, where happiness decreased more than anywhere else in the world. Sadly, the current problems in Venezuela appear to be largely preventable, but a discussion of the causes and solutions is quite beyond the scope of this volume. 7. “Affluenza” is a portmanteau of the words “affluence” and “influenza”, and is defined as “a painful, contagious, socially transmitted condition of overload, debt, anxiety, and waste resulting from the dogged pursuit of more” in the book Affluenza: The All-Consuming Epidemic by de Graaf, J., Wann, D., Naylor, T. H. Berrett-Koehler: Oakland, 2001. 8. Based on Statistics in the CIA World Factbook. www.cia.gov/library/ publications/the-world-factbook/fields/2046.html. 9. Statistics from Strategy for Rural Poverty Reduction in Latin America and the Caribbean. International Fund for Agricultural Development. www.ifad.org/ where/region/resource/tags/pl/1962687. 10. Chan, M. Here’s How Winning the Lottery Makes You Miserable. Time, 2016 (Jan 12). time.com/4176128/powerball-jackpot-lottery-winners/. 11. Maldonado, J. H. The Influence of Microfinance on the Education Decisions of Rural Households: Evidence from Bolivia, 2005. Microfinance Gateway. www.microfinancegateway.org/sites/default/files/mfg-en-paper-theinfluence-of-microfinance-on-the-education-decisions-of-rural-householdsevidence-from-bolivia-aug-2005_0.pdf. 12. Hadi, R.; Wahyudin, U.; Ardiwinata, J. S.; Abdu, W. J. SpringerPlus 2015, 4, 244. 111

13. WHO/UNICEF Joint Monitoring Program for Water Supply and Sanitation. www.wssinfo.org/definitions-methods/watsan-categories/. 14. World Health Organization, Monitoring and Evidence – Water. www.who.int/water_sanitation_health/monitoring/water.pdf. 15. Barlow, M.; Clarke, T. The Struggle for Latin America’s Water. NACLA Report on the Americas. nacla.org/article/struggle-latin-americas-water. 16. Arsenic, for example, is increasingly recognized as a problem; see McClintock, T. R.; et al. Sci. Total Environ. 2012, 429, 76–91. 17. See also Bundschuh, J.et al. Natural Arsenic in Groundwaters of Latin America; CRC Press: Boca Raton, 2008. 18. Improved Sanitation Facilities in Latin America and Caribbean. Trading Economics. tradingeconomics.com/latin-america-and-caribbean/improvedsanitation-facilities-percent-of-population-with-access-wb-data.html. 19. Rodriguez, D. J. Investing in wastewater in Latin America can pay off. The World Bank Water Blog, 2017 (10 May). blogs.worldbank.org/water/howcan-we-make-wastewater-investments-sustainable-latin-america. 20. For more information, see Garwood, A. Network for Biodigesters in Latin America and the Caribbean: Case Studies and Future Recommendations. Inter-American Development Bank, 2010 (December). publications.iadb.org/handle/11319/4848. 21. See also Biodigesters to Improve Milk Production in Bolivia.. Hivos, 2014 (27 Oct). latin-america.hivos.org/news/biodigesters-improve-milkproduction-bolivia. 22. Garfi, M.; Martí-Herrero, J.; Garwood, A.; Ferrer, I. Renewable Sustainable Energy Rev. 2016, 60, 599–614. 23. “El Alto” is the city on the Altiplano (“high plain”) about 1600 feet above the city of La Paz. 24. In contrast with this, I have been in upper-middle class Bolivian homes that were gorgeous - but the tap water still wasn’t safe. 25. “Inadequate housing” in this report included not only structural deficiencies but also lack of utilities. Brief details are available in Development in the Americas: Housing. Inter-American Development Bank. www.iadb.org/en/ research-and-data/dia-housing,6586.html?slideID=5. 26. City Limits. The Economist, 2011 (Aug 13). www.economist.com/node/ 21525915. 27. It is estimated that it would cost $300 billion to solve the issue of inadequate housing in Latin America; see Development in the Americas, 2012. InterAmerican Development Bank. www.iadb.org/en/research-and-data/diadevelopment-in-the-americas-idb-flagship-publication,3185.html?id=2012. 28. In one instance, the local branch of an international aid organization built a housing development on undeveloped land prone to flooding; they did bring in electrical service. Improved drainage and a community water system were implemented later by a different organization and at great expense and effort, but for sanitary facilities each residence either has a pit toilet or must install its own space-restricted septic system. 29. Road data is from the CIA World Factbook, www.cia.gov/library/ publications/the-world-factbook/fields/2046.html. Although Bolivia’s roads 112

30. 31.

32.

33.

34.

35.

36.

37.

38.

are largely substandard, the city of La Paz has a very modern teleférico or tram system. For a modest fare, riders can travel from the lower reaches of the city all the way to the Altiplano, avoiding traffic and enjoying a spectacular view of the city. Seeing adobe homes and dirt streets below while gliding quietly along in a clean and modern tram car does illustrate the socioeconomic dichotomy that exists. Most of the cost of the improvements was paid for by a $250 million loan from the Development Bank of Latin AmericaCAF. Mountainous and hilly terrain features prominently in nearly all Latin American countries. The chance of being hit by falling rocks is fortunately lower than the chance of suddenly finding them on the road ahead; not all will be as large as the truck-sized slab we once found standing in the middle of the road just outside the city of Potosí, Bolivia. Pertinent statistics can be found in the CIA World Factbook, www.cia.gov/ library/publications/the-world-factbook/fields/2046.html. Cuba is the outlier with only 22% cellphone penetration; the Dominican Republic has the next lowest rate at 78%. While cell service wasn’t always available, on an upscale cross-country trip in Costa Rica the shuttle van featured satellite internet service, interrupted only when we passed through tunnels or briefly while circumnavigating steep mountains. A recent article in C&E News addresses these issues with respect to Cuban universities; see Widener, A. Improving Prospects for Chemists in Cuba. C&E News, 2017 (24 April), 34−40. cen.acs.org/articles/95/i17/Improvingprospects-chemists-Cuba.html. The Mars Climate Orbiter, launched in 1998, famously disintegrated upon orbital insertion due to a mismatch in units between two pieces of software; see Mars Climate Orbiter – Mars Exploration Program. mars.nasa.gov/ programmissions/missions/past/climorb/. Trips to Bolivia, for example, could be disastrous without knowing that a visa must be purchased and paid for with crisp $20 bills. (Due to concerns over forged currency, the immigration workers are quite particular about the bills they will accept.) Duolingo is a very popular free, on-line language learning tool, although their materials are crowd-sourced in whole or in part and the consensus may be swayed by regional variations. I tried it for Spanish review and grew frustrated when it would not accept answers that I knew to be correct; thus, it may be better for acquisition of a new language rather than review of one you already have. As of this writing they offer 23 languages, including English, and their website is available in 23 languages, but they are not the same 23 languages. www.duolingo.com. Many people think of Rosetta Stone as the archetypal personal language study course, perhaps due to the influence of airline in-flight magazines. Their reputation is quite good, and in keeping up with the times they’ve moved from a CD-only business to an on-line model. As of this writing they offer instruction in 30 languages, including both “American” and “British” English. www.rosettastone.com. 113

39. If you don’t wish to be tied to your computer, highly-regarded Pimsleur may be the right option as their lessons are provided in mp3 format. They offer instruction in 50 languages (9 of those being regional variants, e.g., Brazilian vs European Portuguese), plus English as a Second Language for students from 14 different language backgrounds. www.pimsleur.com. 40. I have no pecuniary nor other interest in the previously mentioned language learning businesses. Other options are easily found using your favorite online search engine, and the best one is the one that works for you. 41. Speakers of Romance languages may be the ones to benefit most from cognates (words that are the same or very similar in two different languages). There are caveats, however – one famous example is the Spanish word embarazada, which does not translate to “embarrassed” but rather “pregnant”. 42. Carnaval is actually celebrated throughout Latin America to various extents and in various ways. In Oruro, Bolivia the parade can last all day (and the participants tend to dress in warmer clothing); throughout the country, Carnaval is also a time to play with water using squirt guns, water balloons, buckets, etc. This is ironic in regions where water is often a scarce resource. 43. I’ve never quite figured out the holiday in Potosí, Bolivia on which they decorate their dogs with colored paper polka dots...but I imagine that our Groundhog Day has them baffled in exchange. 44. From its “birth” in 1969, UNIX has endured nearly half a century and looks poised to continue for a long time to come. See The UNIX® Evolution: An Innovative History. The Open Group. blog.opengroup.org/2016/02/23/theunix-evolution-an-innovative-history. 45. Insufficient education, coupled with a misunderstanding of the community’s wants and needs, led to this frustrating but instructive outcome: for water purification, a community had been given biosand filters built in plastic barrels; a year later, most of the recipients had emptied out the barrels and were using them for rainwater collection. With better up-front information gathering, additional empty barrels could easily have been provided; better explanation of the benefits of the biosand filters could have helped community members understand their value. 46. Don’t underestimate the value of that sweat equity! A travel team has limited time to carry out their work plans and the contributed labor of community members is often the only way to get everything done. Before accepting a project, we survey the community members and ask about their skills in order to gauge their ability to help with various aspects of the project. The locals can show you how things are done the local way and probably will get it done faster than you would. Everyone can help dig ditches; I witnessed a middle-aged woman with a baby strapped to her back shoveling vigorously because she was so excited by the prospect of having running water at her home. 47. DEET is my go-to standard repellent, but use what works for you. Also, I highly recommend treating your clothing with permethrin as it should kill the insects that are undeterred by the repellent. Insect netting pretreated with permethrin is available; this makes it less likely that a mosquito will bite you 114

48.

49.

50.

51.

52.

53.

54.

through the net while you sleep. Depending on where you travel, antimalarial medication may be appropriate (ask your health care provider). Our travel teams always include two or more people with a current Wilderness First Aid certification, and the teams discuss and train for the kinds of incidents that could arise during the course of travel and work. We always carry a first aid kit with supplies appropriate to the expected hazards, and individual team members are encouraged to have personal first aid kits with things they are likely to need (adhesive bandages and loperamide tablets get used more than anything else). Major milestones and project completion are logical times for parties to be organized, which may feature food, speeches, music, dancing, and so forth as an expression of community gratitude. Appreciation for your in-country partner should not be neglected; it would be polite to offer to bring them something. One person with whom we work always enjoys a bag of a particular snack food for which he developed a fondness while living in the US. Taking candy from strangers isn’t stigmatized in developing countries like it is in the US, and offering candy to kids can melt their reticence to interact. (For the sake of propriety and safety, of course, don’t be alone with the children; even an accusation of impropriety could lead to a highly unpleasant judicial experience.) Sadly, proper disposal of rubbish is still a cultural problem in much of Latin America; I was dismayed to see one of our hired cooks throwing garbage out the window as we traveled. While it would not solve the underlying problem, the development and adoption of biodegradable wrappers would mitigate the symptoms. When your gastrointestinal tract is in turmoil and you are laid low, nibbling on that comfort food may mean the difference between having enough fun to want to travel again and being so miserable that you’ll never go back. Our students typically go on summer internships, and we encourage them to seek opportunities to share their humanitarian efforts with their summer colleagues (who have never failed to be impressed). On such occasions they are not to solicit contributions, but invariably those in a position to help offer to do so.

115

Chapter 8

Distributed Pharmaceutical Analysis Laboratory (DPAL): Citizen Scientists Tackle a Global Problem Sarah L. Bliese, Margaret Berta, Nicholas M. Myers, and Marya Lieberman* Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, United States *E-mail: [email protected].

The Distributed Pharmaceutical Analysis Laboratory (DPAL) leverages the chemical testing capacity at academic institutions to determine analytically the quality of medicines collected from low- and middle-income countries (LMICs). ACS-accredited degrees in chemistry require an analytical chemistry course, which often includes the use of high performance liquid chromatography (HPLC) to identify and quantify organic substances. DPAL provides an opportunity for instructors to teach about HPLC with an additional goal of finding low quality medicines in LMICs. Participation in DPAL demands a high level of accountability and responsibility from students and instructors. Participants must demonstrate system suitability of analytical instrumentation, follow standard operating procedures, determine if medicines are compliant with regulatory specifications, keep intelligible records that can be shared with other DPAL participants or with regulatory agencies, and co-author reports to health authorities when low quality medicines are discovered. DPAL can provide unique opportunities for students in the lab to witness their diligence in scientific research trigger regulatory investigations in other countries. Ultimately, the partnership of academic institutions in DPAL generates more data about compliance breaches in medicine quality, and could allow regulatory authorities in LMICs to intervene, thereby protecting public health.

© 2017 American Chemical Society

Substandard and falsified pharmaceuticals are a world-wide problem, with the largest impact in low- and middle income countries. According to recent published findings, at least 30% of pharmaceuticals being sold in many low and moderate income (LMIC) countries of Africa, Asia, and Latin American are substandard or falsified (1). A comprehensive literature review (2) provides a nuanced picture of how heterogeneous the quality of medicines is, and how sparse the published work on this important topic. Substandard pharmaceuticals can cause drug resistance, increased mortality and morbidity, and lead to a loss of confidence in the healthcare system (3). Other concerns arise from pharmaceuticals that have been adulterated with substitute active pharmaceutical ingredients (APIs) (4) or hazardous materials such as brake fluid (5). Detection of low quality pharmaceuticals is a challenging task. Martino et al. provide a review of a wide spectrum of analysis methods--from field screening tests to sophisticated mass spectrometry and NMR experiments--that have been applied to widely-counterfeited artemisinin antimalarials (6). However, pharmacopeia assays for most dosage forms rely on high performance liquid chromatography (HPLC). The capital and operating costs associated with these analytical instruments make them a scarce resource for low- and middle-income countries. An HPLC can cost tens of thousands of dollars not including the cost of purified solvents, analytical grade balances and glassware, columns, and pharmaceutical standards that are necessary for analysis. Additionally, complex business and technological infrastructure--consistent power, a clean laboratory environment, reliable transportation of supplies, availability of trained operators as well as technicians and resources for maintenance and repairs, and proof of a high level of training and documentation--are required for sustainable operation. All of these factors make it difficult for pharmaceutical analysis to take place in low resource settings. In response to the lack of access to analytical capacity in LMICs, new approaches for surveillance of post-market pharmaceuticals are being tried (7). Chapter 9 in this Symposium Series by S. Pastakia et al. describes a risk-based screening method developed by a group of pharmacists in Kenya. This screening program is the main source of pharmaceuticals for the DPAL project described in this chapter. Briefly, covert shoppers collect samples of pharmaceuticals from small medicine shops in cities and towns across Western Kenya (Figure 1a). The samples are brought to Moi Teaching and Referral Hospital (MTRH), where the sample metadata (brand, expiration date, lot number) are transcribed onto a spreadsheet. Figure 1b shows how the samples are stored after they have arrived at the University of Notre Dame. Table 1 lists the pharmaceuticals collected in 2016. One crushed pill from each sample is analyzed with a paper analytical device (PAD) to detect falsified products (8). As shown in Figure 2, a sample of the pill is applied to the paper and twelve chemical tests are simultaneously run to generate colors that reflect the chemical composition of the pill’s active ingredients and excipients. These colors result in a unique “color barcode” that allows for identification of different pharmaceuticals. The images of the PADs are uploaded to a Dropbox site where human readers and computer image analysis programs can determine the test outcomes. If the sample does not have the expected barcode, 118

then it is flagged as suspicious and moved higher in the queue for chemical assay. In addition, a portion of the samples are selected randomly for assay in order to detect substandard products, which are not directly detected by the PAD analysis. The University of Notre Dame serves as the clearinghouse for the Distributed Pharmaceutical Analysis Lab (DPAL). Samples are shipped to Notre Dame for analysis about once every 3-4 months from MTRH. Table 1 summarizes the number and types of samples collected within a typical year. A comprehensive sample intake protocol is conducted once the samples arrive. All samples are assigned a unique Notre Dame identification number (NDID), which is used for internal sample reporting for DPAL. Sample metadata regarding manufacturing and location of purchase is recorded in a separate spreadsheet, but is not included in the information available to DPAL participants. During sample intake, a brief physical examination of each sample is conducted to identify packaging issues that could lead to product degradation, or which indicate sloppy manufacturing. Any sample exhibiting one of the following criteria is recorded: incomplete seal of blister packs, packaging printing errors (Figure 3a), and tablets or capsules that have no stamped or printed identifiers on the pill, or have poor quality markings (Figure 3b).

Figure 1. a) Sampling locations in 2016. b) DPAL samples ready for storage after intake. All samples are stored individually in zip-top bags which are grouped by active pharmaceutical ingredient (API) type in sealed plastic boxes. After sample intake, samples are stored in a 2°C refrigerator until they are sent for analysis. Samples are shipped to participant institutions upon request; they are packed with an inventory and a cover letter indicating their research purpose. The Distributed Pharmaceutical Analysis Lab started in 2014 and involves participants from 20 institutions (Figure 4a and 4b). Four have access to DPAL for data analysis projects and 16 participants are in some phase of chemical analysis for the Distributed Pharmaceutical Laboratory project. Four of these institutions are analyzing samples, and nine are conducting system suitability experiments that are required before sample testing can occur. DPAL continues to increase its analytical testing capacity as new institutions are added and current participants complete system suitability tests. 119

Table 1. Pharmaceuticals Collected in 2016. The pharmaceuticals collected are antibiotics, anti-malarial or anti-tuberculosis drugs. Pharmaceutical

Number of Samples

Acetaminophen

120

Albendazole

90

Amoxicillin

146

Amoxicillin-Clavulanate

88

Ampicillin

72

Anti-Tuberculosis Drugs

30

Azithromycin

101

Ceftriaxone

80

Cefuroxime

80

Cephalexin

49

Ciprofloxacin

80

Doxycycline

82

Enalapril

80

Levofloxacin

82

Losartan

45

Metformin

80

Figure 2. PAD Schematic. The powdered sample is wiped across the twelve lanes (left image) and then the bottom edge of the PAD is placed in water (center image). The water wicks up the lanes in 3 minutes, dissolving reagents stored in the twelve lanes so they can react with the sample. These reactions form a color barcode (right image) characteristic of the functional groups and materials in the sample. Other features are printed on the test card to assist in computer image analysis of the color barcode. 120

Figure 3. a) Poor quality stamping on amoxycillin capsule. b) Amoxycillin-clavulanic acid tablets with name of one of the APIs mis-spelled on the package.

Figure 4. DPAL participants a) International Participant Map. Map data: Google. b) US Participant Map. Map data: Google. DPAL has participants from the following institutions: Andrews University, AstraZeneca, California State University Fullerton, Calvin College, Coe College, DePauw University, Ghent University, Grand View University, Hamline University, Juanita College, Kean College, Liverpool School of Tropical Medicine, Moi Teaching and Referral Hospital Eldoret Kenya, Niagara College, Saint Mary’s College, St. Edward’s University, Skidmore College, University of California Santa Barbara, University of Notre Dame, and University of San Diego. Participant institutions must have the basic instrumentation required for pharmaceutical analysis. At a minimum, participants must have access to a properly calibrated analytical balance, a high-performance liquid chromatograph with ultraviolet or photodiode array detector, software for collecting and analyzing their chromatograms, and an apparatus for degassing HPLC solvents. Additional instrumentation that is required for select methodologies is a pH meter, a refrigerator for sample storage, a -80°C freezer for preserving sample solutions, and a sonicator. Generally, Chemistry departments whose analytical laboratories offer some kind of HPLC experiment are already are equipped with the required instruments. The cost of analytical standards (secondary standards calibrated vs. USP or BP primary standards) and HPLC solvents is comparable to the cost of supplies for other undergraduate HPLC experiments, so the DPAL experiments fit into existing budgets for undergraduate analytical or instrumental analysis courses. In cases where participants needed to purchase a new HPLC column, either funding has been obtained through the home institution, or in some cases the DPAL program provided a donated column. 121

To join the Distributed Pharmaceutical Analysis Lab, the participants must first join the DPAL Open Science Framework (OSF) project (9). The OSF site is the primary means of communication and collaboration with participant institutions. It provides access to the HPLC Methodology Manual, a continuously updated document which defines the operating procedures for carrying out pharmaceutical assays, and also provides a set of checklists and Excel spreadsheets for recording analytical results and keeping track of experiments. The OSF site allows a project to contain multiple “components” which are sub-sections of the whole project. In DPAL, each participant school has its own component site which contains their institution’s analytical information and data. Each contributor is given “read-only” access to the DPAL program site, and “read and write” access to his or her institution’s component. This allows individuals to download and review files posted to the DPAL main page. The individual who is leading analysis at the participant institution (professor or principal investigator) may grant read and write access for their institution’s site to other individuals involved in the DPAL analysis at their discretion. By accepting the invitation to the DPAL OSF site, participant researchers must agree to adhere to DPAL policies regarding data security, integrity and publishing. All contributors can upload and edit files in their own institution’s site, where their raw data and documents are stored. Final HPLC results are posted to the DPAL main site through a Google Forms interface, so no participants are able to edit the final data from another institution. This helps to protect the integrity of the project data. This set-up creates a community of institutions that are committed to a common goal. Participants are encouraged to review one another’s data and results to learn from one another. This group proof-reading encourages members to maintain high quality analysis that is imperative for reliable reporting. Publishing features of OSF provide additional data security, in addition to creating citable references for DPAL data. The registration function in OSF creates a frozen version of the entire project that can never be edited or deleted--essentially, a snapshot of the project. Registration does not change the project itself, and new data can continue to be added and edited. The archived registered versions help to ensure data security. Additionally, registered versions can be issued a Digital Object Identifier (DOI) which creates a citable entity for the project, allowing researchers to reference specific versions of the project in presentations and publications. The entire DPAL project is registered quarterly, and participants can create individual registrations for their institution’s site whenever necessary. DPAL is not a certified pharmaceutical analysis laboratory; participants perform single-tablet API assays and do not conduct full compendial testing on pharmaceutical products. The data generated by DPAL cannot be used in a legal context to conclude that a medicine is of good quality. The main goal of the project is to report suspicious samples to regulatory agencies that ARE equipped to perform compendial testing. In order to provide reliable and transparent information, DPAL requires that each participant adhere to detailed standard operating procedures (SOPs) so that uniform techniques, procedures and calculations are employed at all institutions and the materials, raw data and calculations can be traced back and checked for error. Many measures in the 122

SOP are derived from “WHO Good Practices for Pharmaceutical Quality Control Laboratories (10),” “WHO Guidelines for Preparing a Laboratory Information File (11)” and Good Clinical, Laboratory and Manufacturing Practices: Techniques for the QA Professional (12). In addition to addressing procedural protocols, the HPLC Methodology Manual explicitly states the expectations for quality and data security. The motivations and global context for protocols are explained to emphasize the importance of adherence. Legal considerations of pharmaceutical analysis are discussed to ensure that all participants fully understand how to correctly report and present DPAL results. The analytical standard operating procedures defined in the HPLC Methodology Manual include System Suitability Requirements, analytical metrics (13), sample storage and tracking, sample preparation, column storage, conditioning and washing, and sample assay and quality control procedures. After choosing an analyte and an assay based on USP or BP methodology, the DPAL participant must demonstrate system suitability through a series of specific tests based on standards laid out in USP and USP . These tests determine whether the methodology employed and the HPLC system are working properly. The results of the system suitability tests must be within acceptable limits to be considered valid. The series of system suitability experiments evaluates the precision, linearity, accuracy and range, accuracy via spike recovery, specificity, limit of detection and lower limit of quantification for the method. Participants show their results in an Excel spreadsheet to prove that they have hit the metrics for each of these experiments. The DPAL program requires that all participants successfully complete all system suitability requirement experiments and submit the data and results for review before samples from LMICs are sent for analysis. Once the system suitability experiments have been completed, the lab does not need to perform the tests again for that analyte unless the operating parameters change significantly (for example, switching to a new brand of column, or moving the assay to a different HPLC instrument). System suitability experiments include: •

•

The precision of a method is its ability to obtain reproducible results. It is imperative that methods used for DPAL have acceptable precision to ensure that there is minimal variation between samples during analysis. To evaluate the precision of a method, one sample at 100% of the expected concentration is injected six consecutive times. The relative standard deviation of the integrated intensity for each run is calculated, and must be less than 2% to be accepted (14). There is not a precision requirement between samples but before each day’s first batch of unknowns, five injections of an external standard are made to check precision, and this calibration standard is rechecked every five samples to be sure the integration stays within the 2% RSD limit. If this calibration check fails, the five preceeding samples must be re-run. Linearity describes how well a calibration curve generated by the method follows a straight line. It is important that the linearity is properly demonstrated since sample analysis calculations require a calibration 123

•

•

•

•

•

curve to determine the amount of API. To meet the DPAL requirements for system suitability, the y intercept must fall within the error of zero, and the R2 value should be greater than 0.98. The sample concentration should be within this linear range for analysis. The accuracy and range experiment proves that the optimized method is accurate for various sample concentrations. It is important to ensure accuracy of the method is not compromised at higher or lower concentrations which could be encountered during sample analysis. To evaluate the accuracy and range, four solutions are prepared: an overdosed sample with ~150% of the standard sample, a normal sample that is ~100% of the standard, a deficient sample that is ~35% of the normal standard sample and a blank which contains no API. The overdosed, normal, deficient, and blank samples are run in triplicate. The measured concentrations of the samples should be within 2% of their true concentration. Accuracy via spike recovery is an additional means of testing the accuracy of the optimized methodology. For this experiment, a pharmaceutical dosage form of the analyte (supplied by DPAL) is required to make the standard solution. One sample solution is prepared with an additional 30% spike of API standard. The spike is determined by comparing the sample assay to the spiked sample assay, and the percent recovery of the spike is recorded. An acceptable spike recovery is between 90-110% of the spike. This metric also has some capacity to evaluate intermediate precision because there are three independent sample preparations at each level. The specificity of the method can be demonstrated by a good spike recovery from a "dirty" matrix, such as one that contains degradation products of the API. An old sample may be used as the matrix, or one that has been thermally or chemically degraded. The samples should be run according to the spike-recovery method to calculate percent recovery. The retention times for degradation products and their resolution from the API peak should be recorded for this experiment. The retention times for this test and others should be within 0.5 minutes between runs. The limit of detection (LOD) is calculated to determine the smallest quantity detectable that is significantly different from zero. The experiment is conducted via the slope-standard deviation method (13), with the standard deviation generated by running six samples, at concentrations 2-3 times the expected LOD as estimated from the linearity plot. The system suitability requirements also include a control chart which is a record of operation (15). The control chart includes information about the peak shape, retention time, resolution and integrated intensity. This document is not only used as a record of activity for each day, but functions as a diagnostic reference when issues arise (16). In general, if a peak retention time varies by more than 30 seconds or the chromatogram fails the peak asymmetry or resolution metrics listed in the SOP, it is a sign that something is amiss with the system. 124

After the participant institution meets the system suitability requirements, assays are performed to test pharmaceutical samples from LMICs countries. Due to the small number of tablets or capsules in each sample, the assays do not follow the normal compendial procedure, which requires pooling 20-50 pills. Instead, only one tablet or capsule is taken for analysis. For each assay, the mass of the pill or tablet and the stated API content are recorded and used as the reference for determining the total amount of active pharmaceutical ingredient in the sample. If the pill does not meet Pharmacopeia specifications (generally 90-110% of stated API content) then two additional pills are assayed. Samples that are found to be substandard or low quality are sent back to the University of Notre Dame for additional testing, and the student data (Figure 5) are included in reports to country regulatory agencies and the WHO RapidAlert program. The poor quality of the product in the top trace in Figure 5 was confirmed by analysis of pills from other packages with the same lot number. This product constituted 37% of the pool of amoxicillin-clavulanate collected in Western Kenya by our Kenyan partners in 2014-2015. The drug regulatory agency in Kenya confirmed our findings by independent lab analysis of packages of this product obtained in Nairobi. In consultation with regulators at the Pharmacy and Poisons Board of Kenya, a packaging problem was identified and brought to the attention of the manufacturer. Subsequent samples of this product have been of good quality. This outcome demonstrates that detection of a poor-quality product can lead to improving the quality of medicines without reducing access.

Figure 5. HPLC data from analysis of (bottom trace) amoxycillin and clavulanate standards, (middle trace) a good quality amoxicillin-clavulanic acid pill, and (top trace) a poor-quality amoxicillin-clavulanic acid pill. 125

The analytical requirements for the Distributed Pharmaceutical Analysis Lab make it a versatile student project. The system suitability components of the DPAL program are challenging experiments that can serve as independent research or senior thesis projects. Alternatively, demonstration of system suitability can be done as a tag-team project in an analytical chemistry or instrumental analysis lab, in which individual students perform a share of the 40-45 necessary injections over the course of several weeks; this is a good option when only one HPLC is available. After completion of the method validation experiments, sample assays can be performed as part of a standard analytical chemistry laboratory experiment, as an undergraduate research project, or even as a chemistry club service project. Due to the multi-stage nature of DPAL, the program can easily be adapted to fit many different academic settings. The utility of the DPAL program is limited by logistic factors. Participants must carry out a time-consuming system suitability test, request samples for analysis, and upload data swiftly. The DPAL program coordinators must give feedback on the uploaded results, get samples in the mail promptly, and follow up on assay results. In our experience, these steps take 1-2 semesters. Some samples pass their expiration dates during this timeframe, which means that assay results will have much less impact on manufacturers and regulators. Dissemination of standard operating procedures and data upload and feedback through Open Science Framework has helped to speed up the steps, and we are working with OSF to develop additional tools such as video FAQ sessions, automated emails, and social media links for training, tracking and motivating participants. Although pharmaceutical analysis is a mature area of analytical chemistry, the instrumentation needed to check the quality of medicines is costly and difficult to keep running, so poor quality pharmaceuticals are a persistent and widespread problem in many LMICs countries. The Distributed Pharmaceutical Analysis Laboratory (DPAL) engages colleges and universities that maintain HPLC instruments for analytical lab courses to conduct assays of medicines from LMICs countries. The analytical tasks for DPAL participants are designed to fit into the scope and structure of instrumental analysis and analytical chemistry lab courses, and can also be carried out in the framework of undergraduate research. In order to assure that the results are reliable, each DPAL participant must demonstrate system suitability before analyzing samples. The transparency of the DPAL results is maintained by posting raw data, calculations, and results for all participants to view on Open Science Framework. Citizen scientists have already had an impact on medical care in Kenya by discovering poor quality antibiotics and reporting them to the national drug regulatory agency.

126

References 1. 2. 3. 4.

5. 6. 7.

8. 9. 10. 11. 12.

13. 14. 15. 16.

Almuzaini, T.; Choonara, I.; Sammons, H. BMJ Open 2013, 3, e002923DOI:10.1136/bmjopen-2013- 002923. Kelesidis, T.; Falagas, M. E. Clin. Microbiol. Rev. 2015, 28, 443–464. Newton, P.; Green, M.; Fernandez, F. Trends in Phamacol Sci. 2010, 31, 99–101. WHO Medical Product Alert No. 4/2015 Adverse reactions caused by Falsified Diazepam in Central Africa; 2 July 2015; Ref. RHT/SAV/MD/4/ 2015. Polgreen, L. New York Times. http://www.nytimes.com/2009/02/07/world/ africa/07nigeria.html (accessed 2 April 2017). Martino, R.; Malet-Martino, M.; Gilard, V.; Balayssac, S. Anal. Bioanal. Chem. 2010, 398, 77–92. Tran, D.; Njuguna, B.; Mercer, T.; Manji, I.; Fischer, L.; Lieberman, M.; Pastakia, S. Cardiology Clinics 2017, 35, 125–134, ISSN 0733-8651, DOI:10.1016/j.ccl.2016.08.008. Weaver, A.; Lieberman, M. Am. J. Trop. Med. Hyg. 2015, 14-0384. Published online April 20, 2015; DOI:10.4269/ajtmh.14-0384. Archived version of DPAL project as of 4/4/2017; DOI: 10.17605/OSF.IO/ TR9Y7. WHO. Good Practices for Pharmaceutical Quality Control Laboratories. World Health Organization WHO 2010, 957, 81–129. WHO. WHO Guidelines for Preparing a Laboratory Information. World Health Organization File. 2011, 961, 403–408. Anderson, A.; Maxwell, J.; Hill, H. In Application of GLP in Analytical Chemistry with Cross Reference to GMP and GCP; Carson, P., Dent, N., Eds.; Good Clinical, Laboratory and Manufacturing Practices: Techniques for the QA Professional; 2007; pp 279−303. Harris, D. Quantitative Chemical Analysis; W.H. Freeman and Company: New York, 2007; Vol. 7, pp 86. U. S. Pharmacopeia. https://hmc.usp.org/sites/default/files/documents/ HMC/GCs-Pdfs/GC_pdf_USP38/c1225.pdf (accessed 5/27/2017). Harris, D. Quantitative Chemical Analysis; W. H. Freeman and Company: New York, 2007; Vol. 7, pp 663. Schazmann, B.; Regan, F.; Ross, M.; Diamond, D.; Paull, B. J. Chem. Educ. 2009 September, 86 (9), 1085–1090.

127

Chapter 9

Addressing the 3A’s (Availability, Accountability, Adherence) of Supply Chain Systems in Western Kenya Rakhi Karwa,1,2 Dan N. Tran,1,2 Mercy Maina,3 Benson Njuguna,3 Imran Manji,3 Paul Wasike,2 Edith Tonui,3 Gabriel Kigen,2,3 and Sonak D. Pastakia*,1,2 1Purdue University College of Pharmacy, West Lafayette, Indiana, 47907, United States 2Moi University, School of Medicine, Department of Pharmacology, Eldoret, Kenya 3Moi Teaching and Referral Hospital, Eldoret, Kenya *E-mail: [email protected].

The right to access essential medicines and medical technologies is crucial to attain the highest-quality health care for all citizens of the world. Unfortunately, in many low- and middle-income countries (LMICs) around the world, patients’ ability to access quality essential medicines still remains a critical challenge. Barriers that impact the quality of essential medicines from chronic communicable and chronic non-communicable diseases lie within three specific areas (3A’s): availability, accountability, and adherence. First, unnecessarily complex supply chain management, poor operational procedures, and inadequate financing for health lead to low availability of medicines. Second, corruption contributes to falsified and substandard medicines and low accountability of the supply chain to the patients who rely on it. Lastly, poor patient adherence to medicines is affected by low health literacy, lack of communication between providers and patients, and social stigma of diseases. Based on our on-the-ground experiences working in western Kenya, we propose solutions that target each of these challenges to improve access and quality of medicines.

© 2017 American Chemical Society

Through this chapter, we hope to compel chemists to apply and focus their efforts to create transformative chemical techniques with the potential to significantly improve quality of medicines, to improve patient outcomes, and to alter the delivery of care to patients all over the world.

Introduction Access to quality healthcare services has long been recognized as a human right. In 1948, the World Health Organization (WHO) Constitution stated: “The enjoyment of the highest attainable standard of health is one of the fundamental rights of every human being without distinction of race, religion, political belief, economic or social condition (1).” As a result, the right to access essential medicines and medical technologies must also be recognized as a crucial part of attaining the highest-quality healthcare for all citizens of the world. Indeed, one of the United Nations’ Sustainable Development Goals (SDG) to transform our world identified the importance of achieving access to quality, safe, effective, and affordable essential medicines in SDG 3 by the year of 2030. Unfortunately, in many low- and middle-income countries (LMICs) around the world, patients’ ability to access quality essential medicines still remains a critical challenge. This challenge of access is further complicated by the penetration of low-quality medicines in LMIC healthcare systems and has become a significant public health problem, leading to drug resistance, inadequate treatment, and increased global morbidity and mortality (2). Past efforts to improve access to quality medicines have focused primarily on regulation and policy with the aim of strengthening healthcare systems and improving the supply chain for essential medicines. More importantly, technological innovations, including those in the field of applied chemistry, have also contributed to the expansion of access to quality medicines. The concept of transforming chemistry knowledge and bringing chemical analysis out of the laboratory settings and into the real world has begun to get healthcare providers more enthusiastic about scalable, implementable, and affordable new technologies that can impact patient lives all over the world. The need for new technologies and interventions must involve a deep understanding of the supply system in which these technologies aim to address. Consequently, in this book chapter, we aim to provide a practical example of the supply chain system primarily within which we have been working in for the past two decades through the Academic Model Providing Access To Healthcare (AMPATH) in western Kenya. AMPATH has established themselves as pioneers in service delivery as they have leveraged their unique academic model supported by Moi University, Moi Teaching Referral Hospital, and a consortium of North American Universities to provide care services to a population of over 4 million people living in western Kenya. Through our team’s experiences working within the AMPATH program, we propose that the barriers that impact the quality of essential medicines from chronic communicable and chronic non- communicable diseases lie within three specific areas (3A’s): availability, accountability, and 130

adherence as illustrated in Figure 1. In this chapter, we further describe solutions that have been implemented to address the barriers each of the identified areas.

Figure 1. Barriers to the 3A’s of supply chain systems in Kenya.

Availability Problem Statement Well-functioning supply chain systems for medicines must be consistently reliable and responsive to the priority health care needs of the patient populations that they serve. Ideally, at any health service delivery point, patients should be able to access all necessary medicines in a reliable, affordable and high-quality manner. In 1977, the WHO published its first Model List of Essential Drugs in which it identified 208 medicines deemed to provide safe and effective treatment for communicable as well as non-communicable diseases worldwide. Since then, the Essential Medicines List (EML) has continued to evolve to include more than 300 medicines (3). The EML is meant to serve as a guide for the procurement and 131

supply of medicines in the public sector, medicine reimbursement, donations, and local drug production (4). Despite this effort, in 1999, the WHO still showed that a large fraction of the world’s population still had poor access to appropriate, affordable, and high-quality essential medicines, with the limitations being especially pronounced in remote, rural areas where many resource constrained populations reside (5). In the public sector, the median availability of essential medicines was reported to be 40%, much lower when compared to 78.1% in the private sector (6). In many LMICs, stock-outs of essential medicines are common occurrences in public health facilities. The WHO and Health Action International also reported that the availability of essential generic medicines in low-income countries as being at an average of 36.1% in the public sector, with countries in Africa having a mean availability of 29.4% in public health facilities (7). The availability of medicines for chronic conditions in LMICs is even less. Medicines for cardiovascular diseases, for example, have been reported to have availability as low as 3% in some settings (8). Low medicine availability makes it difficult for patients with chronic conditions to have routine access to chronic disease medicines that they are meant to take on a long-term basis and could potentially affect medication adherence as well as adherence to clinic visits. In Kenya, a survey carried out by the WHO in 2009 showed a median availability of essential medicines of only 67% in public hospitals countrywide (9). In this section, we analyze the gaps within the supply chain system from a pharmaceutical policy as well as an on-the-ground perspective. Drawing from our practical experiences in Kenya, we further describe examples of successful programs where attempts have been made to fill these gaps. Obstacles to Efficient Supply Chain Systems in Kenya and LMICs Dysfunctional Supply Chain Management In most LMICs, drug supply is coordinated by the government using Central Medical Stores (CMS), which procures and distributes medicines to public health facilities for dispensing (10). In Kenya, the CMS is known as the Kenya Medical Supplies Authority (KEMSA) and is a state corporation under the Ministry of Health (MOH) (11). Previously, KEMSA was financed by the central MOH to procure and distribute medicines across the country based on individual facility orders; however, health financing was transferred from the central government to the county governments in 2013. Currently, KEMSA supplies individual counties based on orders made by the county health ministries who pay for the subsidized costs of medicines and their distribution (10, 12). Unlike many other LMICs, KEMSA contracts with several transport companies to distribute the medicines directly to the health facility. In other countries, the government typically owns a transport fleet that distributes to regional warehouses that then transport the supplies to the individual facilities or the facilities are expected to collect their orders from the regional warehouses which is challenging when facilities have limited vehicles or limited funds for fuel or vehicle maintenances (10). This unnecessarily complex design coupled with multiple tiers of stock 132

management leads to increased opportunities for the system to break down causing interruptions in supply chain. In addition to government-coordinated procurement and distribution of essential medicines, developing countries have a large private pharmacy sector, with a number of private wholesalers and importers who regularly distribute medicines to retail outlets (13). Non-governmental and faith-based organizations also play a role in the supply of medicines in developing countries.

Inadequate Financing for Health Uncertainties and inefficiencies in health financing can lead to ineffective supply chains. The complex bureaucratic procedures and inefficiencies in the health and finance ministries of most LMICs result in long lead times before funds are even disbursed from the government treasury to procure medicines (10). In Kenya, this complexity has been further complicated by the devolved structure of government. Specifically, each of the 47 counties requests for funds from the government, which they then have to allocate to various functions other than healthcare. A specific amount from these funds are then used to purchase medicines from KEMSA. Consequently, there may be large variability in the budgetary allocation for drug procurement across the counties because each county may have differing priorities and political agendas (14). The entire procedure adds yet more inefficiency in ensuring medicines are made available in good time to various health facilities (14).

Inefficient Health Information Systems Another challenge with government-coordinated supply chains lies with the inefficient health information systems that should provide adequate data to allow for planning and forecasting of needs. Yadav describes a phenomenon known as “the bullwhip effect” in which small variations in the information communicated across the various levels of the supply chain end up being amplified, resulting in too large or too small quantities of medicines being supplied to health facilities (10). One reason for this is insufficient and weak communication across multi-tiered distribution systems. These systems use a funnel model of communication such that multiple lower tiers (i.e. primary care centers) funnel their drug orders to a middle tier (i.e. secondary care facilities), which then make orders for them to the central drug supplier. Various primary care centers have no real-time knowledge on each other’s drug stocks. One facility may be having a shortage of crucial drugs, but these drugs may be available at another facility in large quantities where they are not been consumed. This is further complicated by the fact that there are long intervals between delivering supplies to individual facilities; with the aim of reducing transport costs, most CMS distribute medicines on a quarterly basis. However, with its long lead time, it is difficult to forecast the needs leading to stock-outs or wastage (10). Furthermore, not enough data is collected at the health facility level that could provide accurate information about utilization for 133

appropriate planning and ordering. Hence, there is a disconnect between the actual need and what is supplied to the facility. Much of this stems from inadequate funding of operating costs for the supply chain including the lack of systematic investment in supply chain data management systems in the pharmaceutical sector (9, 15).

Unaffordable Drug Pricing The private pharmaceutical sector in most developing countries is a thriving one with wholesalers and distributors often having a monopoly for particular products (13). There may also be several tiers in the supply chain, with each tier adding a price mark up. Thus, prices of medicines in private pharmacies may be quite high and unaffordable to many. The analysis by Cameron et al. on prices and affordability of essential medicines in developing countries showed that private sector mark ups could range from 10% to more than 500% leading to exorbitant prices of medicines in the private sector (7). This can be attributed to poor drug pricing policies that allow private sector players to mark-up prices.

Poor Outreach to Rural Areas Another challenge with private sector supply is that it has poor reach into rural areas (10, 13). Most wholesalers distribute to cities and towns but not to densely populate villages. This then forces retailers in rural areas to find their own means of purchasing and transporting medicines from larger towns. This also has a negative impact on the price of the medicines because the additional transport cost is added to the mark up. Therefore, patients in rural areas, who are typically facing greater financial constraints to begin with, end up paying much more for essential medicines in comparison to urban residents. The resulting situation from all these barriers is that a large proportion of the population, consisting particularly of lowincome earners in rural areas, is unable to access medicines in both public health facilities, because of poor availability, and from private pharmacies because of the high costs. It is for this population that targeted innovative solutions improving access to essential medicines are needed.

Proposed Solutions In order to mitigate some of the most pressing challenges of the supply chain system, in Kenya, several efforts have been conducted to bridge the gaps within the public health sector to improve the availability of medicines for chronic communicable and non-communicable diseases. In this section, we document two successful programs in Kenya that highlight the process of implementation, evaluation, outcomes, and their significant impact on patient lives.

134

The KEMSA Case Study: The Push and Pull System As generally states above, KEMSA is the entity within the Kenyan government, which is responsible for sourcing, storing and supply of medicines and other health related products to both government hospitals and some selected non-governmental organizations. Despite facing many challenges, KEMSA has managed to supply commodities to more than 4000 health institutions in Kenya (16). Because of the lack of accurate projections of needs and poor record keeping, KEMSA relied primarily on the “push” model of distribution, where predefined amounts of medications were periodically distributed to health facilities based on somewhat arbitrary allocation rules and catchment populations (10). The push system often results in a mismatch between supply and demand leading to the wastage of many unnecessary medications and shortage of medications that have higher consumption. The difficulties with the push system coupled with increased demand for timely deliveries have led to change in policies pertaining to medicines supply within KEMSA. As a result, recently, KEMSA has utilized new approaches that aim to improve the supply chain within Kenya. One such intervention is the utilization of the pull system, which involves fulfilling orders based on the clients’ (hospitals) demands. Through the pull system, KEMSA utilizes an in-house Logistics Management Information System (LMIS) in inventory tracking and management. Facilities can also place orders via KEMSA’s, e-mobile platform. KEMSA has also incorporated Zidi™, a phone-based model that tracks stock movement in real time in addition to making estimates for reorder quantities before the next ordering cycle (16). All these interventions have led to improved pharmaceutical supply chain performance especially in the public sector leading to improved stock monitoring, reduction in quantities of expired medicines and overall reduction in overstocking of medicines (16).

HIV Drug Procurement at AMPATH AMPATH was created initially as an HIV focused care program that was established in 2001 through a partnership between Moi Teaching and Referral Hospital (MTRH), Moi University College of Health Sciences, and a consortium of North American universities and academic medical centers (17). AMPATH has a tripartite mission of care, education and research, serving a catchment population of 4 million people in western Kenya. Through close partnership and collaboration with the Kenyan MOH, AMPATH has worked closely with Kenya’s MOH, the United States Agency for International Development (USAID), and the President’s Emergency Plan for AIDS Relief (PEPFAR) to build a reliable supply chain system for antiretroviral (ARV) drugs and to provide comprehensive care and treatment for HIV-infected patients in Kenya. Many lessons can be learned from understanding the supply chain management of ARV drugs at AMPATH as a case example. With funding from USAID and PEPFAR, Kenya Pharma was established to create a reliable and uninterrupted supply chain for ARV drugs to ensure 135

HIV patients across the country could continue to derive the benefits from PEPFAR supported HIV programs (18). Since 2009, Kenya Pharma has worked in multiple cross-cutting areas to achieve these aims. Besides conducting regular quality assurance performance reviews and making sure that medicines are properly stored, the project has managed to strengthen the ARV supply chain by prioritizing these following activities: (1) quantifying antiretroviral and opportunistic infection drugs, (2) analyzing consumption patterns, (3) forecasting needs based on the most updated data, (4) procuring required pharmaceuticals, and (5) distributing medicines to all sites in a timely, efficient, and consistent manner (19). The creation of a reliable supply chain system for ARV drugs has helped ensure that patients sustain the life-saving benefits of HIV treatment. Through this program, AMPATH has been able to ensure medication access for ARV drugs and medications for AIDS-related opportunistic infections for more than 150,000 ever-enrolled HIV patients across western Kenya without any reported stock-outs at more than 500 MOH facilities across western Kenya (20). As PEPFAR/USAID continue to emphasize the importance of country owned and operated programs, PEPFAR is currently transitioning responsibility for supply chain to KEMSA. Revolving Fund Pharmacies History In 2011, revolving fund pharmacies (RFPs) were developed by AMPATH with the aim of ensuring sustainable and reliable access to quality and affordable medicines for patients with chronic diseases outside of HIV (21). The idea behind this RFP model came from the revolving drug fund (RDF) concept, which dated back to 1989 when an RDF was introduced in Ghana (22). In the RDF model, seed funding was obtained for the purpose of procuring an initial stock of essential medicines. These medicines are later sold at a slightly higher price, in order to generate sufficient profit that can be used to replenish drugs and to support administrative costs. Learning from criticism, challenges, and successes of RDF projects in various other settings, Kenya’s RFPs were set up to address the unmet needs of the public sector to consistently access essential medications (23, 24).

Guiding Principles for Setting Up RFPs RFPs are located within public health facilities, however, the operational aspects of the pharmacy are separated from that of the government pharmacies. Indeed, RFPs serve as “backup” pharmacies to the government facility, with the medicines being sold to patients only when the government pharmacies are not able to supply patients with the essential medications that they need. Revolving fund pharmacies are typically initiated in a stepwise fashion with the process starting with a thorough needs assessment of the medication availability, supply chain issues, staffing and security issues at each site. Based on collected data and documented needs, key stakeholders including the MOH 136

Facility Management team, the AMPATH RFP team, and members of the local community in which the public health facility is located, are engaged and form a management committee. As a unified team, the three parties create a memorandum of understanding that governs daily operations to ensure patient needs, patient safety, and optimal workflow. Specifically, the MOH facility management team avails RFP space and offer day to day oversight of activities, including if necessary, shifting staff members already employed by the facility to manage the RFPs to minimize cost of hiring new staff. The AMPATH RFP team is responsible for stocks management including regular audits, report generation, and drug re-supply. The local community representatives ensure that community needs are continuously met and any community concerns are allayed. The novelty in the RFP model, and why it has been functioning well in our setting, is based on several guiding principles, as summarized in Table 1. The MOH serves as the primary supplier of drugs for patients seeking care at the facility while the RFP serves as a back-up for patients in the case of MOH facility stock-outs. All prescriptions filled in the RFPs represent drugs that otherwise would have been inaccessible, of possible poor quality or unaffordable to patients. Autonomy and sustainability are of utmost importance to the RFP model. An operational procedure, distinct from the MOH’s system is put in place to ensure separation of medication stocks, records and cash, which are all under the management of the above mentioned committee. As accountability is of utmost importance to maintain the RFP implementation all RFPs are audited by a member of the AMPATH staff on a weekly basis during the first 1-2 months of operation, followed by a monthly or bi-monthly basis. This procedure facilitates not only transparency in cash collection, but also efficient and timely procurement of drugs. Most importantly, RFPs operate in an access-maximization model where patients should not be denied life-saving medications. A waiver system is established to identify patients who are unable to pay.

Outcomes Availability of essential medicines in the three initial pilot RFPs increased from 40%, 36% and