Criteria Air Pollutants and their Impact on Environmental Health [1st ed. 2019] 978-981-13-9991-6, 978-981-13-9992-3

Table of contents :
Front Matter ....Pages i-xiv
Introduction (Pallavi Saxena, Saurabh Sonwani)....Pages 1-6
Criteria Air Pollutants: Chemistry, Sources and Sinks (Pallavi Saxena, Saurabh Sonwani)....Pages 7-48
Primary Criteria Air Pollutants: Environmental Health Effects (Pallavi Saxena, Saurabh Sonwani)....Pages 49-82
Secondary Criteria Air Pollutants: Environmental Health Effects (Pallavi Saxena, Saurabh Sonwani)....Pages 83-126
Policy Regulations and Future Recommendations (Pallavi Saxena, Saurabh Sonwani)....Pages 127-157

Citation preview

Pallavi Saxena · Saurabh Sonwani

Criteria Air Pollutants and their Impact on Environmental Health

Criteria Air Pollutants and their Impact on Environmental Health

Pallavi Saxena • Saurabh Sonwani

Criteria Air Pollutants and their Impact on Environmental Health

Pallavi Saxena Department of Environmental Sciences Hindu College, University of Delhi New Delhi, Delhi, India

Saurabh Sonwani School of Environmental Sciences Jawaharlal Nehru University New Delhi, Delhi, India

ISBN 978-981-13-9991-6 ISBN 978-981-13-9992-3 https://doi.org/10.1007/978-981-13-9992-3

(eBook)

# Springer Nature Singapore Pte Ltd. 2019 This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. The publisher, the authors, and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, expressed or implied, with respect to the material contained herein or for any errors or omissions that may have been made. The publisher remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. This Springer imprint is published by the registered company Springer Nature Singapore Pte Ltd. The registered company address is: 152 Beach Road, #21-01/04 Gateway East, Singapore 189721, Singapore

Foreword

Increasing urbanization and industrialization are the basic key factors in deteriorating the air quality at a large scale. The anthropogenic factors are mainly responsible for the production of primary as well as secondary air pollutants. These substances include gases like sulphur dioxide, nitrogen oxides, carbon monoxides, hydrocarbons, etc.; particulate matter like smoke, dust, fumes, aerosols, etc.; radioactive materials; etc. The effects of air pollution on living systems like plants, animals and human beings and other materials are worse. It may affect the biochemical and physiological processes of plants and ultimately lead to yield loss. The need to check air pollution arises due to its health consequences. Numerous outdoor and indoor air pollutants affect human health and pose significant threats to individuals worldwide, such as cardiovascular or respiratory disorders, asthma and lung cancer, which can be fatal. Given that an individual inhales more than 10,000–20,000 litres of air per day, it becomes obvious that air pollutants pose significant dangers for human health. According to the World Health Organization, more than two million premature deaths each year can be attributed to the effects of urban outdoor and indoor air pollution. Hence, it is of utmost importance for an environmentalist to pay attention towards the burning issue of air pollution. This book is focused on one of the major categories of air pollutants, i.e. criteria air pollutants, and their possible impact on environmental health. This class of air pollutants mainly concern the harmful impacts on health and community. This book is written by experienced researchers in the field of atmospheric sciences and addresses various aspects of criteria air pollutants, their mechanisms, interactions, productions, impacts and possible control measures for the same. This book discusses an important issue of criteria air pollutants and their impact on environmental health as limited information is available in the literature for the same. Therefore, this book has a valuable contribution to an urgent environmental challenge facing our society and will be beneficial for graduate, postgraduate and research students and for the whole scientific community. CSIR-Central Road Research Institute (CRRI) New Delhi, India

Anuradha Shukla

v

Preface

Bad air quality is one of the key factors that affects human as well as plant health. Over a number of times, strong interrelationships have been developed between environmental health and air pollutants. Among all the classes of air pollutants, criteria air pollutants are of most concern as they pose more impact on environment than other air pollutants. A whole target species can be exposed to criteria air pollutants, which may increase during times of particular vulnerability. The correlation between criteria air pollutants and environmental health has been studied on a large scale since several years. “Losses” to human health have been depicted in economic terms, as well as in terms of years of life lost. Moreover, the benefits due to the decline in human exposure to pollution have also been examined. In this context, different assessment methodologies have also been developed and utilized for dose-response relationships for these selected pollutants. On the basis of such associations, such exposure-related research works have come into existence from the following: the identification of human exposure, the emissions derived from manmade and natural sources, the establishment of policies and the assessment of the cost of reduction of this exposure. Criteria Air Pollutants and Their Impact on Environmental Health book covers the basics of criteria air pollutants and their importance in daily lives in a more simplified way. The impacts of this pollution on environmental health receive more attention, as these are more harmful to human health in particular. It also summarizes the conditions of criteria air pollutants in developed and in developing countries. On the basis of discussion of a number of issues, it has been noticed that the problem of air pollution particularly of criteria air pollutants in Asian cities still persists because of the increasing number of vehicles. This book, Criteria Air Pollutants: Impact on Environmental Health, covers the important topics related to criteria air pollutants; their chemistry, sources, sinks and impacts; and control strategies. Chapter 2 provides a comprehensive overview and classification of the origin of criteria air pollutants. To explain their impact on the environment, Chap. 3 describes about the same and explains the classification of criteria air pollutants into primary and secondary in detail. However, its main focus is on primary criteria air pollutants, viz. NO2, SO2, PM, Pb and CO, and their impact on plant and human health. Chapter 4 explains the secondary criteria air pollutant, i.e. tropospheric ozone, and highlights its significance both at international and national levels. The vii

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Preface

lack of control technologies and policies is responsible for worsening air quality that leads to increase the concentrations of air pollutants, which have increased and crossed the national as well as international ambient along with health-based air quality standards. Hence, control policies and recommendations are needed to reduce the emissions of these air pollutant concentrations considerably. Thus, Chap. 5 highlights control and mitigation strategies to combat these air pollutants which are affecting plants/vegetation, human health and other environmental concerns along with their sources. This book acts as a valuable tool for students in Environmental Science, Biological Science and Agriculture, as well as for environmental consultants and professionals involved in air quality research and the application of air quality guidelines and advice. New Delhi, India

Pallavi Saxena Saurabh Sonwani

Contents

1

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.1 General Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.2 Summary of Chapters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.3 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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1 1 4 5 6

2

Criteria Air Pollutants: Chemistry, Sources and Sinks . . . . . . . . . . 2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2 Air Pollution Sources and Their Emissions . . . . . . . . . . . . . . . . 2.2.1 Anthropogenic Sources . . . . . . . . . . . . . . . . . . . . . . . . 2.2.2 Natural Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.3 Stationary Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.4 Mobile Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3 Particulate Matter (PM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3.1 Particulate Matter in Atmosphere . . . . . . . . . . . . . . . . . 2.3.2 Health Effects of PM10 . . . . . . . . . . . . . . . . . . . . . . . . . 2.3.3 Chemistry of Particulate Matter . . . . . . . . . . . . . . . . . . . 2.3.4 Ambient PM and Their Atmospheric Processes . . . . . . . 2.4 Carbon Monoxide (CO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4.1 Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4.2 CO Level and Trend . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4.3 Chemistry and Sink of CO . . . . . . . . . . . . . . . . . . . . . . 2.5 Lead (Pb) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5.1 Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5.2 Levels and Distribution of Lead . . . . . . . . . . . . . . . . . . 2.5.3 Exposure, Chemistry and Sink of Lead . . . . . . . . . . . . . 2.6 Nitrogen Dioxide (NO2) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.6.1 Sources of NO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.6.2 Levels and Distribution of NO2 . . . . . . . . . . . . . . . . . . . 2.6.3 Chemistry of NO2 in the Atmosphere . . . . . . . . . . . . . . 2.6.4 Sink of NO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.7 Sulphur Dioxide (SO2) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.7.1 Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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7 7 8 8 10 10 12 12 12 16 16 18 19 19 20 20 22 23 23 25 25 26 26 28 32 32 33 ix

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2.7.2 Emissions of Oxides of Sulphur . . . . . . . . . . . . . . . . . . 2.7.3 Levels and Trend of SO2 . . . . . . . . . . . . . . . . . . . . . . . 2.7.4 Chemistry of SO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.7.5 Sink of SO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.8 Tropospheric Ozone (O3) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.8.1 Chemistry of Tropospheric Ozone . . . . . . . . . . . . . . . . . 2.8.2 Sinks of the Tropospheric Ozone . . . . . . . . . . . . . . . . . 2.9 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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33 34 36 37 37 38 40 40 41

3

Primary Criteria Air Pollutants: Environmental Health Effects . . . 3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2 Environmental Health Effects . . . . . . . . . . . . . . . . . . . . . . . . . 3.2.1 Impact of SO2 and NO2 on Environmental Health . . . . . 3.2.2 Particulate Matter and Its Impact on Environment . . . . . 3.2.3 Impact of Carbon Monoxide on Environmental Health . . 3.2.4 Impact of Lead and Environmental Health . . . . . . . . . . . 3.3 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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49 49 51 51 55 70 74 77 77

4

Secondary Criteria Air Pollutants: Environmental Health Effects . . 4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2 Secondary Criteria Air Pollutant: Tropospheric Ozone . . . . . . . . 4.2.1 Tropospheric Ozone Formation . . . . . . . . . . . . . . . . . . . 4.2.2 Overall Trends of Tropospheric Ozone Levels: Present Status and Future Predicted Trends . . . . . . . . . . . . . . . . 4.2.3 O3 Concentrations Predictions . . . . . . . . . . . . . . . . . . . 4.3 Impact of Tropospheric Ozone on Climate . . . . . . . . . . . . . . . . 4.4 Impact of Tropospheric Ozone on Human Health . . . . . . . . . . . 4.4.1 Acute Health Impacts . . . . . . . . . . . . . . . . . . . . . . . . . . 4.4.2 Chronic Health Impacts . . . . . . . . . . . . . . . . . . . . . . . . 4.4.3 Guidelines for Human Health: Ozone Exposure . . . . . . . 4.5 Impact of Tropospheric Ozone on Plant Health . . . . . . . . . . . . . 4.5.1 Ozone Relationship with Oxidative Stress and Other Physiological Responses . . . . . . . . . . . . . . . . . . . . . . . . 4.5.2 Characterization of Ozone Exposure . . . . . . . . . . . . . . . 4.5.3 Ozone Deposition Mechanism . . . . . . . . . . . . . . . . . . . 4.5.4 Effects of Ozone on Physiology and Biochemistry of Plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.5.5 Impact of Tropospheric Ozone on Photosynthetic Rate, Stomatal Conductance and Photosynthetic Output Rate . 4.6 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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83 83 85 85

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88 91 91 93 94 96 97 97

. 99 . 102 . 104 . 105 . 110 . 113 . 113

Contents

5

Policy Regulations and Future Recommendations . . . . . . . . . . . . . . . 5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.1.1 Source Emission Control . . . . . . . . . . . . . . . . . . . . . . . . 5.2 Choice of Fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.3 Fuel Cleaning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.4 Selection of Technology and Methods . . . . . . . . . . . . . . . . . . . . 5.4.1 Emission Control Approaches . . . . . . . . . . . . . . . . . . . . . 5.5 Particle control system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.5.1 Gas- and Vapour-Phase Control System . . . . . . . . . . . . . 5.5.2 Policy Rules and Regulation . . . . . . . . . . . . . . . . . . . . . . 5.6 Stringent Measures Taken to Control Sector-Wise Emissions . . . . 5.6.1 Transport Sector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.6.2 Industrial Sector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.6.3 Agricultural Sector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.7 Pollutant-Wise Mitigation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.8 Carbon Monoxide (CO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.9 Nitrogen Oxides (NOx) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.10 Sulphur Dioxide (SO2) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.11 Lead (Pb) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.12 Ozone (O3) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.13 NOx Reasonably Available Control Technology (RACT) . . . . . . . 5.14 Ozone Transport Region (OTR) NOx Cap and Allowance Trading Program . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.15 EPA’s Ozone Transport NOx SIP Call . . . . . . . . . . . . . . . . . . . . 5.16 Particulate Matter (PM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.17 Policy Initiatives in India . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.18 Legal Framework . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.19 Legislation of Environment Programmes . . . . . . . . . . . . . . . . . . 5.20 Odd-Even Plan in Delhi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.21 Strict Emission Norms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.22 Restructuring the Growth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.23 Institutional Framework . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.24 Green Technology in India . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.25 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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127 127 129 130 130 130 131 131 132 133 136 136 141 141 144 144 145 145 146 147 148 148 148 149 149 150 150 151 151 152 152 152 153 154

About the Authors

Pallavi Saxena She is an Assistant Professor, Environmental Science, Hindu College, University of Delhi, Delhi, India. She had been awarded DST Fast Track Young Scientist Award for handling 31.50 rupees lakhs project for 3 years, i.e. from 2014 to 2017, at the School of Environmental Sciences, Jawaharlal Nehru University, New Delhi, India. She had also completed her postdoc from Space and Atmospheric Sciences Division, Physical Research Laboratory (PRL), Ahmedabad, Gujarat, India, from 2013 to 2014. She had also completed her graduation, postgraduation, master of philosophy and doctor of philosophy in Environmental Science from the University of Delhi. She has defended her work on the “Effect of Photochemical Pollutants on Plant Species” (2007–2013). Her area of interest is air pollution and plant physiology. She has been working in this area from last 12 years. She has been elected as Chair of South Asia and Middle East Region of Early Career Scientist Network of iLEAPS community, UK (2018–2019). She has also been awarded UGC JRF (2007–2008), Jawaharlal Nehru Doctoral Scholarship (2009–2010) and CSIR SRF (2012–2013) during her doctoral studies. She has been a Recipient of postdoctoral fellowships like DOS Fellowship at PRL (2013–2014) and DST Fast Track Young Scientist at the School of Environmental Sciences to pursue her independent project over there (2014–2017). She has published 21 research papers in international and national journals with high-impact factor. She has also been an Invited Speaker on “Variation in the Concentration of VOCs in Atmosphere at Selected Sites in Delhi” at the “bVOCs Monitoring and Modelling” workshop at Lancaster Environment Centre, Lancaster University, UK (2011). She is also a coauthor and collaborator from India of TOAR International Meeting which focuses on tropospheric ozone and its impact on vegetation from 2015 onwards. In addition to that, she has been a recipient of various awards like Young Scientist Award from the Indian Society for Plant Physiology (2013) and DBT BioCaRe Award (2014) and several travel grant awards from WMO, IGAC and NOAA to participate as an expert in Ozone Pollution and Its Impact on Vegetation in TOAR Meeting (2015–2016). She has also reviewed research articles for reputed journals like Atmospheric Environment (Elsevier), Mitigation and Adaptation of Strategies for Global Change (Springer), Environmental Technology (Taylor & Francis), Polish Journal of Environmental Studies, Environmental Monitoring and Assessment (Springer) and International Journal of Physical Sciences (Academic Journal). xiii

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About the Authors

She has participated in various national (10) and international conferences (16) and workshops and trainings (19) in the area of air pollution and plant physiology and has presented several papers. Saurabh Sonwani is currently working as Assistant Professor at Department of Environmental Sciences, Zakhir Hussain Delhi College, University of Delhi. He had completed his PhD and MPhil in Environmental Sciences from the School of Environmental Sciences, Jawaharlal Nehru University (JNU), New Delhi, India, and his MSc in Environmental Sciences from Banaras Hindu University (BHU), Varanasi, India. He has worked in the area of atmospheric sciences for more than 6 years. Till now, his work is focused on carbonaceous aerosols, organic pollutants such as polycyclic aromatic hydrocarbons (PAHs), volatile organic compounds (VOCs) and trace metals. He is also involved in conducting source apportionment, impact and climate change-related studies. He was awarded a Junior Research Fellowship (JRF) by the Council of Scientific and Industrial Research (CSIR) in the subject of Earth, Atmospheric, Planetary and Ocean Sciences in 2012. He had also qualified the National Eligibility Test (NET) from the University Grants Commission (UGC) in the subject of Environmental Sciences, conducted by the Government of India. He had also been awarded several reputed travel grants by the American Geophysical Union (AGU) and International Centre for Integrated Mountain Development (ICIMOD) and corpus fund from Jawaharlal Nehru University. He has written several research papers in reputed journals such as Current Science, Journal of Atmospheric Chemistry (JAC) and Aerosol and Air Quality Research (AAQR) (under review) in the related area. He has also contributed several book chapters published by several publishers of international reputation such as Springer, CABI, NOVA and ANE. He is a Lifetime Member of several scientific communities such as Asia Oceania Geosciences Society (AOGS), American Geophysical Union (AGU), Vijaya Bharathi (VIBHA), Indian Aerosol Science and Technology Association (IASTA) and School on Analytical Chemistry (SAC), Bhabha Atomic Research Centre (BARC). He has also presented several papers/posters in several reputed international and national conferences and workshops. In addition, he has worked as a Trainer and Volunteer in several workshops, training programmes and conferences since 2010.

1

Introduction

Abstract

The problem of air pollution is one of the greatest challenge worldwide and unfortunately it has not been solved even after the implementation of various technologies and policy actions. Drastic increase in urbanization and industrialization has resulted in elevated increase in primary as well as secondary air pollutants which ultimately affect the plant as well as human health. In particular, criteria air pollutants are some of the significant air pollutants that are more strongly supposed to be hazardous to human health and plant life. These air pollutants are showing drastic increase in their levels especially in developing countries and very few studies have been reported collectively to depict about their impacts and possible controls. Therefore, there is a stringent need for implementation of control policies and technologies to mitigate these kinds of air pollutants. Hence, this chapter focus on the overview of criteria air pollutants and also summarizes the brief introduction of different chapters highlighting about various aspects of criteria air pollutants. Keywords

Air pollution · Plant and human health · Criteria air pollutants · Control policies

1.1

General Introduction

Air pollution is one of the major issues in today’s world irrespective of developing or developed countries. Rapid increase in population and demand for energy have resulted in emission of toxic air pollutants that affect the surrounding environment as well as human health. According to the World Health Organization (WHO), about four million deaths along with numerous cases of respiratory illnesses annually result from air pollution in developing countries (WHO 2015, 2016). Human health, plant health, meteorological phenomena, agriculture yield, buildings and materials are immensely affected by various types of air pollutants emitted by various sectors # Springer Nature Singapore Pte Ltd. 2019 P. Saxena, Criteria Air Pollutants and their Impact on Environmental Health, https://doi.org/10.1007/978-981-13-9992-3_1

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1 Introduction

like transport, commercial, residential, institutional, domestic, power and vegetation zones. Both gaseous and particulate pollutants, heavy metals, biological pollutants, etc. play a significant role in affecting various atmospheric phenomena like climate change, secondary product formation, cloud formation and other transformations. To become more specific, there are some air pollutants which are designated under the Clean Air Act of 1971, which are more strongly suspected to be harmful to public health and the environment as compared to other primary and secondary pollutants; they are termed as criteria pollutants. There are six criteria air pollutants as per the Act list, viz. nitrogen dioxide (NO2), sulphur dioxide (SO2), particulate matter (PM), lead (Pb), carbon monoxide (CO) and ozone (O3). These air pollutants affect the air quality severely. Regulation of criteria pollutants mandates development of air quality standards, which vary from country to country. The “non-criteria pollutants” do not have an air quality standard assigned to them and include the entire range of air contaminants including toxic and hazardous substances, most of which are volatile organic compounds (VOCs). Gases such as carbon dioxide (CO2) and methane (CH4), co-emitted with various criteria pollutants, are studied under the realm of “greenhouse gases” because of their significant control on the radiative balance of the earth’s atmosphere and hence its climate. Many short-lived air pollutants also influence the radiative balance of the earth by absorbing the terrestrial infrared radiation (e.g. tropospheric O3), absorbing (e.g. black carbon) or scattering (sulphate aerosols) solar radiation or by interacting with clouds. These influences on radiation induce changes in the earth’s climate. Therefore, such radiatively active pollutants are also known as short-lived climate forcers (IPCC 2013). Emission sources of pollutants are either localized (e.g. industrial chimneys, traffic along highways) or confined to a small region (e.g. biomass burning related to deforestation in tropical areas, an industrialized urban environment). The dense urban regions are the major “hotspots” of air pollutants. The interplay between emission and transport controls the levels of pollutants in local, regional and global scales. Through the transport of atmospheric pollutants, the human-induced activities have global consequences, which is one of the most important issues for global climate change and health studies. One of the most prominent evidences of the impact of atmospheric pollution emission and transport on the composition of the global atmosphere is the Antarctic “ozone hole”: large reduction in the levels of stratospheric ozone over the southern polar cap in each spring due to the reaction with chlorofluorocarbons carbon (CFCs) (Molina and Rowland 1974; Crutzen and Arnold 1986; Solomon et al. 1994). The Arctic haze (the phenomenon of a visible reddish-brown springtime haze in the atmosphere) caused by industrial pollution from Europe is also another example of the transport-driven impact of atmospheric pollutants on the remote regions (Barrie 1986). The emission of air pollutants from anthropogenic activities has now surpassed their natural emissions. The upsurge in the abundance of air pollutants can be largely attributed to increased combustion of fossil fuels, to meet the growing demands for energy and transportation, for supporting the growing human population on earth. Hazardous pollutants/contaminants can escape to the atmosphere by sporadic accidental events or can be released by numerous anthropogenic activities. These air contaminants or pollutants have the potential to be hazardous to the nourishment

1.1 General Introduction

3

and health of life (humans, animals and plants) on earth. Notable incidents such as toxic smog over Meuse Valley in Belgium (Nemery et al. 2017) and London (Bell et al. 2004) resulted in immediate acknowledgement of lethality of air pollution on the human health. It is unquestionable that the increased concentration of atmospheric contaminants can be linked to the increase in mortality and/or serious ailment and poses serious hazards to the human health (Sriramachari 2004; Bell et al. 2004; Anderson et al. 2012). With human population on earth setting new records in the Anthropocene, the demand for energy has also increased tremendously over the last century, resulting in increased combustion of fossil fuels and emission of various atmospheric pollutants (Crutzen 2006). In developing countries like India, very drastic change in the quality of air has been observed during the past two decades. Many cities in Asia, Africa and Latin America are facing major challenges of air pollution (Ashmore 2005). Delhi (the capital city of India) is also facing the problem of severe air pollution in spite of the implementation of CNG-driven public transport (Saxena et al. 2012). The air quality in Delhi has been the worst among 1600 cities of the world (WHO 2014–15). According to the estimates, around 1.5 million people are killed every year. India has the world’s highest death rate from chronic respiratory diseases and asthma. The effects of air pollution on living systems like plants, animals and human beings and other materials are worse. Air pollutants particularly ozone and sulphur dioxide affect the plant metabolism and lead to huge yield loss (Heck et al. 1988). On the other hand, air pollutants have caused high risk of cardiovascular diseases, lung diseases and diabetes in adults as well as in children (Sadanaga et al. 2003). Tropospheric ozone (O3) is a phytotoxic agent and can affect vegetation adversely which results in stunted growth of plant species. These impacts can consequently imbalance the CO2 uptake system from the atmosphere and produce alteration in the physiology of plant species. Acid rain also affects the plant biochemical and physiological metabolism severely. The acid-forming products during the acid rain like sulphuric acid and nitric acid affect membrane permeability, stomatal conductance and enzyme activity to a larger extent (Pant and Harrison 2013). The major source of acid rain is industrial activity which ultimately causes the natural rain 100 times more acidic. Acid rain can have more harmful impacts in both terrestrial and aquatic systems. The soil quality can also be deteriorated due to heavy deposition of acids which ultimately alter the physicochemical properties (Liu and Diamond 2005; Davis 2008). The contamination of ambient (outdoor) air has considerable impact on the human health. Contact with the air pollution occurs primarily by inhalation and ingestion. Contamination of ambient air and subsequent fallout of pollutants further contributes to contamination of water and food, posing additional hazard towards ingestion of pollutants. There is no doubt over the association of air pollution with the health hazards in living beings. Some of the notable sporadic high pollution intensity incidents such as toxic smog over Meuse Valley in Belgium (Nemery et al. 2017) and London (Bell et al. 2004) and leakage of highly toxic methyl isocyanate (MIC) during the Bhopal gas tragedy (Sriramachari 2004) have already highlighted the lethal effects of air pollution on health. It has been well established that the fatality and hospital admissions are linked proportionately to the quality and quantity

4

1 Introduction

of pollutants in the ambient air (Brunekreef and Holgate 2002; Fischer et al. 2004; Liu et al. 2013). The hazard and lethality of air pollution are primarily governed by these key factors: (i) composition (quality) of the air pollution, (ii) concentration (quantity) of pollutants in the air and (iii) duration of exposure to the air pollutants. The health effects of air pollution can vary from minor (such as breathlessness, nausea, skin and respiratory tract irritation) to major (such as asthma, bronchitis and cancer). The air pollution can also drive some indirect health effects, such as birth defects and acute delays in development of children (Ritz et al. 2002). Exposure to contaminated air may also suppress the immune system, causing other ailments (Calderón-Garcidueñas et al. 2008). Both long-term and short-term exposures to the air pollution are hazardous to health, leading to various diseases and mortality in the most acute cases.

1.2

Summary of Chapters

On the basis of discussion of a number of issues, it has been noticed that the problem of air pollution particularly of criteria air pollutants in Asian cities specifically still persists because of increasing number of vehicles. This book, Criteria Air Pollutants: Impact on Environmental Health, covers the important topics related to criteria air pollutants, their chemistry, sources, sinks, their impacts and control strategies. Chapter 2 provides a comprehensive overview and classification of the origin of criteria air pollutants. This chapter particularly highlights the chemistry, interrelationships among pollutants, major sources and sinks of all criteria air pollutants. It also explains about national and international studies related to them with respect to their source apportionment and trends in the past few years and in future times. This is an important chapter because it forms a fundamental base to all the readers which includes the basic information about criteria air pollutants. During the past few decades, fossil fuel combustion has contributed large emissions of different air pollutants which are harmful for humans, vegetation, ecosystem and environment. In relation to criteria air pollutants, very less information is available both nationally and internationally. To explain their impact on the environment, Chap. 3 describes about the same. This chapter explains the classification of criteria air pollutants into primary as well as secondary criteria air pollutants in detail. The main focus of these primary criteria air pollutants is NO2, SO2, PM, Pb and CO and their impact on plant and human health. It also explains the role of all primary criteria air pollutants in the atmosphere. In addition to that, this chapter also specifies the national and international outlook of plant and human health and their impact on the atmosphere. The focus of secondary criteria air pollutant, i.e. tropospheric ozone, has been well explained in Chap. 4. This chapter highlights the significance of secondary criteria air pollutant, i.e. tropospheric ozone, both at international and national levels. Relatively, developing countries are more prone to tropospheric ozone pollution due to high anthropogenic activities. As tropospheric ozone is secondary product due to reactions among precursors like NO2, VOCs and CO in the presence of sunlight, therefore its chemistry is a challenging aspect. Increasing concentrations of ozone

1.3 Conclusion

5

leads to climate change due to its major role in greenhouse effect. In case of human health, major observations show a clear relation between acute exposure and lung function decrements, lung inflammation, lung permeability, symptoms of pain and cough on deep inspiration, immune system activation and epithelial injury. Ozone exposure studies also lead to permanent damage. In case of plants, tropospheric ozone is the most dangerous pollutant that is why it is called as phytotoxic agent. Ozone causes visible injury, impaired photosynthesis and altered stomatal behaviour, decreases growth and productivity and alters the metabolic pathway of plants. Ozone increases incidence of pest and disease attacks on plants. O3 induces crop yield and quality losses. Changes in forage quality through shift in pasture communities leading to change in herbivory pattern are also found under ambient levels of O3. Criteria air pollutants affect a quarter of the world’s population, resulted on a large scale from anthropogenic activities like biomass burning, industrialization and vehicular activities. These air pollutants also damage buildings, crops, ecosystems and wildlife populations. Lack of control technologies and policies is responsible for worsening air quality and leads to increase in concentrations of air pollutants. The concentrations have increased and cross the national as well as international ambient along with health-based air quality standards. Hence, control policies and recommendations are needed to reduce the emissions of them considerably. Hence, Chap. 5 highlights about control and mitigate strategies to combat these air pollutants which are affecting plants/vegetation, human health and other environmental concerns along with their sources. These various control strategies designed by national as well as international agencies are significantly needed to combat the deleterious concentrations of criteria air pollutants. Control strategies include various norms, implementation of clean air act policies, mitigation protocols and laws and legislations.

1.3

Conclusion

An overview of all studies concludes that criteria air pollutant concentrations are still increasing and crossing their permissible limits particularly in developing countries even after the implementation of several control policies and strategic plans. Overall, very less studies have been reported collectively with respect to criteria air pollutants and their impact on environmental health. Therefore, their sources, sinks and interrelationships are still not studied worldwide. Impact studies related to them with respect to plant, human and atmosphere health are needed to be addressed on a serious note because death toll rate has been increasing rapidly day by day. At this emergent situation, there is an urgent need for stringent control policies and plans to mitigate and curb these types of air pollutants. Thus, different chapters in this book highlight the important concepts of criteria air pollutants which give the overall view at both national and international regimes. Moreover, impact studies on plant, human and environment as a whole have also been discussed at wide scale. This book ends with the possible control methods and policies to curb criteria air pollutants.

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1 Introduction

References Anderson JO, Thundiyil JG, Stolbach A (2012) Clearing the air: a review of the effects of particulate matter air pollution on human health. J Med Toxicol 8:166–175 Ashmore MR (2005) Assessing the future global impacts of ozone on vegetation. Plant Cell Environ 28:949–964 Barrie L (1986) Arctic air pollution, vol 328. Cambridge University Press, Cambridge Bell ML, Davis DL, Fletcher T (2004) A retrospective assessment of mortality from the London smog episode of 1952: the role of influenza and pollution. Environ Health Perspect 112:6–8 Brunekreef B, Holgate ST (2002) Air pollution and health. Lancet 360:1233–1242 Calderón-Garcidueñas L, Solt AC, Henríquez-Roldán C, Torres-Jardón R, Nuse B, Herritt L, Villarreal-Calderón R, Osnaya N, Stone I, García R, Brooks DM, González-Maciel A, Reynoso-Robles R, Delgado-Chávez R, Reed W (2008) Long-term air pollution exposure is associated with neuroinflammation, an altered innate immune response, disruption of the bloodbrain barrier, ultrafine particulate deposition, and accumulation of amyloid β-42 and α-synuclein in children and young adult. Toxicol Pathol 36:289–310 Crutzen PJ (2006) The “Anthropocene”. In: Ehlers E, Krafft T (eds) Earth system science in the Anthropocene. Springer, Berlin/Heidelberg, pp 13–18 Crutzen PJ, Arnold F (1986) Nitric acid cloud formation in the cold Antarctic atmosphere: a major cause for springtime ‘ozone hole’. Nature 324:651–655 Davis LW (2008) The effect of driving restrictions on air quality in Mexico City. J Polit Econ 116:38–81 Fischer PH, Brunekreef B, Lebret E (2004) Air pollution related deaths during the 2003 heat wave in the Netherlands. Atmos Environ 38:1083–1085 Heck WW, Taylor OC, Tingey DT (1988) Assessment of crop loss from air pollutants. Elsevier Applied Science, London IPCC (2013) Climate change 2013. In: The physical science basis. IPCC, Geneva, pp 119–1523 Liu JG, Diamond J (2005) China’s environment in a globalizing world. Nature 435:1179–1186 Liu H-Y, Bartonova A, Schindler M, Sharma M, Behera SN, Katiyar K, Dikshit O (2013) Respiratory disease in relation to outdoor air pollution in Kanpur, India. Arch Environ Occup Health 68:204–217 Molina JS, Rowland FS (1974) Stratospheric sink for chlouoromethanes: chlorine atom-catalized destruction of ozone. Nature 249:810–812 Nemery B, Hoet PHM, Nemmar A (2017) The Meuse Valley fog of 1930: an air pollution disaster. Lancet 357:704–708 Pant P, Harrison RM (2013) Estimation of the contribution of road traffic emissions to particulate matter concentrations from field measurements: a review. Atmos Environ 77:78–97 Ritz B, Yu F, Fruin S, Chapa G, Shaw GM, Harris JA (2002) Ambient air pollution and risk of birth defects in Southern California. Am J Epidemiol 155:17–25 Sadanaga Y, Matsumoto J, Kajii Y (2003) Photochemical reactions in the urban air: recent understandings of radical chemistry. J Photochem Photobiol C: Photochem Rev 4:85–104 Saxena P, Bhardwaj R, Ghosh C (2012) Status of air pollutants after implementation of CNG in Delhi. Curr World Environ 7(1):109–115 Solomon S, Burkholder JB, Ravishankara AR, Garcia RR (1994) Ozone depletion and global warming potentials of CH3I. J Geophys Res 99:20929–20935 Sriramachari S (2004) The Bhopal gas tragedy: an environmental disaster. Curr Sci 86:905–920 WHO (2014–15) Air quality guidelines for Europe, European series, 2nd edn. WHO Regional Publications, Copenhagen, p 91 WHO (2015) World health statistics report. World Health Organization, Geneva. http://apps.who. int/iris/bitstream/10665/170250/1/9789240694439_eng.pdf WHO (2016) World health statistics report. World Health Organization, Geneva. http://apps.who. int/iris/bitstream/10665/206498/1/9789241565264_eng.pdf

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Criteria Air Pollutants: Chemistry, Sources and Sinks

Abstract

Ambient air pollution is the foremost reason for global death and disease. An estimated premature death globally is related to ambient air pollution, mainly from emphysema, obstructive bronchiolitis, lung cancer, heart disease, stroke, and severe respiratory problems in children. The criteria air pollutants include particulate matter (PM), ozone (O3), nitrogen dioxide (NO2), sulphur dioxide (SO2) and lead (Pb). The present chapter provides a summary of the types of criteria air pollutants, their National Ambient Air Quality Standards and their emission sources. This chapter also explains their level distribution and chemistry, and the sink in the earth’s environment of these criteria pollutants is studied extensively. Description of global, regional emissions of criteria air pollutants, their contribution from different sectors, and efficiency of control strategies in developed and developing countries are also focused.

2.1

Introduction

Air pollution is one of the rapidly growing problems of today’s world. The pollutant is emitted from different sources directly or indirectly to the ambient atmosphere. When one or several pollutants are present in the air in such a level for a long period of time, that can have some harmful effects on human, animal, plant and/or material properties which is called air pollution. It also affects the global economy, Earth Radiation Budget and climate change in the long-term perspective. Air pollution is now considered as the world’s biggest threat to the environmental health and responsible for the seven million deaths over the world per year. It causes a number of deleterious effects and causes pulmonary illness, asthma and cardiovascular diseases after long-term exposure. Short-term exposure also creates problems like headache, mood alteration, dizziness, eye-irritation, nausea, coughing, etc. US Environmental Protection Agency (USEPA) has set up the National Ambient Air Quality Standards (NAAQS) for six pollutants, viz. particulate matter, carbon # Springer Nature Singapore Pte Ltd. 2019 P. Saxena, Criteria Air Pollutants and their Impact on Environmental Health, https://doi.org/10.1007/978-981-13-9992-3_2

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Criteria Air Pollutants: Chemistry, Sources and Sinks

monoxide, nitrogen dioxide, sulphur dioxide, ground-level ozone, and lead which is also known as “criteria air pollutants” or criteria pollutants. These criteria pollutants harm the environment and their components after their emission or after atmospheric transformation reactions such as oxidation/reduction. The atmospheric chemistry along with their source and sink information provides a clear picture about the criteria air pollutant in the atmosphere. A brief description of the origin (sources), chemical transformation and sinks of the criteria pollutants has been discussed in the present chapter. As far as emission concerns, criteria pollutants have varieties of origin including natural and anthropogenic sources. Natural sources include volcanic eruption, forest fire, lightning strikes and biological emissions. The anthropogenic sources include emissions from industries, vehicles, biomass burning, cooking activities and resuspension of soil/road dust. These pollutants either originate directly by primary emission sources or originate through their precursors via chemical transformation reactions into the atmosphere. The increasing burden of these in the atmosphere causes several harmful defects on the plants and animals including human being. There are complex relationships between the air pollutants’ atmospheric criteria pollutant levels, chemistry, sources and their sink. To identify the increasing atmospheric pollution levels, the ambient air quality standard is developed as a policy guideline that regulates the effect of human activity upon the environment so that pollutant emission into the air can be regulated. These standards are developed by several agencies such as US Environmental Protection Agency (USEPA), Central Pollution Control Board (CPCB) and many more across the world. Table 2.1 shows the National Ambient Air Quality Standards (NAAQS) reported by USEPA and CPCB for the six designated criteria air pollutants.

2.2

Air Pollution Sources and Their Emissions

There are two major categories among the air pollution sources, viz. anthropogenic and natural.

2.2.1

Anthropogenic Sources

Anthropogenic sources are the results of various human activities such as fossil fuel combustion, industries emissions (cement factories, oil refineries, electroplating), emission from thermal power plants, emissions from agriculture activities (crop burning and ploughing), transportation emission (light motor vehicles and heavy-duty vehicles), mining, cooking, refuse burning, etc. The most widespread anthropogenic sources are identified and classified by using emission factors and further used to plan the air quality management programme (Boubel et al. 1994). The clear picture of distribution of anthropogenic emissions from different sectors is shown in Fig. 2.1.

Carbon monoxide (CO)

Lead (Pb)

Nitrogen dioxide (NO2)

Ozone (O3)

Particulate matter (PM)

2.

3.

4.

5.

6.

Primary Secondary Primary and secondary Primary and secondary

Primary Primary and secondary Primary and secondary

24 h

1 year 1 year 24 h

8h

1h Annual

150 μg/m3

12.0 μg/m3 15.0 μg/m3 35 μg/m3

0.070 ppm

100 ppb 53 ppb

NAAQS (USEPA) 75 ppb 0.5 ppb 9 ppm 35 ppm 0.15 μg/m3

60 μg/m3 100 μg/m3

60 μg/m3 100 μg/m3

60 μg/m3

60 μg/m3 24 h Annual 24 h

100 μg/m3 180 μg/m3 40 μg/m3

100 μg/m3 180 μg/m3 40 μg/m3

Ecologically sensitive area 20 μg/m3 80 μg/m3 2 mg/m3 4 mg/m3 0.50 μg/m3 1.0 μg/m3 30 μg/m3 80 μg/m3

8h 1h Annual

NAAQS (CPCB) Avg. Industrial, residential, rural time and other areas Annual 50 μg/m3 24 h 80 μg/m3 8h 2 mg/m3 1h 4 mg/m3 Annual 0.50 μg/m3 24 h 1.0 μg/m3 Annual 40 μg/m3 24 h 80 μg/m3

USEPA United States Environmental Protection Agency, USA; CPCB Central Pollution Control Board, India

PM10

PM2.5

Pollutant Sulphur dioxide (SO2)

S. No. 1.

NAAQS (USEPA) Primary/ secondary Avg. time Primary 1h Secondary 3h Primary 8h 1h Primary and Rolling 3 months secondary average

Table 2.1 National Ambient Air Quality Standards (NAAQS) for six criteria air pollutants

2.2 Air Pollution Sources and Their Emissions 9

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Criteria Air Pollutants: Chemistry, Sources and Sinks

Fig. 2.1 Global distribution of anthropogenic emissions from different sectors in relation to air pollutants. (Source: IPCC 2014)

2.2.2

Natural Sources

Natural sources linked to the earth’s processes, which release huge quantities of pollutants into the atmosphere within a very short period, include volcanic eruption, dust storms and forest fire. Few other natural sources/activities also released some amount of the pollutants but in significant amount such as grazing animals and lightning. Biogenic emissions are also a part of natural sources and emitted chemicals and gases through their biological activity, e.g. vegetation and microbial activity in soils (Zunckel et al. 2007). The global distribution of natural sources from different sectors is shown in Fig. 2.2. Based on the nature of sources, anthropogenic and natural sources can be further classified as mentioned below.

2.2.3

Stationary Sources

Stationary sources of air pollution are limited to a particular region while emitting pollution and typically connected with fixed structures like buildings and frequently release noxious wastes that remain moderately steady in due course of time, e.g. factories, refineries, boilers, power plants, etc. Stationary sources can have further subsections.

2.2.3.1 Point Source Point source is a single, identifiable source of pollution with fixed geographical coordinates; they are usually high over the ground level with a small outlet diameter.

2.2 Air Pollution Sources and Their Emissions

11

Fig. 2.2 Global distribution of natural emissions from different sectors in relation to air pollutants. (Source: IPCC 2014)

The term point source is frequently used for industrial smoke stacks and flare stacks. There are several point source processes, which released a significant amount of the criteria air pollutants into the atmosphere such as external combustion boilers (ECB), internal combustion engines (ICE), industrial processes, petroleum and solvent evaporation, etc.

2.2.3.2 Area Sources Area sources are unlike point sources and have relatively larger horizontal dimensions. This is an area where several stationary sources are grouped together whose collective emissions can be significantly high as compared to the individual emissions. Thus, geographically they are considered as an area, and emissions are represented as a combined value. In this case, a residential area having several braziers continually emitting pollutants may be considered as area source. Mines and quarries are also considered as area sources. 2.2.3.3 Fugitive Sources Fugitive sources are indefinable sources, which are difficult to identify. It may include seepage from the industries, oil spills, leak valves and pipes and pumps that release pollutants into the atmosphere. Such fugitive emissions only can be determined by using specific estimation techniques. 2.2.3.4 Volume Sources Volume sources have comparatively huge horizontal and vertical dimensions. Examples include material sand piles, limestone piles and coal piles where wind may liberate particulate matter or dust.

12

2.2.4

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Criteria Air Pollutants: Chemistry, Sources and Sinks

Mobile Sources

Mobile sources are mostly associated with transportation and may be classified into on-road vehicles (motorcycles, passenger cars, trucks and commercial trucks and buses) and non-road vehicles and engines (aircraft, heavy equipment, boats, locomotives, marine vessels, farm machinery, recreation vehicles, etc.). Sometime, an unpaved road can also termed as mobile source because the allocation of emissions (primarily dust) is alike to that of a motor vehicle, i.e. the pollutants are emitted along a path. Briefly, criteria pollutants can be classified into the following.

2.3

Particulate Matter (PM)

Particulate matter (PM) refers to a suspension of solid, liquid or a combination of solid and liquid particles in the air (Hinds 1999). Particulate matters produced from both man-made and natural sources can be categorized into primary and secondary pollutants on the basis of their origin. Primary particulate matters are emitted directly from emission sources, and they are often associated with combustion sources. Secondary particulate matters are formed in the atmosphere by various photochemical reactions from primary pollutants like NOx, SOx and VOCs (Ito et al. 2005). The particulates emitted directly from their sources (construction sites, unpaved roads, fields, smokestacks or fires) are known as primary particulates like sulphur dioxides and nitrogen oxides that are emitted from power plants, industries and automobiles, while secondary particulates are formed by chemical reactions in the atmosphere. Sometimes outdoor particulate sources also contribute to indoor air pollution, apart from the outdoor PM sources: cooking, combustion activities such as use of unvented space heaters or kerosene heaters, candle burns, use of fireplaces and cigarette smoking. Indoor PM can also be of biological origin.

2.3.1

Particulate Matter in Atmosphere

Particulate matter of 10 micrometers or less in diameter is considered as PM10. They are capable of penetrating deep into the lungs which causes severe respiratory problems. The fine particulates (aerodynamic diameters lesser than 2.5 μm) are the most harmful among air pollutants. PM2.5 particles can easily enter the alveoli and consequently be stuck to the lung parenchyma (Dockery 2009). PM2.5 can cause various adverse health effects and cause cardiovascular problems, respiratory diseases and lung cancer (Hoek et al. 2013; Brook et al. 2010). The PM2.5 is identified as a high-risk factor and placed on the ninth position out of all health risk factors in a study about the global burden of disease conducted in 1990–2010 (Lim et al. 2012). Figure 2.3 showed the annual PM10 distribution over the world considering periods from 2008 to 2015. It was mentioned that Eastern Mediterranean cities (Riyadh, Ma’ameer, Dora and Abu Dhabi) were observed with very high

Fig. 2.3 Annual average 10 μm or less (PM10) over the world for 2008–2015 (World Health Organisation 2016)

2.3 Particulate Matter (PM) 13

14

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Criteria Air Pollutants: Chemistry, Sources and Sinks

average concentration (>200 μg/m3) over the world; the second highest level were observed in the cities of Southeast Asia (Delhi, Dhaka, Colombo and Karachi) with high annual average concentration (150–200 μg/m3). The Western Pacific region was noticed with slightly low average levels but lies in the range of 100–149 μg/m3, whereas Africa region was found with relatively high concentration as compared to the levels of PM10 observed in America and Europe. I) Urban Aerosols These are complex mixtures of primary pollutants (release directly from the sources such as motor vehicles, power plants, industries, forest fire, volcanic eruptions, etc.) and secondary pollutants (formed into the atmosphere through atmospheric transformation reactions such as gas-to-particle conversion mechanisms). Urban aerosol is rich in smaller particles (90%) are released from the emission generated from the combustion of leaded petrol emission with inorganic particles such as PbBrCl, whereas the rest of the 10% lead are dominated by organic lead (predominantly lead alkyls). In contrast to the above-mentioned, predominance of the coarser particles came into the existence in the vicinity of smelters, which may be deposited at few hundred meters. Lead either deposited onto land/ocean by dry or wet deposition processes. The deposition of the lead-containing particles depends on several factors such as rainfall, wind speed, wind directions and the emission height. The fallout of lead-based compounds is released from the industrial emission and depends their distance from sources. Moreover some of the authors found lead deposition at a long distances and has been confirmed by determination of glacier ice and snow deposited at distant location, like Greenland, until about 1960 (Murozumi et al. 1969). Nevertheless, successive analysis showed a descending trend in the same glacial strata (Boutron et al. 1991).

2.6 Nitrogen Dioxide (NO2)

2.5.3

25

Exposure, Chemistry and Sink of Lead

Most of the lead in the atmosphere are present along with the fine particulate matter and easily undergo into the human respiratory system through inhalation and may be easily retained and absorbed into the body. The particle size distribution and ventilation rate are the factors affecting absorption of particles through the respiratory system. The absorbed portion of lead is circulated in several important components such as blood, soft tissues, bones and teeth. An adult human contains most of the lead (95%) in their bones, while it may found up to 70% in children (Barry 1981). About 99% of the lead in the circulatory system is bound to red blood cells. The level of lead in the body increases over time/ age, more frequently in males especially in their bones (Barry and Mossman 1970). Some of the studies also confirmed the mobilization of lead during pregnancy (Gulson et al. 2016; Wells et al. 2011). Some reports also indicate that children, mostly infants, have a larger level of lead (USEPA 1994). Another recent study also found an inverse connection between blood lead concentration and IQ score (Lanphear et al. 2005). The chronic exposure of lead in human leads to the development of cancer, elevated blood pressure and neurodegradation. Blood, urine, bone, tooth and hair are identified as major biomarkers related to lead exposure. There can be several pathways for the lead metabolism at cellular levels, but at molecular levels, the replacement of Zinc (Zn) with lead (Pb) in zinc proteins with functional consequences is one of the major paths. Despite the fact that scientist detected the hazards of the lead exposure from several decades, vagueness remains as to the threshold for adverse effects on our health and the low concentrations of exposure during our life as a risk factor for chronic disease (Maret 2017). Lead is basically removed by the several processes such as rainfall, sedimentation and snowfall from the atmosphere. Thus the soil and sediments are the ultimate sinks for lead, whereas an average healthy man is exposed by a mean of about 300 mug of lead/day in his food with a range of 100–400 mug (Haar 1975). Lead is transported continuously among different matrices such as air, water and soil through natural and physicochemical processes such as weathering, runoff, wet and dry deposition and stream/river flow; nevertheless, soil and sediments are identified as important sinks for lead.

2.6

Nitrogen Dioxide (NO2)

Nitrogen dioxide is a reddish-brown gas with an unpleasant and annoying odour. This is a primary gas released into the atmosphere after burning of fuel. NO2 is a strong oxidizing agent that plays an important role in atmospheric transformation reactions and converted into gaseous nitric acid, toxic organic nitrates and tropospheric ozone (major component of smog). Due to its contribution in the formation of photochemical smog, it is identified as one of the important air pollutants having significant impacts on human health. The elevated concentration of NO2 causes health-related problems such as problems related to short-term exposure

26

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Criteria Air Pollutants: Chemistry, Sources and Sinks

(cardiovascular and respiratory) and long-term exposure (cancer and mental development in children). Apart from the above-mentioned, nitrogen dioxide also reacts with different atmospheric pollutants and produces high levels of ozone (which also have adverse impacts on human and plants).

2.6.1

Sources of NO2

Atmospheric oxidation of ammonia, microbial activities in soil and lightning are the most important natural processes resulting to the formation of the NO2 (Lamarque et al. 1996; Lee et al. 1997). The anthropogenic sources are of more significance than natural sources in terms of the NO2 and O3 air pollution, as they are more concentrated in the more populated areas. The high-temperature fuel combustion in vehicles and in industrial and utility boilers is the main man-made source of NO2 emissions. The emissions from power plants, motor vehicle and off-road equipment are the other major sources for nitrogen dioxide in the atmosphere. Petrol and metal refining, manufacturing and food processing industries also released a significant amount of NO2 into the atmosphere. The oxides of nitrogen are emitted in the form of NO, but it readily converts into the NO2 due to the oxidation processes in the atmosphere. In the presence of O3, the reaction happens at a very high rate. In most of the cases, formation of NO2 is under the influence of ground-level O3.

2.6.2

Levels and Distribution of NO2

In the ambient atmosphere, oxides of nitrogen exist in the form of nitric oxide (NO) and nitrogen dioxide (NO2). Both act as the pollutants in the lower atmosphere, whereas nitrous oxide (N2O) acts as a greenhouse gas. It can be emitted in the form of NO, a colourless, tasteless gas. NO2 is a gas with pungent, irritating odour with strong oxidizing properties. In the atmosphere, it is readily converted to the nitric acid and ammonium salts. In dry atmospheric condition, the nitrogen oxide is converted to the nitrate aerosols. These chemicals are removed from the atmosphere through wet and dry deposition process. Around 10% and 90% of the total NOx was contributed by natural and anthropogenic sources, respectively (Godish 1991). The natural sources include lightning, volcanic eruption and photochemical destruction of the nitrogenous compounds in the upper atmosphere. Fossil fuel burning, thermal power plants and vehicular emission are the major activities contributing NO2 in the atmosphere and contribute about 50% of the total anthropogenic emission. Other source includes incinerators, mining activities, welding process, etc. Global annual emissions of the nitrogen oxides are found to be 50 million metric tons (World Resources Institute 1994). The USA produces around 20 million metric tons (MMT) of NOx, and it is 40% of the NOx produced by mobile sources, whereas about 11–12 MMT of NOx is produced from stationary sources, out of which around 30% is the result of fuel combustion and 70% is from electric utility furnaces (Cooper and Alley 1986).

2.6 Nitrogen Dioxide (NO2)

27

Table 2.3 Sector-wise global NOx emission and projections in Mg Sector Petroleum refining plants Commercial and institutional plants Residential plants Plant related to agroforestry and aquaculture Combustion-based industrial plants Public power sector District heating plants Oil/gas extraction Total

2010 1544 878

2015 1404 699

2020 1404 667

2025 1404 647

2030 1404 625

2035 1404 602

6617 705

5519 747

4726 892

4751 1056

4796 1220

4859 1292

5941

4843

4150

3965

3782

3647

16,146 2766 6490 41,087

9341 2713 5454 30,719

9424 2180 6007 29,450

9439 2356 8039 31,659

10,701 2203 9555 34,287

11,500 2790 9452 35,546

Data Source: Nielsen et al. (2013)

The global annual average of NO2 in urban areas is observed in the range of 20–90 μg/m3. Hourly averages near busy roads usually exceed 1000 μg/m3 (World Bank 1998). The picture of NOx emissions would be more clear if the projection issues can be brought into focus; therefore, Table 2.3 shows clearly the NOx projections in different years. The ambient concentration of the NO2 depends on several factors such as day timing, season and meteorological parameters. The high value of the NO2 is observed usually in the typically, urban concentration peak in the morning and afternoon rush hours due to the high volume of traffic on road. The winter season was observed with a higher level of NO2 as compared to other seasons across the world, and it is due to the traffic conjunction in foggy days and increased use of heating fuels and low mixing height. Since, the change of NO2 from NO depends on its concentration in the atmosphere and solar intensity. The levels of NO2 are usually found higher during warm and sunny days. NOx levels drop speedily as distance increases from its source. Levels of NOx in rural areas are very close to its background concentrations in the absence of any major source (USEPA 1990). Nevertheless, oxides of nitrogen may participate in the long-range transport, and thus they participate in the acid rain formation/deposition and elevated ozone in the upper atmosphere even in the absence of nearby emission sources. The indoor levels of the NOx found relatively high as compared to the outdoor level of NOx, thus one of the major causes of concern for indoor environment and human health. Sources of indoor NOx include cigarette smoke, cooking appliances and space heaters. The level of NO2 may exceed up to 200 μg/m3 over a period of several days. The realtime NO2 concentration may reach up to 500–1900 μg/m3 during cooking and 1000–2000 μg/m3 where a gas-fired water heater is also in use. The smoke of single cigarette may have 150,000–225,000 μg/m3 of NO and some quantity of NO2 (Canada, Federal-Provincial Advisory Committee on Air Quality 1987). The findings reflected that tropospheric NO2 column concentration has raised in China (11  2.6%/yerr), South Asia (1.76  1.1%/year), Middle East (2.3  1%/ year) and South Africa (2.4  2.2%/year). Tropospheric NO2 column concentration

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confirms some drop in the Eastern USA (
2  1.5%/year) and Europe (0.9  2.1%/ year). It was drawn that even though tropospheric NO2 column concentration drops in the main developed countries in the past few years, the current tropospheric NO2 column concentration in these countries is still considerably more than those found in newly and rapidly developing countries (excluding China). Tropospheric NO2 column concentration is observed with some drop in South America and Central Africa, characterized by main biomass burning area in the Southern Hemisphere. Ghude et al. (2013) reported the situation for India and observed a growth rate of 3.8% 2.2% year
1 between 2003 and 2011 for man-made sources, which is significantly linked to the escalation in oil and coal utilization in India. Hilboll et al. (2013) observed tropospheric NO2 column concentration to be drastically rising over China, the Middle East and India, with values over East-Central China tripling from 1996 to 2011. An important concentration of NO2 drops during the period, which is observed in the USA, Western Europe and Japan. In terms of citywise emissions, Dhaka, Bangladesh (+27.2  3.9% year
1), and Baghdad, Iraq (+20.7  1.9% year
1), were at a higher level, while Los Angeles, USA, (
6.00  0.72% year
1) was at the lower position. Megacities (population > 10 million) in China, India and the Middle East have indexed increasing NO2 columns of +5 to 10% year
1. Lamsal et al. (2011) observed a rise in man-made NOx release over land by 9.2% globally and by 18.8% from East Asia throughout 2006–2009. The emission from North America observed to drop by 5.7% in the similar period. Delmas et al. (1997) found fossil fuel burning (50%) and biomass burning (20%) as dominant sources of NOx globally. Natural sources (lightning and microbial activity in soils) are observed by contributing less than 30% of total emissions. Huntrieser et al. (2002) observed that a higher NOx is originated by lightning (mean 3 TgN year
1) as compared to the NOx released by aircraft (0.6 TgN year
1) for Europe as well as on a global scale. Figure 2.6 shows a world map of nitrogen dioxide tropospheric column density.

2.6.3

Chemistry of NO2 in the Atmosphere

Atmospheric photochemical reactions are particularly related to meteorological parameters such as temperature, pressure, wind speed and solar radiation. It also depends on the absolute concentration and the relative ratios of NOx (NO, NO2) and volatile organic carbons (VOCs) (Nevers 2000). The magnitude of ozone concentration variation is high in clear days as compared to cloudy days. Several studies found the relative higher concentration of ozone in weekends as compared to weekdays due to the relative low concentration of the ozone precursors (NOx and VOCs) at weekends (Cleveland et al. 1974; Sakamoto et al. 2005 and Qin et al. 2004). In the urban areas, NO is released from different emission sources and decreases the ground-level ozone concentration in absence of solar radiation, while in the rural areas, ozone concentration shows the comparatively less diurnal variability due to absence of NOx emission sources (Frey et al. 2013). Sillman (1999), Kley et al. (1999) and Jenkin and Clemitshaw (2000) have reported complete information of the

Fig. 2.6 World map of nitrogen dioxide tropospheric column density (1015 molecules/cm2) based on ozone monitoring instrument (OMI) onboard NASA’s Aura satellite during 2011. (Source: https://en.wikipedia.org/wiki/Nitrogen_dioxide)

2.6 Nitrogen Dioxide (NO2) 29

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ground-level ozone formation. The general mechanisms for catalytic O3 formation from the oxidation of VOCs and NOx by sunlight are well characterized. NOx are emitted into the atmosphere in the form of NO (nitric oxide) after the burning of fossil fuels. NO is transformed quickly (reaction (2.1)) during daytime to NO2 (nitrogen dioxide) via reaction with O3 already present at the surface. NO þ O3 ! NO2 þ O2

ð2:1Þ

Due to photolysis reactions (reaction (2.2)), nitrogen dioxide is again transformed to NO. In general, this particular reaction produces no net flux in reactions as a photo-stationary state is reached where concentrations of NO and NO2 becomes related to O3: NO2 þ hυ ðwavelength < 420 nmÞ ! O
O 3 P þ O2 ðþMÞ ! O3 ðþMÞ

3

P




ð2:2Þ ð2:3Þ

Though other daytime reactions (Jenkin and Clemitshaw 2000) change NOx, those are the consequences of the photooxidation of carbon monoxide (CO) and VOCs. The transitional compounds formed through those processes generate highly reactive free radicals, including the hydroperoxyl radical (HO2) and organo-peroxy radicals (RO2). These radicals also convert NO to NO2 (reactions (2.4) and (2.5)) but, in so doing, do not consume O3. Hence, the photolysis of NO2 (reaction (2.2)) followed by reaction (2.3) results in a net source of ozone. HO2 þ NO ! OH þ NO2

ð2:4Þ

RO2 þ NO ! RO þ NO2

ð2:5Þ

In particular conditions, formation of secondary aerosols during night-time conversion from NOx (including nitric acid, HNO3) at a particular geographic location, related transport and deposition was observed by Takemoto et al. (2001). Krupa (1997) reported an everyday pattern of urban O3 concentration and its precursors in the atmosphere, which emphasize the prevalence of daytime O3 production. The concentrations of nitric oxide and VOCs in the morning are high due to the presence of high volume of traffic on roads. These exhausts clean some of the O3 present (reaction (2.1)) and responsible for the production of NO2. A time later in the day, NO concentration reaches its height when NO is oxidized to NO2 without completely consuming O3. The above-mentioned reaction is balanced due to the presence of high quantity of hydrocarbons, mainly aldehydes in the atmosphere which lead to high NO2: NO ratio and a peak in O3 concentrations in mid- to late afternoon. Afterward throughout the day, NO2 exchange decreases (lower sunlight), and new exhaust of NO depletes the accessible O3.

2.6 Nitrogen Dioxide (NO2)

31

Apart from the above-mentioned, a significant chemistry also plays an important contribution in atmospheric chemistry in the absence of sunlight during night. Thus the night-time levels of OH are (approximately) zero. As an alternative, the nitrate radical, NO3, is formed during night by the reaction of NO2 with ozone. Moreover, NO3 radicals react with NO2 to set up a chemical equilibrium with N2O5 NO2 þ O3 ! NO3 þ O2

ðaÞ

NO3 þ NO2 $ N2 O5

ðbÞ

Reaction R6 occurs over the daytime. Nevertheless, NO3 is rapidly photolysed by sunlight, and as a result NO3 and its equilibrium associate N2O5 are both greatly dormant during the daytime. NO3 þ light ðλ < 590nmÞ ! NO2 þ O 3 P




ðcÞ

Figure 2.7 gives an impression of night-time chemistry. It is important to note that night-time chemistry could not be in isolation from daytime chemistry: reaction R6 needs ozone to oxidize NO2 to NO3, and ozone is a result of daytime photochemistry. The chemistry of the two most significant night-time variety, NO3 and N2O5, is explained below.

Fig. 2.7 Night-time chemistry in troposphere. The species coloured in red are generated only at night. DMS, dimethyl sulphide; hν represents a photon of light. (Source: ECG Environmental Briefs, ECGEB No. 3)

32

2.6.4

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Criteria Air Pollutants: Chemistry, Sources and Sinks

Sink of NO2

Wet and dry depositions are the two important processes for the atmospheric scavenging of the NO2 from lower atmosphere. Globally 24 (+ 9) million tonnes of average annual nitrogen removal is determined as –NO3 and HNO3 through dry and wet deposition, while a total of seven million tonnes of atmospheric N is scavenged by dry deposition of NO2 per year (Ehhalt and Drummond 1982). Crutzen expected that the worldwide sink for NOx ranges within 25 and 85 million tonnes of nitrogen per year (Crutzen 1983). Biological processes such as plant metabolism are also involved in the NOx exchange at the earth’s surfaces by plants. There are several factors affecting the exchange of NOx between plant canopy and atmosphere, and these factors include stomata gas exchange, light intensity, wind speed, canopy height, pollutant level in atmosphere and their solubility in aqueous medium (Johansson 1989; Fraquhar et al. 1983). The efficiency of these metabolic processes for NO2 assimilation is also studied (Rogers et al. 1979). NO2 is taken up by plants very fast than NO due to its high solubility of NO2 as compared to NO2 (Fraquhar et al. 1983; Johansson 1987). NO is also absorbed by the microbial activities, but the rate of absorption is relatively less as compared to NO2 absorption (Johansson and Galbally 1984). Both NO and NO2 are somewhat soluble in aqueous media, and the rate of their sink in surface waters is very small in absence of reactions in the water (Lee and Schwartz 1981). The nitrogen dioxide is removed from the atmosphere as nitric acids and nitrates through dust fall and rainfall. In these series of complex reactions involving OH radicals, NO2 combines with water vapour to form nitric acid. The overall reactions as follows: 4NO2 þ 2 H2 O þ O2 ! 4HNO3 Most of this nitric acid are formed in the aqueous phase aerosols. Some of the nitric acid reacts with ammonia and metallic particles in the atmosphere to form nitrates of ammonium. HNO3 þ NH3 ! NH4 NO3 Such type of particles is deposited after dissolution of nitrates in rain and snow. Thus the combine fallout contributes to acid deposition.

2.7

Sulphur Dioxide (SO2)

Sulphur is emitted into the atmosphere in various states of oxidation. Despite its ubiquity in all spheres of the globe, the most recognizable form of sulphur in the atmosphere is SO2 as it is a precursor for sulphate aerosol – a key component of PM. Sulphur dioxide is a colourless gas with nasty and sharp smell. About 99% of the sulphur dioxide in the atmosphere is released from anthropogenic sources.

2.7 Sulphur Dioxide (SO2)

2.7.1

33

Sources

The atmospheric sources of SO2 are natural as well as anthropogenic, but over the years, the anthropogenic component has increased overwhelmingly. The primary source of SO2 is combustion of coal and oil (which contain 1–2% sulphur by weight) with smaller contributions from other industrial activities such as metal smelting and manufacture of H2SO4 and industrial activity with material processing containing sulphur, e.g. the generation of electricity from coal, oil or gas that contains sulphur. Some mineral/ore processing industries also released sulphur dioxide into the atmosphere after mineral/ore processing containing sulphur. In the mineral processing, several types of gases and elements are released such as sulphur and sulphur dioxide. SO2 is the important result, produced after fossil fuels combustion. Motor vehicles are also important sources of sulphur dioxide in the atmosphere. SO2 can be oxidized to sulphur trioxide, which can be further transformed into sulphuric acid mist in the presence of water vapour. SO2 is a precursor to sulphates, which are one of the main components of respirable particles in the atmosphere. It simply reacts with other compounds to form toxic substances, like sulphurous acid (H2SO3) and sulphate particles.

2.7.2

Emissions of Oxides of Sulphur

The bottom-up mass balance approach is taken into consideration for the estimation of the global SO2 emission from 1850 to 2005, and the country level record data is generated through coal burning, petroleum processing, oil leakage from shipping, natural gas manufacturing steps, biomass combustion, pulp and paper processing, metal smelting and crop residue burning (CRB). The global emission found at highest in the 1970s and reduced until 2000, but further increase is observed with increasing emissions from China, international shipping and developing countries (Smith et al. 2011). It ascribed the decreasing tendency to alteration in fossil fuel use, rise in the quantity of sulphur release from oil and non-ferrous metals and control on coal-fired power plants. Several other emission estimates of quantification are comparatively mentioned in Smith et al. (2004). It was also found that North America and Europe are accountable for around 50% of the total global SO2 emission in 1990, whereas up to 50% or less represents the emissions from Asia in 2010 (Klimont et al. 2013). The directions to control emission from the power plants decrease the total emissions. Emissions and levels of pollutants in the Eastern USA largely affected the annual concentration of SO2 in the USA. At the end of the industrial revolution, Western Europe was identified as the highest global SO2 emitter in the world (Smith et al. 2011), whereas it was observed somewhat higher as compared to the USA and Canada. The highest SO2 concentration in Western Europe was observed during the 1970s, and after that there was a decline. The concentration of the SO2 emission in 2005 was found comparable to the 1890–1900 levels. The SO2 emission in USSR decreased after the collapse of USSR, whereas it was rapidly increasing in the 1940.

34

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The Chinese SO2 releases increased in the year 1940s and 2005, whereas a sharp increase in the emission is observed in the 1980s in India. Thus, overall SO2 emission in different countries was found in the order of China, USA, Europe, South and East Asia (Smith et al. 2011). Figure 2.8 indicates a world map describing region
/country-wise SO2 release during 2010. The high growth in the energyrelated sectors the coal combustion activities also raised leads to rise in the SO2 emission up to 73% in China (Gao et al. 2009). Other study indicated that around 53% of the total emission rose in years 2000–2006 due to its emission from power plants in China (Lu et al. 2010). After the policy implementation to curb air pollution emission (released from power plants), the emission growth rate becomes slower in the 2005, and decreasing emission was observed after 2006. The transport of the SO2 from the Asian continent to the SW area of Japan was also studied even though SO2 has short lifetime. Several air pollution reduction techniques are used to reduce the SO2 emissions from the power plants after 1990 and reported by the US Energy Information Administration (US EIA). These techniques include scrubbers, flue gas desulfurization (FGD) and use of coal having low sulphur content. Coal production was more in 2007 where an important amount of SO2 reduced (US EIA 2012). A long-term analysis (1989–2010) determination of SO2 concentrations was carried out in South Korea from 1989 to 2010 (Ray and Kim (2014). The investigators found that lower SO2 levels are observed from 2000 to 2010, which was 3–5 times higher than the values reported in the period of 1989 to 1999.

2.7.3

Levels and Trend of SO2

The global SO2 emissions were of the order of 115 Gg-SO2 during 2005 with China contributing 32 Gg-SO2 (~28%, Smith et al. 2011). Due to its profound impacts on human health and aquatic and terrestrial ecosystems including acid rain, SO2 has been regulated in power plants and transport sectors in various developed countries employing desulfurization and end-of-pipe abatement techniques. However, over the Asian region, anthropogenic SO2 emissions are not well-controlled and projected to increase under current regulations (Wang et al. 2013). SO2 can be toxic at high levels causing reduced respiration, inflammation of the airways and lung damage (ATSDR 1998). Plants exposed to high levels of SO2 incur acute foliar injury, where it can be oxidized to sulphite, which is very toxic and can interfere with photosynthesis and energy metabolism. The SO2 emissions over India were estimated at 8.8 Tg for 2010 with sector-wise contribution of 66% and 32% from power plant industries and fuel-wise contribution of 76 and 19% from coal and oil, respectively, to the national SO2 emissions (Lu et al. 2010). High SO2 levels have been detected in ambient air of megacities like Beijing (60 ppbv in winter, Lin et al. 2011) and Kolkata (6.4 ppbv in winter, Mallik and Lal 2014). For India, the National Ambient Air Quality Standards require annual average SO2 to be less than 30, 23 and 5.7 ppbv for industrial, residential and sensitive areas, respectively. Several precursors of SO2 in lower oxidized state (reduced sulphur compounds, RSCs), including dimethyl

Fig. 2.8 Anthropogenic emissions of sulphur dioxide in 2010, gridded by 0.5x0.5 degree. (Source: Klimont et al. 2013)

2.7 Sulphur Dioxide (SO2) 35

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Criteria Air Pollutants: Chemistry, Sources and Sinks

sulphide (DMS), hydrogen sulphide (H2S), carbon disulphide (CS2) and carbonyl sulphide (COS), contribute significantly to the global sulphur budget. Once released into the atmosphere, these are oxidized to produce SO2. Landfills are a major source of anthropogenic RSCs. Due to its comparatively long lifetime, COS is able to penetrate into the stratosphere where its photolysis and subsequent oxidation contributes to the stratospheric sulphate layer. Being the major precursors of sulphate aerosols which exert a negative radiative forcing on the atmosphere, sulphur gases indirectly play a crucial role in the earth’s radiative balance and are of great interest to geoengineering (climate engineering) experts.

2.7.4

Chemistry of SO2

Sulphur dioxide in the atmosphere reacts with oxygen and generates sulphur trioxide (SO3), which then reacts with water vapours to form sulphuric acid. The hydroxyl radicals and few reactions in sequence participated in the mechanism and mentioned as follows: SO2 þ OH0 ! HSO03 HSO03 þ O2 ! SO3 þ HOO0 ðgÞ H2 SO4 þ H2 O ! H2 SO4 ðaqÞ This freshly generated sulphuric acid in the atmosphere concentrated near the base of cloud, where the pH levels near about or below 3 have been recorded. In the presence of significant amount of the water in air, some of the atmospheric SO2 get dissolved into it. In this case, most of the oxidation of SO2 to H2SO4 occurs in the liquid phase rather than the gas phase. After the dissolution of the SO2 in water, it easily converted to sulphurous acid (H2SO3). SO2 ðgÞ þ H2 O ðaqÞ $ H2 SO3 ðaqÞ The levels of the H2SO3 is analysed by the equilibrium constant for this reaction. H2SO3 has a large enough Ka (1.7x10
2) that in the atmospheric aerosols it consequent ionized to HSO3-, bisulphite ion:
H2 SO3 $ HSO
3 ðaqÞ þ H ðaqÞ

Due to the equilibrium between gaseous SO2 and dissolved H2SO4 (aq), that [H2SO3(aq)] corresponds to only H2SO3 that does not ionized to bisulphite, and it remains at constant 1.0  10
7 M. The dissolved SO2 is oxidized by minute quantity of hydrogen peroxide (H2O2) and ozone (O3) that are also present in aerosol droplets to sulphate ions (SO42
). In the further step, the ozone and hydrogen peroxide are the products of the

2.8 Tropospheric Ozone (O3)

37

photodissociation reactions in the photo chemical smog. The reactions can be written as follows:
HSO
3 þ H2 O2 $ H2 O þ HSO4

This is the acid-catalysed reaction but the reaction with ozone is unaffected from acid.
HSO
3 þ O3 $ O2 þ HSO4

Oxides of sulphur become adsorbed onto the particle surfaces and may be carried out to the larger distances from their sources before their deposition (dry/wet deposition). Like nitric acid and nitrate formed from NOx, sulphuric acid, sulphate and particulate all contribute to acid deposition.

2.7.5

Sink of SO2

There are three most important pathways for the removal of the SO2 from the atmosphere: (1) oxidation (gas-phase homogeneous photochemical reaction with other minor components in cloud droplets), (2) wet deposition of SO2 (in-cloud scavenging or below-cloud scavenging) and (3) direct deposition of SO2, at the land. It has been observed that in the polluted area, the direct deposition of the SO2 may play a major role for the atmospheric removal of SO2 (Garland and Branson 1976). The observation of the SO2 dry deposition have been done at different land use pattern and topography in the last few decades, including grassland, desert area, bare soil, croplands and forest (Brook et al. 1999). Scavenging through aerosol and its deposition to the ocean’s plane are the important sinks for SO2. No studies reported a comparative significance of these elimination methods, due in large part to the lack of an autonomous technique for determining SO2 deposition to the surface (Faloona et al. 2009). The ocean deposition flux is measured by a Pacific Atmospheric Sulfur Experiment (PASE), which has two main advantages over field experiments in the assessment of marine sulphur budget: (1) the dimethyl sulphide (DMS) ocean flux is calculated, by suppressing the major source of sulphur in the atmosphere, and (2) the SO2 deposition to the ocean surface is also directly calculated limiting major sinks.

2.8

Tropospheric Ozone (O3)

Ozone is found both in the troposphere and in the stratosphere. Tropospheric ozone contributed about 10% of the total ozone present in the atmosphere. It is also called as the bad ozone due to its very significant role in the formation of photochemical air pollution and oxidizing nature in the atmosphere (Krupa and Manning 1988). It is one of the important greenhouse gases present in the atmosphere. The permissible limits of the tropospheric ozone are already mentioned in Table 2.1. Ozone

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Criteria Air Pollutants: Chemistry, Sources and Sinks

concentrations in the lower atmosphere typically range from less than 10 ppb (remote tropical oceans) to 100 ppb (upper troposphere) and usually surpass 100 ppb downwind of polluted metropolitan cities (IPCC 2001). The stratospheric ozone layer is the naturally occurring jacket of O3 molecules, while most of the tropospheric ozone is formed via man-made sources (Aneja et al. 2001). Stratospheric O3 is helpful in protecting the biosphere, but the tropospheric O3 is harmful to the plants (Aneja et al. 1991). Ozone is heavier than air; it is brought down from the stratosphere by vertical winds produced during electrical storms (Kasibhatla 1993). However, the tropospheric O3 is produced when sunlight reacts with nitrogen oxides, and hydrocarbons are emitted by the combustion of coal or petroleum fuels (Finlayson-Pitts and Pitts 1997). When oxidant levels in the air are high, more than 90% of the air is ozone. These levels are usually at their highest point in the afternoon and are relatively low at night (Atkinson 2000). The formation of the tropospheric ozone is a non-linear process and form from the various precursors such as volatile organic carbon (VOCs), oxides of nitrogen (NOx) and carbon monoxide (CO). The formation of the ozone can also be affected by the regional pollutants (NOx and VOCs) transported from a distant location through long-range transport under the influence of the regional weather patterns. The ambient level of O3 is highest during summer, calm, spring and sunny days where primary pollutants are already present in the atmosphere. It was reported that the O3 levels can be higher in the rural area as compared to the urban. It was also observed that the O3 at high altitude can be comparatively stable all over the day and night (Seinfeld and Pandis 1998). The tropospheric O3 is of global concern due to its importance in greenhouse effect. OH radical (oxidizing agent) is one of the important precursors of the tropospheric ozone. Several models have been developed for the understanding about the factors controlling the tropospheric ozone concentration which further help for better understanding of emission control studies for ozone (NRC 1991). But these models are basically limited to the study performing for the identification of the ozone levels and its precursors such as HOx, NOx and hydrocarbons. Wet deposition can have an important but indirect role in the atmospheric scavenging of the tropospheric ozone, which was found involved in the scavenging of nitric acid and hydrogen peroxide which are pools for NOx and HOx. It was also mentioned earlier that a simple below-cloud scavenging of nitric acid and hydrogen peroxide parameterization can explain the wet deposition in the ozone model (Giorgi and Chameides 1985). It is also mentioned that the precipitation form, cirrus, may be a significant sink for the nitric acid in the upper atmosphere (Lawrence and Crutzen 1998).

2.8.1

Chemistry of Tropospheric Ozone

Figure 2.9 is an explanation of gas-phase O3 chemistry in the troposphere highlighting the pairing within the cycles of O3, HOx and NOx. Ozone is transported from stratosphere to troposphere via stratosphere-troposphere exchange (S-T exchange). It is removed by dry deposition onto the surfaces. A fraction is consumed

Fig. 2.9 A schematic diagram of the sources and sinks of O3 in the troposphere. (Source: IPCC Fourth Assessment Report Working Group I Report “The Physical Science Basis”)

2.8 Tropospheric Ozone (O3) 39

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Criteria Air Pollutants: Chemistry, Sources and Sinks

in chemical reaction within the troposphere. For budgeting purpose, one has to calculate the chemical production and loss of O3 with all precautions in order to reduce uncertainty especially in the troposphere (Wang et al. 1998; Hauglustaine et al. 1998)

2.8.2

Sinks of the Tropospheric Ozone

First processes involved in the sink of the tropospheric ozone are the photochemical reaction (y1), where O3 molecules break by sunlight. In the presence of an environment rich in NO, the reaction (y2) controls the ozone destruction.
O3 þ hν ðλ < 320 nmÞ ! O2 þ O 1 D

ðy1Þ

O3 þ NO ! O2 þ NO2

ðy2Þ

On contrary, in NO-deficient atmosphere, the oxidation of CO2 can lead to ozone loss. After the y3 and y4 reactions, the produced HO2 reacts with ozone as an alternative to reaction y5: OH þ CO ! H þ CO2

ðy3Þ

H þ O2 þ M ! HO2 þ M

ðy4Þ

HO2 þ NO ! OH þ NO2

ðy5Þ

HO2 þ O3 ! OH þ 2O2

ðy6Þ

Further, ozone can be destroyed by the direct reaction with OH radical: OH þ O3 ! HO2 þ 2O2

ðy7Þ

After the chemical dissociation, O3 is eliminated from the atmosphere through dry deposition, which is highly effective during unstable atmospheric conditions. Since ozone is considered as a phototoxic agent, it has the most damaging impact on plant metabolism as compared to other pollutants in the troposphere.

2.9

Conclusions

Till now, several studies have been involved in the determination and identification of the source, atmospheric chemistry and sink of the criteria pollutants. The criteria air pollutants are the pollutants responsible for several deleterious health effects after their exposure to the human being. Of the many pollutants, particulate matter, sulphur dioxide, nitrogen dioxide, carbon monoxide, lead and tropospheric ozone are ubiquitous and widely monitored for ambient levels, sector-wise contributions,

References

41

regional emission inventories and global trends over the past decades. These criteria pollutants also have air quality standards associated with them to enable their monitoring and regulation. Fossil fuel combustion is a major anthropogenic source of NOx, and over 60% of the global energy demand is met by coal and oil followed by natural gas, renewable and nuclear energy. The concentration of O3, CO, NOx and hydrocarbons greatly influences the radical balance and the self-cleaning capacity of our atmosphere. A very high concentration of sulphur dioxide was observed in the 1970s after the industrial revolution and was found decreasing in the late twentieth century. Nevertheless, China and other developing countries were observed with a high level of increasing SO2 in recent time. The daytime and night-time chemistry of the pollutants is widely discussed by several authors in different atmospheric conditions. The initial initiatives to curb air pollution were taken in the transport sector by switching fuel, changing emission norms and the involvement of the new pollution control technologies especially for the control of PM in the developed nations in the world. The reduced lead level in petrol also changes the lead concentration in the ambient atmosphere. The technological modifications in power plants are one of the leading causes for the significant decline in the total PM pollution. The well-established link between human emissions/ activity and climate and its repercussions is a matter of serious concern. The impact of human activities on the earth system has been so profound that scientists are pressing for a declaration of “Anthropocene” as an epoch. The damages cannot be undone completely and people, societies and governments must seriously start making concerted efforts to limit and abate polluting the atmosphere as each of us is a stakeholder in the present and future of the earth’s atmosphere and climate.

References Abraham FF (1974) Homogeneous nucleation theory. Academic, New York. Air quality criteria for carbon monoxide. Washington, DC. US Environmental Protection Agency, Office of Research and Development, 1991 (publication no. EPA-600/B-90/045F) Altshuller AP (1983) Review: natural volatile organic substances and their effect on air quality in the United States. Atmos Environ 17(11):2131–2165 Aneja VP, Businger S, Li Z, Claiborn CS, Murthy A (1991) Ozone climatology at high elevations in the southern appalachians. J Geophys Res Atmos 96(D1):1007–1021 Aneja VP, Agarwal A, Roelle PA, Phillips SB, Tong Q, Watkins N, Yablonsky R (2001) Measurements and analysis of criteria pollutants in New Delhi, India. Environ Int 27(1):35–42 Anisimov MA (2003) Nucleation: theory and experiment. Russ Chem Rev 72:591 Atkinson R (2000) Atmospheric chemistry of VOCs and NOx. Atmos Environ 34(12–14):2063– 2101 ATSDR (1998) Agency for toxic substances and disease registry. Toxicological profile for sulfur dioxide. US Department of Health and Human Services, Public Health Service, Atlanta Barry PSI (1981) Concentrations of lead in the tissues of children. Br J Ind Med 38:61–71 Barry PSI, Mossman DB (1970) Lead concentrations in human tissues. Br J Ind Med 27:339–351 Boubel RW, Fox DL, Turner DB, Stern AC (1994) Effects on materials and structures, fundamentals of air pollution, 3rd edn. Academic Press, New York Boutron CF et al (1991) Decrease in anthropogenic lead, cadmium and zinc in Greenland snows since the late 1960s. Nature 353:153–156

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3

Primary Criteria Air Pollutants: Environmental Health Effects

Abstract

A polluted air is a harmful complex combination of primary and secondary pollutants in the atmosphere. The US Environmental Protection Agency (USEPA) listed the six most common air pollutants as criteria air pollutant under the Clean Air Act. The primary criteria air pollutants (CO, SO2, NO2, PM and Pb) are released into the atmosphere directly from their emission source. Due to their highly reactive nature, they get easily participated in a variety of reactions during atmospheric chemical transformation reactions. Due to the dry and wet deposition process, they may easily settle down onto ground/vegetation/ ecosystems/water surfaces/building materials and show negative impact on their health/life/durability/beauty. The primary criteria air pollutants also produce adverse health effects to human being after their short-term/long-term exposure. Asthma, bronchitis, lung cancer and cardiopulmonary problems are the major noticed due to inhalation exposure of these pollutants. Mental disorder, kidney disorder and abortion are other harmful impacts. The WHO reported the level distribution and harmful effects of air pollutants several times in the past few decades. The direct and indirect effects of criteria air pollutants in changing climate are also discussed. Keywords

Air pollution · Human health · Atmospheric processes · Impacts

3.1

Introduction

The Clean Air Act (CAA) of 1970 identified six common air pollutants of concern, called criteria air pollutants, viz. particulate matter, tropospheric ozone, carbon monoxide, nitrogen dioxide, sulphur dioxide and lead. The previous chapters of this book already discussed about the sources, level distributions, atmospheric chemistry and sinks of these criteria pollutants. As per the origin/emission, criteria # Springer Nature Singapore Pte Ltd. 2019 P. Saxena, Criteria Air Pollutants and their Impact on Environmental Health, https://doi.org/10.1007/978-981-13-9992-3_3

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3 Primary Criteria Air Pollutants: Environmental Health Effects

pollutants are categorized into primary and secondary air pollutants. Primary pollutants are released directly into the atmosphere from their respective sources, whereas the secondary pollutants formed through atmospheric transformation reactions in participation either with primary air pollutants or other chemicals in the atmospheres. The primary criteria pollutants include particulate matter (PM), tropospheric ozone (O3), carbon monoxide (CO), sulphur dioxide (SO2), nitrogen dioxide (NO2) and lead (Pb). Several governmental and nongovernmental agencies have discussed about the burden of primary air pollutants in the atmosphere; they had also discussed about the environmental health impacts due to their increasing levels across the world especially in developing nations. The rapidly growing population, urbanization and industrialization are the most significant factors for degrading the air quality particularly in Asian countries. Urbanization is a significant factor for the increase in air pollution in many cities in Asia, Africa, the Near East and Latin America (Ashmore 2005). In the year 1960, less than 22% of developing world’s population was urban, and the increment is 34% by 1990. As per extrapolations, population is expected to increase by 50% in urban areas by 2020 (World Bank 2009). The uncontrolled use of fossil fuels in industries and transport sectors has also become the dominant source of gaseous pollutants like SO2, NOx, VOCs, etc. and also the particulate matter. These anthropogenic activities pose a huge burden on environmental health and have several impacts such as increased mortalities and morbidities, degradation in ecosystems, impact on crops and biodiversity loss, etc. These conditions of atmospheric pollution significantly affect humans, animals, vegetation, or materials (Seinfeld 1986). The sources of air pollution already discussed in previous chapters briefly include both natural and anthropogenic sources. The natural sources can be forest fire, emissions from trees, lightning, volcanic eruptions and erosion of surfaces of rocks/minerals/buildings. On the other hand, anthropogenic sources comprise of transportation, biomass burning, industrial activities, vehicular emissions, mining, etc. (Chandrappa and Kulshrestha 2015). The exceeding levels of the criteria air pollutants in the atmosphere affect adversely both the living (plants, animals and human beings) and nonliving things (materials and buildings). Earlier the air pollution was considered as a local problem, but now it is a regional and global concern due to the application of tall stacks and long-range transport of pollutants. Remote area also suffers from large amount of pollution load and their impacts due to the transboundary movement. Apart from the urban air pollution sources, rural areas also have large amount of the pollutants into the atmosphere due to the activities such as biomass burning, crop residue burning and cooking activities using dung cake, coal and wood. The impacts of these air pollutions released from different sources not only cause mortalities but also morbidity and shortening of life expectancy. The present chapter focused on the discussion about the environmental health effects by the exposure of primary criteria air pollutants. The environmental effects include human health, acid rain, eutrophication, haze, global climate change and impacts on crops and forests.

3.2 Environmental Health Effects

3.2

51

Environmental Health Effects

Industrialization and urbanization are the major causes for the degradation of the environment. Since the last three decades, many authors explained the untold relationships between air pollution and health effects due to air pollution exposure. Most commonly discussed environmental health-related issues include acid rain, eutrophication, haze, global climate change and impacts on crops and forests. Human health is also considered under the umbrella of environmental health effects, which further includes cardiovascular diseases, respiratory (asthma and changes in lung function) and pregnancy outcome and even deaths.

3.2.1

Impact of SO2 and NO2 on Environmental Health

3.2.1.1 Acid Rain Precipitation in the form of rain, hail or snow is known as acid rain. The term “acid rain” was first used in 1972 after the discovery of acid rain by Robert Smith in 1852. Broadly, wet deposition (rain, cloud water, snow, dew, hail, fog) and dry deposition (SO2, NOx, other acidic gases and particles) of acid compounds are responsible for the acid rain. Natural and anthropogenic sources emitted large amount of the SO2 and NO2 gases into the atmosphere. Both natural sources (volcano emissions, lightning and microbial processes) and anthropogenic emission sources (industrial and vehicular emissions) are the important sources of oxides of sulphur and nitrogen. Both oxides act as precursors for the sulphuric acids and nitric acids in the atmosphere. Acid rain (pH range, 4.2–4.7) is one of the leading problems of regional air pollution. It is the result of transformation of atmospheric sulphur and nitrogen emitted from different sources across the different locations throughout the world. The high level of these gases causes the high acidity. Increased combustion of the fossil fuels after industrial revolution causes acid rain. The atmospheric transformation reactions converted them into the sulphuric acid and nitric acids (Fig. 3.1). The normal pH of the rainwater in the unpolluted atmosphere is around 5.6 due to the presence of carbonic acid formed after dissolution of the carbon dioxide (CO2) in cloud water. CO2 þ H2 O ! H2 CO3 Carbonic acid further dissociates to form bicarbonate ion in the water: þ H2 CO3 $ HCO 3 þH

Further decrease in the rainwater pH in the unpolluted area is due to the presence of the organic acids. Moreover, the formation of the sulphuric acid and nitric acid in the atmosphere is a result of oxidation of the SO2 and NO2.

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Fig. 3.1 Process involved in the acid rain. (Adopted from Sonwani and Maurya 2018)

SO2 þ OHo ! HOSO2 HOSO2 þ O2 ! HO2 þ SO3 SO3 þ H2 O ! H2 SO4 Homogeneous aqueous phase reaction of SO2 takes place by its dissociation in the water. SO2 þ H2 O $ SO2 H2 O þ SO2 :H2 O $ HSO 3 þH  þ HSO 3 $ SO3 þ H

NO2 undergo gas phase oxidation reaction (faster as compared to SO2): NO2 þ OHo ! HNO3 Apart from the above-mentioned reactions, nitric acid also forms by NO3 radical reactions, in which NO3 radical forms by the reaction between NO2 and tropospheric O3 during daytime. NO2 þ O3 ! NOo3 þ O2

3.2 Environmental Health Effects Table 3.1 Showing critical pH level of aquatic animals

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Animal Frogs Perch Salamanders Trout Mayfly Crayfish Bass Snail Clams

Critical pH levels 4.0 4.5 5.0 5.0 5.5 5.5 5.5 6.0 6.0

NOo3 formed at days and is consumed at night after reaction with NO2, resulting in the formation of HNO3: NO 3 þ NO2 $ N2 O5 N2 O5 þ H2 O $ HNO3 Gas-particle reactions of SO2 and NO2 undergo heterogeneous oxidation reaction. SO2 is quickly converted into sulphate by H2O2 in liquid phase. The surface of the freshly emitted soot is involved in the formation of sulphate by oxidation of SO2. But after achieving saturation condition by particle surface, the rate of oxidation reduces. Region having high level of dust, where the oxidation of the SO2 takes place onto the soil dust particles, leads to the formation of the calcium sulphate (CaSO4) rather than sulphuric acids (H2SO4). On the other hand, the oxidation of NO2 takes place with the salts and forms sodium chloride (NaCl) and sodium nitrate (NaNO3). Moreover reactions get slower on saturation of the particles surfaces.

Impact of Acid Rain on Ecosystem Table 3.1 shows the crucial concentrations of different types of organisms at which they may lose their life due to rising acid in their surroundings. An ecosystem is an interface of diverse community of plant or animals with their environment. Any disorder in any part of the ecosystem may damage the function of other life forms significantly.

Impact of Acid Rain on Plants and Trees Plant exposure to acid rain causes several damages related to their foliage and leaf which make them vulnerable for several bacterial and viral infections and harmful UV radiation coming from sun At high altitudes, acidic rain can remove nutrients from trees’ foliage, leaving them with brown or dead leaves. The trees are then less able to absorb sunlight, which makes them fragile and unable to withstand freezing temperatures.

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Impact of Acid Rain on Fish and Wildlife Table 3.1 is showing the critical pH levels for different aquatic animals. The acid rain significantly alters the pH of the aquatic environment such as pond, river, lakes, and marshy lands which ultimately harm the life forms. Acid rain is responsible for lowering the pH of soil and water which makes the water unfit for life forms in water bodies. As it flows through the soil, acidic rain water can leach aluminium from soil clay particles and then flow into streams and lakes. Thus it makes that particular soil deficient in aluminium. Some of the plants and animals tolerate the acidic and aluminium-rich water ecosystem. But several sensitive animals lose their life due to the lowering in pH of water bodies. Generally, young one and elderly animals are very sensitive to these changes. At pH 5, most of the fish eggs cannot hatch. Most of the non-chordates barely survive at pH 5, while frogs have a critical pH around 4, but the mayflies they eat are more sensitive and may not survive pH below 5.5. Some of the areas are not affected by the acid rain, and it is due to the special properties of the soil of that location. This type of soil has some buffering capacity to neutralize the acidity of the rainwater. This property of soil depends on the thickness, composition of the soil, and the type of bedrock underneath it. Episodic Acidification The melting of snow and heavy rain which happen in the absence of soil (with buffering capacity) deposit high amount of acids into the lakes (with very less acidity in normal days). This short duration of higher acidity (i.e. lower pH) may result in a short-term stress on the ecosystem where a variety of organisms or species may be injured or killed. The melting snow and heavy rain shower can cause increase in lake’s acidity known as episodic acidification. Effects of Acid Rain on Materials Acid rain causes the damage in the stone and paint of the building of historic/cultural importance such as monuments, statues, tombstone, and sculptures. Bronze, limestone, carbon steel, marble, paint, and some plastics are the most vulnerable to acid deposition. The materials (foundations and pipes) immersed into the acidified water also suffer the problems of corrosion. With the effect of acid rain, calcium carbonate dissolves in dilute sulphuric acid to form calcium sulphate: CaCO3 þ H2 SO4 þ H2 O ¼ CaSO4: 2H2 O þ CO2 The process causes some effects including the removal of details by breaking stones and build-up of black skin of gypsum (calcium sulphate) in the sink areas in buildings. Once the crystal of gypsum forms into the stone, the procedure may persist up to 50 years, known as memory effect. Several studies were found linked with the impacts of acid deposition on diverse materials. Taj Trapezium Case (also known as MC Mehta Taj Trapezium Case) is one of the good examples of acid rain effects on building material. The yellowing of the Taj marbles was the major issues under Taj Trapezium Case. This petition was related to the deteriorating

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magnificence of Taj Mahal which was invoking for Air Act 1981 and Water Act 1974 and Environmental Protection Act 1986. The purpose behind this petition was to relocate 292 factories to prevent Taj from the emission released by the companies using coke or coal as energy sources. In this case several reports were drafted and presented which relate the pollution emission from Agra-Mathura region and its impact on Taj. These reports include one NEERI report, two Varadharajan reports and reports by the State Pollution Control Board (SPCB). They statistically explained that replacing coal by diesel in the railway yards and closing down two thermal power stations, sulphur dioxide emissions can drop down by 50%. The court on April 11, 1994, after hearing the learned counsel for the parties passed the order indicating that as a first phase, the industries situated in Agra be relocated out of Taj Trapezium Zone (TTZ). The judgement was taken by the court after considering sustainable development principle, precautionary principle and polluter pays principle. The final judgment in this case was given on December 30, 1996, and the bench consisted of Justice Kuldip Singh and Justice Faizan Uddin.

Acid Rain Effects on Human Health Acid rain has no direct role in deteriorating the human health due to their exposure. But, the compounds causing acid rain can drastically harm after their exposure to human. There are a variety of exposure ways such as dermal, ingestion and inhalation through which harmful chemicals/pollutants enter into the human body and create adverse health impacts on human health. The SO2 and NO2 pollution that causes acid rain is more harmful to human health. Particularly, sulphur dioxide and particulate matter in the atmosphere may create chronic pulmonary problems. Furthermore, the oxide of nitrogen is responsible for acid rain and triggers the development of tropospheric ozone. This tropospheric ozone creates pulmonary trouble and is responsible for disease such as chronic pneumonia and emphysema.

3.2.2

Particulate Matter and Its Impact on Environment

Particulate matter (PM) is a solid or liquid and heterogeneous material present in the atmosphere of earth. Due to its spatial and temporal variations, it is hard to find the impacts of the particulates at regional/local scale. Particulate is deposited on the vegitative surfaces of the plant, and thus it significantly affects the plant metabolism after exposure. The impact of particulate on the plant depends on the physicochemical property (size, surface morphology, source origin and chemistry of the PM). Coarse (PM10) and fine (PM2.5) particulate matters have a number of contrasting properties that affect their impact on vegetated systems since two decades. PMs are having a great matter of concern due to its impacts on ecosystem function and huge potential importance for human welfare (Ayensu et al. 1999; Prajapati and Tripathi 2008a, b, c; Telesca and Lovallo 2011).

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3.2.2.1 Deposition of PM This is the process due to which the particulate matter is deposited onto some surface (solid/water/vegetative surface) resulting in the lowering of their concentration in the atmosphere. According to McDonald et al. (2007), plants play a very significant function in filtering ambient air through leaf surfaces. The plants having larger leaf surface area were identified as the efficient PM collector as compared to the trees having less leaf surface area. Similarly, broad leaves with rough surface area are found to be a good PM absorber than other plants having smooth surface (Beckett et al. 2000). Deposition of PM (mixture of organic and inorganic substances as solid and liquid) onto various surfaces at definite mass concentration causes various types of phytotoxic responses (Tasic et al. 2006). Deposition of particulate matter on vegetation includes (a) nitrate and sulphate and their deposition in the form of acidic components and (b) trace element and heavy metals. According to McLachlan (1999) and Welsch-Pausch et al. (1995), particulate-bound trace elements may be absorbed through the stomata or be settled on the leaf. Contrarily, polycyclic aromatic hydrocarbon (PAHs) can be collected in leaves by (i) gas-particle partitioning, (ii) dry vapour deposition and (iii) deposition with particle, depending on the physicochemical nature of the examined compound (McLachlan 1999; Welsch-Pausch et al. 1995) and can also absorbed through soil, after their deposition on to the soil surfaces. 3.2.2.2 Coarse (PM10) and Fine Fraction (PM2.5) Particles Particle size is one of the factors related to the damaging effect of the PM; the larger size particles settle near to their source of emission as compared to the finer particles, which are usually deposited away from their source of origin. This difference is due to the difference in their residence time in the atmosphere, where larger particles have less residence time in the atmosphere as compared to the finer particles. The size of PM correlated significantly with specific leaf area, but Chl a, Chl b, carotenoid and relative water content were negatively correlated with PM fraction (Chen et al. 2015). The size of the particle is also correlated with the chemical constitution of particles (as fine mode particles are found rich in S, N and organic contents, whereas coarser mode particles are rich in base cation and heavy metals). Fine particulate matters are found associated with the combustion-related emission sources, while coarse particles are generally found associated with crustal material. Various meteorological parameters like atmospheric humidity, precipitation and wind speed affects the deposition process through different mechanisms. Figure 3.2 shows examples of particulate matter sources in relation to particle diameter. Fine particulate matter exists in vapour phase in the atmosphere in contrast to the coarse particulate matter which has been produced from point source as fully formed particle. Fine PM is secondary in nature and formed into the atmosphere by chemical reaction from gas precursors through series of process, nucleation, condensation and coagulation. Fine particle contains oxides of nitrogen and sulphur (NOx and SOx). It also consists of volatile organic compounds, volatile metals and products of incomplete combustion. Coarse PM is produced from mechanical processes like crushing,

Fig. 3.2 Particulate matter, size ranges and their sources. (Adapted from Saxena et al. 2016)

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Table 3.2 Type and determinants and factor controlling particulate deposition on vegetation Type of deposition Dry deposition

Wet deposition

Occult deposition

Determinant of deposition Ambient levels

Quantifiable factors Source location, emission potency

Meteorological variables Nature of aerosol particles Surface roughness Vegetation condition Ambient levels

Wind speed, wind direction, dew formation, mixing height, temperature and humidity Chemical reactivity, particle solubility, aerodynamic diameter, bioavailability, hygroscopic nature Terrain type, leaf pubescence, leaf shape, plant tissue arrangement, plant density, branch spacing Surface wetness, salt exudates, organic exudates, insect excreta Source distance, emission potency

Meteorological variables Nature of aerosol particles Surface roughness As above

Mixing height, precipitation time, precipitation intensity, time period of precipitation Chemical reactivity, particle solubility, biological availability Terrain discontinuity, leaf pubescence, leaf area index, nature of exposed bark and stem Combination of above factors

Adapted from Gratz et al. (2003)

abrasion, soil disturbances and expansion of fine particle to coarse PM by the effect of humidity.

3.2.2.3 Mode of Depositions The rate of particle deposition onto the vegetative surfaces depends on dust properties, characteristic of location of plant and nature of receiving material (Grantz et al. 2003; Chen et al. 2015). It also can be associated with several other factors such as diming in solar light, changes in the leaf surface temperature, etc. The exchange of energy into and out of the leaf is highly influenced by particulate matter load, size and colour as compared to gases (Rahul and Jain 2014). The effect of PM onto the vegetation is mentioned in Table 3.2 given by Grant et al. in 2003. There are three major pathways identified for the particulate deposition onto vegetation surface: (1) dry deposition, (2) wet deposition and (3) occult deposition. Dry Deposition Dry deposition is a collective elimination of particles from the atmosphere under the influence of some factors such as gravity, direct interception, impaction and Brownian motion. Dry deposition process is continuous and works under the influence of gravitational force especially for the larger particles (larger than few micrometers in diameters). It is the continuous process as compared to the wet and occult deposition and affects all exposed surfaces (Hicks 1986). Fine particulate

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matters play a very significant role in deposition of the organic compounds (polycyclic aromatics hydrocarbons, dioxins and dibenzofurans,) on to plant surfaces (Lin et al. 1993). PM deposition is also influenced by fog formation through particle removal from atmosphere, through particle growth by aqueous phase oxidation reaction (Pandis and Seinfeld 1989). The atmospheric key pollutant species like 2 NO 3 , SO4 and organics are present in higher concentration in smaller droplets as compared to larger one (Collett et al. 1999). Wet Deposition It is known for the removal of the soluble gases and particulate matter from air through the precipitation events. In wet deposition processes, hydrometeors (raindrop, snow, etc.) play a very important role in scavenging the particulate matter. It is influenced by gravity, Brownian motion and/or turbulent coagulation with water droplets. There are two basic types of wet deposition reported: (a) Below-cloud scavenging (washout): It is the scavenging of aerosol present below the cloud base by raindrop. It scavenges dissolve particle and gases along their fall. It is happening under the influence of interception, Brownian diffusion, impaction and turbulent diffusion. (b) In-cloud scavenging (rainout): It is the condensation of water vapour on aerosol particle during the formation of cloud droplets. These can be brought to the ground surface through precipitation events such as rainfall and snow form during the cloud formation. The wet scavenging for gasses depends on their solubility and parameterization following Henry’s law. Moreover, the scavenging of the aerosol depends on the size, shape and properties of the aerosol. Occult Deposition The windblown mist and fog are usually considered as occult deposition, and such type of wet deposition is not recorded by the rain gausses. Occult deposition is basically linked to the scavenging of the primary air pollutants and removal of the ground-based cloud which is common at high altitude (Fowler et al. 1989). The proportion/dominancy of the type of the deposition of gases and PM depends on the meteorological conditions and location.

3.2.2.4 PM Deposition onto Vegetation and Their Effects Deposition of PM on plants is affected by the particle size, dimensions and density of the foliage elements in the dispersion path. PM can cause several adverse impacts on plants and is responsible for stomata clogging, reduced photosynthetic activity, leaf fall and death of tissues (Farooq et al. 2000; Shrivastava and Joshi 2002; Garg et al. 2000). Due to PM deposition, many physicochemical changes take place on aerial parts of plants (Grantz et al. 2003). A major proportion of the stomata may be covered by PM which reduces the rate of transpiration and rate of evaporative

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cooling (Sharifi et al. 1997). PM deposition on plant materials is also responsible for the chlorosis in the leaf and ultimately affects chlorophyll content (Seyyednejad et al. 2011). Due to the presence of several dust types (fertilizer or lime), a number of adverse effects were caused to the plant after being exposed to PM. These plant responses are the result of the dust chemistry in the atmosphere. Other study also reported the impact of the air pollutants (PM, SO2, NO2 and O3) on crop yield by considering emission trend, movement of air parcel and leaf uptake and plant’s biochemical defence mechanism (Rai et al. 2011). Agrawal et al. (2003) reported SO2, NO2 and O3 and related plant responses measured in terms of physiological characteristics, pigment, biomass and yield and found that air pollutant affects the crop yield negatively. Several chamber-related studies also reveal that particulate air pollution is responsible for commercial yield and biological parameters of several important crops (Wahid et al. 1995; Schenone and Lorenzini 1992; Heggestad and Lesser 1990). Joshi et al. (2009) reported the impact of industrial air pollutants (SPM, RSPM, NOx and SO2) on biochemical parameters like Chl a, Chl b, total Chl, carotenoid and ascorbic acid and yield in wheat and mustard plants. Parish (1910) is the earliest study, concerning cement particulate matter deposition onto shrub and grassland vegetation in California. Due to these cement industries, several plants become extinct like Artemisia californica, Encelia farinosa and Salvia apiana. The most effective deposition of the PM on grassland was reported by Krippelova (1982) near a magnesite factory in Czecho-Slovakia, and it was observed that the deposition of the emission from the industry caused formation of the soil surface crusts having pH ~9.5. Some studies related to limestone PM emitted from limestone processing plants which may affect the lateral growth of the plant in vicinity have been reported. According to Joshi et al. (2009), PM emitted from the stone crushing industry can affect the different plant parameters of some tree species like mohua (Madhuca indica), sonajhuri (Acacia moniliformis), eucalyptus (Eucalyptus citriodora), sal (Shorea robusta) and arjun (Terminalia arjuna). Several types of the micro and macro variations were found, consisting decrees in the quantity of chlorophyll and total carbohydrate in leaf tissues pointing lowering in photosynthesis. According to Anderson (1914) deposition of the PM on stigmatic surfaces may hinder the processes of fruit production. The effect of urban road and traffic emission-related PM was also extensively investigated by several authors, and they reported various types of morphological and biochemical effects (blocked stomata, reduced diffusive resistance, increased leaf temperature, reduced photosynthesis, reduced growth, fruit lesions and partial defoliation) on the plants (Populus tremula, Betula pendula, Rhododendron catawbiense, Acer campestre, Abies alba, Fraxinus excelsior, Viburnum tinus, Mangifera indica, etc.) (Flückiger et al. 1977, 1979; Eller 1974, 1977; Eller and Burnner 1975; Thompson et al. 1984; Rao 1971; Ajuru and Upadhi 2014). Several studies related to PM effects on vegetation were reported by different authors listed in Table 3.3.

3.2.2.5 Plant Responses to Stress Caused by PM According to Billings (1978), minimum three types of interactions occurred in plants and PM: firstly the interaction between single plant and environment, secondly

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Table 3.3 Sources and effects of PM on different aspects of plants species Site Riyadh, Saudi Arabia

Plant species Leguminous crops (Pisum sativum L., Vicia faba L., Glycine max and Vigna sinensis) Cucumis sativus L. and Phaseolus vulgaris L.

Source Heavy traffic and industryrelated sources

Effect Bioaccumulation of heavy metals in plant parts

References Alyemeni and Almohisen (2014)

Mix dust (natural and anthropogenic)

Hirano et al. (1994)

Trachycarpus fortunei, O. fragrans, G. biloba, I. tectorum Pongamia pinnata, Tabernaemontana divaricata, Ipomoea carnea, Ficus religiosa, Ficus benghalensis and Quisqualis indica Hibiscus cannabinus L.

Industrial emission

Effect on leaf temperature and photosynthetic and transpiration rate Loss in relative water content, total chlorophyll and pH Inhibition in pigment content

Uma and Rao (1996)

Udaipur City

Dalbergia sissoo

Kapoor et al. (2013)

Kerala, India

Abutilon indicum, Croton sparsiflorus and Cassia occidentalis Shorea robusta, Madhuca indica, Eucalyptus citriodora, Acacia moniliformis and Terminalia arjuna

Industrial and vehicular emission Industrial and vehicle exhausts

Reduction in total protein, chlorophyll, sugar, lipid and starch Chlorophyll degradation Adversely effects on plant morphology

Sukumaran (2014)

Reduction in Chl a, Chl b, total carbohydrate content, protein contents in foliar tissues Effects on biochemical parameters of leaves

Padhy (2013)

Sakai 593, Japan

Hubei Province, China Sambalpur, Orissa, India

Rajasthan

West Bengal and Bihar, India

Mizoram, India

Gujrat, India

Ficus benghalensis, Psidium guajava, Bougainvillea spectabilis, Mangifera indica, Lantana camara and Artocarpus heterophyllus Arachis hypogaea, Sesamum indicum and Triticum species

Traffic emission

Cement kiln emission

Stone cursing and trafficrelated emission

Road dust

Cement industry emission

Effects on the photosynthetic pigments

Chen et al. (2015) Prusty et al. (2005)

Rai and Panda (2014)

Chaurasia (2013)

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population and its environment and finally plant community and its environment. The reaction of any individual towards any stress depends upon its genotype, growth phase, active resources and microhabitat (Levin 1998). Succession in the polluted environment or in natural disturbed area, energy is transferred from development to reproduction and then to maintenance, and thus succession reaches to its former stage (Waring and Schlesinger 1985). Such disturbed environment potentially affects the ecosystem structure, processes and function like physiology and biochemistry of plants, energy flow, nutrient cycling and biogeochemical cycle (Odum 1993). Deposition of the particulate matter onto soil can affect plant yield, reproduction, flowering and plant growth (Saunders and Godzik 1986). Several studies suggested that chronic pollutant injury to a plant community can result in the loss of tree canopy, sensitive species and safeguarding of a successional plant species (Smith 1974; Miller and McBride 1999). The deposition of PM to any plant surface can cause physical and/or chemical changes in the plant and is generally found associated with chemistry rather than mass of deposited particles (Farmer 1993). Some crustal particles having slightly alkaline pH may injure plant surface due to presence of limestone (Brandt and Rhoades 1972). Several authors reported that PM emitted from cement kiln industries may affect the leaf by destroying its cuticle, hydrolyze the lipid and wax component and denature protein due to the rising alkalinity on the leaves surface by liberation of calcium hydroxide on hydration through cement PM (Guderian 1986; Darley 1966). Some of the microorganism, fungi and arthropod residents on plants play a very significant function in decay of litter fall (Miller et al. 1982; Jensen 1974). Apart from direct effect, some of the indirect effects are also responsible for ecosystem response wrt PM. Indirect plant responses to PM are limited to soil environment (i.e. mineral, organic matter, water, air, variety of bacteria, fungi, protozoan, nematodes and arthropods), depending on chemical composition of every element present in PM. The soil is an important location for the rare biological exchanges (Wall and Moore 1999). Several organisms present in the rhizosphere are responsible for the chemical and biological transformations, which make inorganic materials available for plant uptake (Wall and Moore 1999). PM present in the soil also affects the plant populations indirectly by affecting their nutrient cycling important for plant growth, vigour and health of the biota. Guderian (1986) reported that many of the heavy metals and other contents associated with PM and reaching to the soil surfaces are more harmful than component that penetrates the foliar surfaces.

3.2.2.6 Health Effects of PM Figure 3.3 indicates the deposition of the different size fractions of PMs in the respiratory system. The PM10 and PM2.5 are the respirable fraction of the particulate matter present in the ambient atmosphere and get easily deposited into the respiratory system. The several health defects are caused by the deposition of these particles into the lungs. The defects depend on the size and shape of PM and concentration of the PM in the surrounding environment (Sonwani and Kulshrestha 2016, 2018; Sonwani et al. 2016; Sonwani and Saxena 2016). It also depends on the

Fig. 3.3 (a, b) Deposition of the different size fractions of particulate matter in respiratory system

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people’s age, immunity and gender and occupancy probability of that person in a particular environment (Balakrishnan et al. 2002). Indoor environment is also discussed widely in relation to the PM level, exposure and health effects (Kulshreshtha and Khare 2011; Balakrishnan et al. 2002). Several authors also worked on controlling the air pollution problems by changing the type of fuels from nonrenewable to renewable (Sonwani and Prasad 2016; Carroquino et al. 2018). The health effect of the PM is well-known. The effects are due to the shortterm (hours-days) and long-term (months-years) contact to the PM and cause several health-related defects related to circulatory system and pulmonary system and aggravation of asthma resulting in the rise of the number of patient admissions in hospitals. These patients usually suffered with the cardiovascular and respiratory diseases and from lung cancer. There were good observations found for PM10 short-term exposure in relation to the respiratory health in contrast to the PM2.5. In contrast to this, PM2.5 plays a significant role in causing mortality due to long-term exposure as compared to PM10. Thus, it is clear that the PM2.5 is a stronger risk factor than the coarse part of PM10 (particles in the 2.5–10 μm range). All-cause daily mortality is estimated to increase by 0.2–0.6% per 10 μg/m3 of PM10 (Samoli et al. 2008). Long-term exposure to PM2.5 is linked to the rise in the long-term risk to cardiopulmonary mortality by 6–13% per 10 μg/m3 of PM2.5 (Beelen et al. 2008; Pope et al. 2002). The risks from the exposure of the PM2.5 and PM10 are also reported in the population of Delhi (Sonwani and Kulshrestha 2016). Several other studies also reported the health risk due to the particulate matters containing polycyclic aromatic hydrocarbons (PAHs) and heavy metals (Sarkar and Khillare 2013; Jyethi et al. 2014). Vulnerable group with pre-existing diseases related to the heart/lungs and elderly and children are more susceptible than any other adult person at same environmental conditions. Exposure of PM to children may affect development of lung tissues, and it may also harm the lung function (WHO 2011). But there is no proof of safe levels/ threshold level for exposure identified yet below which no adverse health effects occur. Currently, it was also observed that there are lack of studies reflecting the effects of the particles on the basis of their sources and chemical composition (Stanek et al. 2011). One of the important components of the PM2.5 is black carbon (BC), which recently creates curiosity in scientists working in the area of health and climate sciences due to the significant role of BC in both fields. Several organic, metal and seas salt components are usually found attached with the BC and known as important carcinogens and toxic to the human health. The emission from motor vehicles is identified in relation to the human health and put into group 1 category (IARC 2012). This list also contains several PAHs and associated exposures, as well as the household use of solid fuels (IARC 2010).

3.2.2.7 Burden of Disease Related to Exposure to PM It is observed that cardiopulmonary- and lung cancer-related mortality contributed around 3% and 5%, respectively, due to PM exposure globally. In the European countries, this fraction is 1–3% and 2–5%, respectively, in several sub-regions

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(Cohen et al. 2017). Recent study indicates that the burden of disease connected to atmospheric pollution can be even high. It was also observed that within atmospheric pollution the annual PM2.5 attributed for 3.1 million deaths and approximately 3.1% of world’s disability-adjusted life years (Lim et al. 2012). It is also observed that the exposure of the PM2.5 reduces the average life expectancy in the population of any region, where the traditional health impact assessment methods were used. This study reported that the average life expectancy of a population in many metropolitan cities can be increased by more than 1.5 year after following annual average air quality guideline of WHO for PM2.5 (Fig. 3.4).

3.2.2.8 PM Effects on Climate Atmospheric aerosols affect the climate by controlling the earth radiation budget. This happens through many diverse processes which may be classified into direct and indirect effects. According to the Intergovernmental Panel on Climate Change (IPCC) third assessment report, greenhouse gases are reasonably and highly responsible for the radiative forcing of climate with high accuracy. NASA’s Terra satellite releases world-based observation of the average monthly aerosol amount over the world, and for this Moderate Resolution Imaging Spectroradiometer (MODIS) was used. The satellite measurement of the aerosols was calculated in terms of aerosol optical depth (AOD). AOD is a computation of the extinction of the solar beam by dust and haze. In other words, particles in the atmosphere (dust, smoke particles, mineral dust and biological particles) can block sunlight by absorbing or by scattering light. AOD is a dimensionless numeral specifically linked to the amount of aerosol in the vertical column of atmosphere above the study site. A value of 0.01 represents to a really clean atmosphere, and a value of 0.4 would indicate towards a very hazy state (www.esrl.noaa.gov). Direct Effect The direct aerosol effects include absorption and scattering of the solar radiation. Both short- and long-wave radiation produce net negative radiative forcing depending on the albedo on the primary layer which controls the total amount of radiation absorbed or scattered to space. IPCC classify the radiative forcing as a result of the primary and ultimate aerosol effects, hence classified as a first-order effect. These interactions of the aerosols and radiation are measured in terms of single scattering albedo (SSA), and it is the ratio of scattering alone to scattering plus absorption (extinction) of radiation by aerosol. SSA tends to zero on infinite absorption, increases as absorption decrease and leads towards the unity in the dominance of scattering. PM Indirect Effect on Climate Indirect effect of PM includes the changes in the earth’s radiation budget by changes in clouds by atmospheric aerosols. The cloud droplets formed from the cloud condensation nuclei (CCN). The increasing CCN results a rise in the quantity of the cloud droplets. This directs towards extra scattering of shorter-wave radiation which means more rise in the cloud albedo, also known as the cloud albedo effect,

Fig. 3.4 Model prediction about mean rise in life expectancy (months) for person aged 30 years for a decrease in mean yearly concentrations of PM2.5 down to the WHO AQG yearly average concentration of 10 μg/m3 in 25 European cities contributing in the Aphekom project. (Source: Medina 2012)

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first indirect effect or Twomey effect. On increasing the cloud droplet number concentration, the size of the drop is reduced on introduction of aerosols as similar quantity of the water is separated among more droplets. It increases the cloud lifetime, known as cloud lifetime aerosol effects or Albrecht effect.

3.2.2.9 Acid Rain and Eutrophication Figure 3.5 is showing the eutrophic processes and components in the lake. Eutrophication is a condition of water body enriched with the nutrients such as nitrogen and phosphorus. The atmospheric deposition (e.g., in the form of acid rain) can also affect the nutrient levels in the water body, particularly in the industrial regions. This excess amount of nutrient triggers algal bloom which is ultimately responsible for the loss of animal and plant diversity. Eutrophication is also identified as excessive plant and algal growth due to higher accessibility of one or more limiting factors such as sunlight, fertilizers and carbon dioxide of photosynthesis (Schindler 2006). It is a natural ageing process of any lake due to the deposition of sediment into it over centuries (Carpenter 1981). The N, P and K originated on agricultural land and fertilizers or animal waste are the principal nutrients reaching to the surface water and involved in the eutrophication. Urban and industrial runoff also contributes to eutrophication. Anthropogenic factors also affect eutrophication severely by increasing the rate of adding nutrients into the water bodies. Emissions from thermal power plants and vehicles also contribute a large amount of nitrogen oxides entering aquatic ecosystem. The eutrophication of the lakes can be also deteriorated by climate change on increasing the water temperature. The bacterial activities increase on increasing the

Fig. 3.5 Components and process of eutrophic lake. (Source: Arpa Umbria 2009)

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temperature of water body and result the drop in level of dissolved oxygen content. The warm water bodies are the home of the several fishes which eats on zooplankton (the microscopic animals). The zooplankton depends on the algae for their food; thus they control their number. Daphnia is one of the zooplanktons reported to be efficient and beneficial in controlling the algal population. Eutrophication reduces the algal controlling ability of zooplankton, and hence blue-green alga dominates the lake habitat. Overall, climate change and eutrophication act synergistically to restrict the capacity of the zooplankton to manage the algal population, which enhances the blooming of lakes. Higher nutrient concentration leads to loss of the submerged aquatic vegetation that provides shelter to fishes. There are several steps involved in the eutrophication process; major steps are listed below: Lakes and streams receiving more fertilizers become more productive. The rich nutrient contribution triggers the development of algae to increase their populations. The following are the conditions considered as population explosions or “blooms”: (a) Due to the algal bloom conditions, the diffusion of light into water is diminished which ultimately decreases the productivity of plants in deeper waters. (b) Thus the water becomes depleted in oxygen. Low oxygen results in more algae to die. Low oxygen level also affects the lowering of primary production in the deep water. (c) Low level of oxygen results in the dying of large fishes which required high amount of dissolved oxygen (“DO”), like trout, salmon and other attractive sport fish.

3.2.2.10 Atmospheric Haze Industrialization and urbanization activities over the world have led to a rise in air pollution and haze condition in both developing and developed countries (Fig. 3.6a– f). When sunlight encounters minute suspended particles in the atmosphere, it reduces the visibility called as haze or smog. Power plants, vehicular traffic, industrial facilities and construction activities play significant role in the formation of haze by emitting various pollutant especially fine particulate matters (Watson 2002). High levels of pollutants trigger more the haze due to their absorptive and scattering effects. Haze reduces the clarity and colour of objects we see. Some of the pollutants like sulphate particles may scatter more light during humid conditions (Li-Jones and Prospero, 1998). Haze mainly originates from the cities or crowded area and disperses to the rural and urban background area through wind. Smog can change the weather conditions due to the presence of definite dark particles containing carbon, which play significant role in altering earth radiation budget by scattering and absorbing nature of carbon particles. Haze can decrease the quantity of the solar energy up to 30 percent reaching the earth’s surface (Chameides et al. 1999). Apart from the visibility degradation, air particles are involved in forming cloud condensation nuclei (CCN) which ultimately affect rainfall pattern. Finer particles (apart from soot particle) were found involved in the formation of the CCN. Apart from finer particles, oxides of sulphur and nitrogen are also found involved in haze formation. The scavenging processes (dry and wet deposition) were found involved

Fig. 3.6 (a–f) Haze problem around the different countries around the world from a to f (UK, USA, Singapore, India, China and Pakistan)

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in the cleaning of atmospheric pollutants (Gu et al. 2010; Arakaki et al. 2013; Sonwani and Kulshrestha 2017; Sonwani and Kulshrestha 2019). Therefore, the atmospheric visibility is directly linked to the pollution level in the atmosphere.

3.2.3

Impact of Carbon Monoxide on Environmental Health

The NAAQS suggested highest safe CO level is 10 ppm (parts per million). Many persons do not have sign of the CO toxicity under 70 ppm, but the exposure over this may be responsible for headaches, fatigue and nausea. The signs may be alike to a cold or flu, and several persons mistake CO poisoning for these sicknesses. Levels of 150–200 ppm often result in disorientation/coma and occasionally even death.

3.2.3.1 CO Toxicity In the process of breathing, O2 from air come into the pulmonary system through nasal passage, where it reacts with the red blood corpuscles (RBCs) and is transported to every cell in the body. The haemoglobin (Hb) is the main oxygentransporting protein in RBCs. Every haemoglobin molecule consists of a group of four iron-containing units called haem. In the normal condition (in the absence of CO), every haem reacts with one molecule of oxygen (O2) and forms oxyhaemoglobin complex (Hb(O2)4). Oxyhaemoglobin is a darker red than haemoglobin. The oxyhaemoglobin travels across the body, and when it reaches cells that do not have plenty of oxygen, it frees its oxygen to them. In the normal condition (in absence of CO), Hb reacts with the oxygen and forms oxyhaemoglobin in the blood. HbðaqÞ þ 4O2 ðgÞ $ HbðO2 Þ4ðaqÞ Carbon monoxide is poisonous as it hinders above-mentioned course of action. CO has high binding affinity to haemoglobin than oxygen, and it is about 200 times better. It denotes that the carbon monoxide more easily binds with haemoglobin to form carboxyhaemoglobin (COHb) even in the presence of far more oxygen. Thus, haemoglobin readily reacts with CO instead of oxygen and form carboxyhaemoglobin. HbðaqÞ þ COðgÞ ! HbðCOÞðgÞ As a bioindicator of CO exposure, COHb is accurate and directly related to the mechanisms of toxicity. In inhabitants with comparatively elevated exposure, there are persons continuously exposed to emission of fuel combustion sources at their occupation. These persons were drivers of taxi cars and buses, policemen, garage and tunnel workers and traffic wardens. High exposures were also noticed in the workers in metal industries and petroleum, gas and chemical plants. Currently smokers have more exposures than nonsmokers and high levels of tobacco smoke in residence,

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workplace and restaurant, which may also increase individual exposures significantly (USEPA 1991). Another study observed that the indoor players and skaters are exposed with highly polluted indoor environment due to strenuous exercise causing high breathing rate and poor ventilation linked with exercise levels during the sports activity (Lee et al. 1994; Paulozzi et al. 1993). In healthy people, minute quantities of CO are produced by the breakdown of haemoglobin and other haem proteins. At relax and without exposure, this results in a COHb saturation of 0.4–0.7%. At the time of pregnancy, high maternal COHb concentration of 0.7–2.5% has been found, and the foetuses of nonsmoking pregnant woman have been also observed with rising levels of 0.4–2.6%. Hypermetabolism, particular drugs and haemolytic anaemia may raise endogenous COHb concentration by up to 4–6% (ACGIH 1991a, b; USEPA 1991). The toxicity of CO is governed by these factors and by exposure duration, respiratory minute volume, cardiac output, tissue oxygen demand and blood haemoglobin concentration (Lee et al. 1994). The rate at which arterial blood reaches equilibrium with the inspired concentration of CO is affected by the diffusion capacity of the lungs and alveolar ventilation and the duration and concentration of exposure. This model, in its non-linear form, may be used to predict CoHb levels at high CO exposures, whereas in linear form it can be made applicable to typical air pollution situations.

3.2.3.2 Health Effects The emission and related exposure to the human being was among the top most discussions during the UN Commission for Sustainable Development 2006. There are several studies that found the evidence (COHb) of the carbon monoxide in the blood in relation to the dose responses (in the areas having high CO levels), which has the most significant health effects. Several organs are affected by the high CO exposure including circulatory system, nervous system and skeletal muscles. It also creates several long-term and short-term symptoms and effects such as headache, dizziness, vision and hearing impairment, low oxygen level in body, cerebral obstruction, oedema and death (USEPA 1991; ACGIH 1991a, b; WHO 1979). Apart from the above-mentioned health defects, some studies also mentioned other health-related problems such as tuberculosis, cataracts, different types of cancers, low birthweight, still birth and heart disease. Effects on Humans Neurological and Behavioural Effects

It is implausible that CO has any direct impacts on the lung function but at very high level. Its poisonous impacts on man are because of hypoxic condition, which becomes prominent in organs and tissues with high oxygen utilization including the heart, brain, exercising skeletal muscle and the foetus under development. It is worth motioning that due to the acute CO poisoning, the condition of severe hypoxia occurs, which may create both reversible, temporary nervous disorder and severe, regularly delayed, neurological damage (ACGIH 1991a, b). At a COHb concentration of around 10%, it may create a symptom of headache, but at relatively high

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concentration, it may create the symptoms of dizziness, nausea and vomiting. At a higher percentage levels (~40%) of COHb, it may cause unconsciousness and death, whereas 50–60% of CO is often lethal (USEPA 1991). The impact of low-level dose of CO that may affect human behaviour has been analysed by several authors (Laties and Merigan 1979; Benignus 1994). But COHb levels below 18% create no significant defects on visual or behavioural functions in normal healthy subjects. Earlier studies referred that the impacts begin from very low level of 3–5% in some cases. According to one school of thought, the highest sensitivity to carbon monoxide is because of its single blind in design, whereas some other studies says that it have been double blind which is the clear cause for the discrepancy in this point (Benignus 1993). In usual conditions, higher error may be observed in the behavioural tests where lower COHb concentration is observed at resting situation. It is also promising that unusual cardiovascular problems and disease increase the sensitivity of diseased person to CO-induced behavioural impacts (Benignus 1994). Cardiovascular Effects

In order to identify the impact of the low-level CO toxicity during physical exercise on cardiopulmonary function due to its exposure, several subjects (healthy and person with ischemic heart disease) are taken into the consideration for the observation. During these experiments, the peoples are exposed with fresh air and air with CO level inside a chamber or through a face mask. After exposure, the concentration of the blood COHb is determined, while the person is engaged in an exercise. In somewhat healthy person, the maximum exercise interval and the maximum oxygen expenditure have lowered at COHb concentration as low as 5%. The relation between percentage loss in maximum oxygen consumption and the percentage rise in COHb level appears to be linear, with about a 1% fall in oxygen expenditure per 1% point rise in COHb level above 4% (USEPA 1991; Bascom et al. 1996). Patients with heart disease, particularly ischemic heart disease, are expected to be especially sensitive to CO. Atherosclerotic (tapering of the coronary arteries) and damaged expansion mechanism limit blood flow to the muscular tissue of the heart and prevent physiological return for poor oxygen supply caused by increasing concentration of COHb. The early studies of Aronow et al. (1972), Aronow and Isbell (1973) and Anderson et al. (1973) have observed inhalation of air having low CO level responsible for 2.5–3.0% of COHb levels. The high threat amongst the tunnel officers decreased importantly in few years after the stop of the occupational exposure, and there has also been an important decrease from 1970, when the introduction of new aeration systems decreased the CO concentration in tunnels and tunnel stalls (Aronow et al. 1972). Full-day average CO levels in tunnel were observed around 57 mg/m3 (50 ppm) in 1961 and 46 mg/m3 (40 ppm) in 1968. During peak period traffic in 1968, CO levels in tunnel toll stall were found high (74–189 mg/m3 (65–165 ppm)), and in 1970 the average level during 38 days was 72 mg/m3 (63 ppm). In another study, USEPA reported that the epidemiological observations and laboratory animal analysis suggest that common environmental exposures to carbon monoxide do not leave any atherogenic effects on humans (USEPA 1991).

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Developmental Effects The exposure of the CO also leaves several adverse effects to both pregnant lady and newborn infant. At the time of pregnancy, the endogenous generation of CO can rise up to three times, the level of mother’s haemoglobin is usually declined and mothers may have physiological hyperventilation. Due to this condition, the normal COHb level increased by 20% in pregnant woman as compared to the non-pregnant woman. CO defuses readily from the placenta, which easily binds with the foetal Hb as compared to the adult Hb due to its high affinity. Furthermore, CO is unoccupied more gradually from foetal blood than from maternal blood, whereas a high level (10–15%) of average foetal COHb is observed as compared to the maternal COHb level (USEPA 1991; Longo 1977). It was scientifically and theoretically proven that the foetus and the developing organs are more susceptible to CO level. The developing brain has one of the highest CO sensitivities in comparison with all other organs. There is a direct relation between the maternal smoking and weight of the developing foetus at 2–10% of COHb level. It also depends on the dose-dependent prenatal death and behavioural changes in the infants. CO is most likely one of the most significant etiological factors (factor responsible in the development of any disease) for these effects, even though there are several other toxic pollutants in tobacco smoke (Longo 1977).

3.2.3.3 Impact of Indoor CO Emissions of CO in the domestic environment may be classified as accidental or as resulting from the intentional use of combustion devices. Accidental emissions may result from the improper use of combustion appliances and from faulty appliances; other unintentional sources include the ingress of polluted air from attached garages or from the outdoor environment. Accidental emissions can lead to very high indoor CO levels, which may result in acute and sometimes fatal health effects. Most CO emissions come from the intentional use of partially vented or unvented combustion appliances such as gas cookers and other appliances including water heaters and unvented gas space heaters, along with wood or other solid fuel burning appliances. CO emissions are highly variable between gas cookers as well as between individual burners on the same appliance. Operating a gas cooker with an improperly adjusted flame can lead to very high emission rates (up to and above a fivefold increase compared with a properly adjusted flame). Emissions from unvented gas space heaters are very variable but tend to be comparable with gas cooker emissions. Infrared gas space heaters produce higher emissions than convective or catalytic appliances. For unvented kerosene space heaters, radiant appliances produce higher emissions than convective appliances. For these types of sources, the wick setting has a significant effect with a low setting producing the highest CO emission rates. Amongst wood and other solid fuel burning appliances, the non-airtight wood burning stoves and fireplaces may produce substantial amounts of CO compared with airtight appliances. Tobacco smoking is also a source of indoor CO with emission rates varying between tobacco brands and with the total number of cigarettes smoked. As people spend a considerable amount of time indoors, levels of CO inside the home can have a significant impact on personal exposure levels

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(although particular subgroups such as commuters and those working in certain occupations may be more affected by outdoor levels). For example, in UK homes with CO sources such as gas cookers, peak concentrations of up to 60 mg/m3 (52.4 ppm; the WHO air quality guideline for a 30-minute exposure to CO) have been recorded (Longo 1977), and in other cases much higher peak levels have been associated with malfunctioning combustion appliances. However, long-term CO concentrations are generally much lower. In other indoor microenvironments in which internal combustion engines are operated with insufficient ventilation, mean levels of CO can rise to above 115 mg/m3 (100.4 ppm) for prolonged periods, with much higher short-term values.

3.2.4

Impact of Lead and Environmental Health

3.2.4.1 Lead Sources and Routes of Exposure The most common route of the exposure for any pollutants/chemicals present in the environment has been shown in Fig. 3.7. There are occupational and environmental sources for the atmospheric lead exposures, and due to the inhalation exposure of lead particles released from the burning materials containing lead such as stripping leaded paint, smelting, recycling and using leaded gasoline or leaded aviation fuel, caused harmful impacts on human health. The most common way for the lead exposure is through inhalation, and human can be also affected through definite types of unregulated cosmetics and medicines. Young children are predominantly vulnerable to lead poisoning because they soak up four to five times as much ingested lead as adults from a particular source. A significant quantity of lead released through the mining and battery recycling activity and exposure through lead-contaminated soil/aerosol cause deaths in young children in several countries such as Nigeria, Senegal and other countries. After the exposure of the lead in the body, it can be easily distributed all over the body organs such as the liver, kidneys, brain and bones. Lead can be easily accumulated into the bones and teeth and transferred into the blood at the time of pregnancy, and thus it is exposed to foetus. Undernourished (children with deficiency of nutrients such as calcium and iron) children may easily get affected from the lead exposure due to their more susceptibility towards lead. Developing foetus and newborn babies are very prone to the lead exposure and at highest risk to get affected from lead exposure. The severity of lead exposure and symptom to the people depends on the exposure pathway and exposure type. Some of the person may not have any symptom at low level of lead exposure, whereas the symptom also depends on the sensitivity and immunity of the people. The acute lead poisoning may occur due to the exposure of high levels of lead. The symptoms may include headache, fatigue, muscle pains, seizures, abdominal pains, nausea, vomiting and coma. The chronic exposure of the lead may produce symptoms such as irritability, lack of energy, loss of appetite, learning disabilities and behavioural problems. Lead exposure may also cause many unnecessary effects (disruption of the biosynthesis of haemoglobin and anaemia, an increase in blood pressure, kidney damage,

Fig. 3.7 People’s exposure to chemicals in the environment and the effect of such chemicals on human health

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Table 3.4 Blood lead levels and related exposure in children and adults Blood lead level Blood lead levels below 5 μg/dL

Blood lead levels below 10 μg/dL

Health effects Children: Low educational success, low IQ and low in specific cognitive measures and attention-related and behavioural problem Adults: Kidney malfunction, maternal blood lead linked with reduced foetal growth Children: Late puberty, decreased postnatal growth, low IQ and hearing impairment/loss Adults: Rise in blood pressure, elevated risk of hypertension and increased incidence of essential tremor

miscarriages/abortions, nervous disruption, declined fertility of men through sperm damage, diminished learning abilities of children, behavioural disruptions of children, such as aggression, impulsive behaviour and hyperactivity).

3.2.4.2 Effects of Lead in Children Table 3.4 shows major health-related problems due to the blood lead levels. Lead exposure can have deleterious impact to the children health. The high exposure of the lead can cause serious health-related problems to the central nervous system (including the brain and backbone) which may lead to coma and even death. The nervous disorder and behavioural effects due to the lead exposure are usually irreversible. Low concentration levels pose no adverse impact on the human health, but higher concentration creates broad-spectrum injury and leads to multiple organ failure. It affects the developing brain and causes low intelligence quotient (IQ), low education achievements, increased antisocial activity, behavioural changes, etc. The other adverse impacts include reproductive system failure, anaemia, low immunity, renal dysfunction and hypertension. Till now there is no safe limit for lead in blood that has been decided. But, it is noticed that the severity of the symptom and effects are directly proportional to the lead exposure. Yet blood lead levels as low as 5 μg/ dL, once considered as a “safe level”, can be linked to lowering intelligence in children, behavioural problems and education difficulties. 3.2.4.3 Effects of Lead in Adults Several health impacts are observed in adult human after lead exposure. The increased blood lead concentration (>15 μg/dL) causes many problems related to fertility, cardiovascular system, nerve disorders and decreased kidney function. It may be also responsible for the late formation and negative effects on sperm and semen, such as their counts and motility. 3.2.4.4 Environmental Effects of Lead The leaded gasoline causes the lead contamination in the environment. Other sources for the lead contamination in environment include anthropogenic activities such as solid waste combustion, industrial processes and fuel combustion which contribute in the rising lead level significantly. The presence of lead in water and soil may be due to the corrosion of the leaded pipelines in water transportation system and also

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through corrosion of leaded paints. After their release/emission from source, it can never be broken down but can be converted from highly toxic to less toxic forms. Lead easily gets accumulated into the different organisms after exposure. The water and soil organisms are also severely affected by the lead toxicity. Even at very low level, lead can affect shellfish. The increasing level of lead causes body dysfunction of phytoplankton (an important source of energy and oxygen in sea/ocean). Thus the health impact on phytoplankton affects the health of ocean and large sea animal and plays an important role in global balance. The soil properties and functions are also adversely affected by the presence of lead level in the soil close to the highways and farmlands. A very high level can be present. The accumulation of the lead is dangerous for organisms and ultimately for the entire food chains.

3.3

Conclusions

The environmental effects of air pollution are tremendous and are emerging due to high rate of urbanization and industrialization. These anthropogenic activities together with natural events release a large amount of toxic/harmful pollutants, responsible for their high loading to the ambient atmosphere. This chapter discussed about the wide range of the primary criteria air pollutants (SO2, NO2, CO, PM and Pb) with special reference to their environmental and health impacts. Acid rain, eutrophication, haze formation, climate and health effects are discussed in detail. The impact of the criteria air pollutants on environment has been discussed with proper explanation and chemical reactions. The exposure assessment, health risk assessment and total global mortality are also discussed on the basis of results discussed by several authors in their literatures. An alternative clean energy source can be a good alternative to reduce the burden of these primary criteria pollutants which ultimately decrease these environmental and health-related problems caused by their exposures. The policymakers may play a very significant role by amending the existing policies in order to keep this upsurge in air pollution under control.

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Jensen V (1974) Decomposition of angiosperm tree leaf litter. In: Dickinson CH, Pugh GJF (eds) Biology of plant litter decomposition, vol I. Academic Press, London, pp 69–104 Joshi N, Chauhan A, Joshi PC (2009) Impact of industrial air pollutants on some biochemical parameters and yield in wheat and mustard plants. Environmentalist 29(4):398–404 Jyethi DS, Khillare PS, Sarkar S (2014) Particulate phase polycyclic aromatic hydrocarbons in the ambient atmosphere of a protected and ecologically sensitive area in a tropical megacity. Urban For Urban Green 13(4):854–860 Kapoor CS, Bamniya BR, Kapoor K (2013) Efficient control of air pollution through plants, a costeffective alternative: studies on Dalbergia sissoo Roxb. Environ Monit Assess 185(9):7565– 7580 Krippelova T (1982) The influence of emissions from a magnesium factory on ruderal communities. In: Bornkamm R, Lee JA, Seaward MRD (eds) Urban ecology. Blackwell Scientific Publications, Oxford, pp 334–335 Kulshreshtha P, Khare M (2011) Indoor exploratory analysis of gaseous pollutants and respirable particulate matter at residential homes of Delhi, India. Atmos Pollut Res 2(3):337–350 Laties VG, Merigan WH (1979) Behavioral effects of carbon monoxide on animals and men. Annu Rev Pharmacol Toxicol 19:357–392 Lee K et al (1994) Carbon monoxide and nitrogen dioxide exposures in indoor ice skating rinks. J Sports Sci 12:279–283 Levin SA (1998) Ecosystems and the biosphere as complex adaptive systems. Ecosystems 1 (5):431–436 Li-Jones X, Prospero JM (1998) Variations in the size distribution of non-sea-salt sulfate aerosol in the marine boundary layer at Barbados: impact of African dust. J Geophys Res Atmos 103 (D13):16073–16084 Lim SS, Vos T, Flaxman AD, Danaei G, Shibuya K, AdairRohani H et al (2012) A comparative risk assessment of burden of disease and injury attributable to 67 risk factors and risk factor clusters in 21 regions, 1990–2010: a systematic analysis for the Global Burden of Disease Study 2010. Lancet 380:2224–2260 Lin JM, Fang GC, Holsen TM, Noll KE (1993) A comparison of dry deposition modeled from size distribution data and measured with a smooth surface for total particle mass, lead and calcium in Chicago. Atmos Environ Part A 27(7):1131–1138 Longo LD (1977) The biological effects of carbon monoxide on the pregnant woman, fetus, and newborn infant. Am J Obstet Gynecol 129:69–103 McDonald AG, Bealey WJ, Fowler D, Dragosits U, Skiba U, Smith RI, Donovan RG, Brett HE, Hewitt CN, Nemitz E (2007) Quantifying the effect of urban tree planting on concentrations and depositions of PM10 in two UK conurbations. Atmos Environ 41(38):8455–8467 McLachlan MS (1999) Framework for the interpretation of measurements of SOCs in plants. Environ Sci Technol 33(11):1799–1804 Medina S (2012) Summary report of the APHEKOM project 2008–2011. Saint-Maurice Cedex, Institut de Veille Sanitaire. www.endseurope.com/docs/110302b.pdf. Accessed 28 Oct 2012 Miller P, McBride JR (1999) Oxidant air pollution impacts in the montane forests of Southern California: a case study of the san Bernardino Mountains. Ecological studies, vol 134. SpringerVerlag, New York. 424 pp Miller P, Taylor OC, Wilhour RG (1982) Oxidant air pollution effects on a western coniferous forest ecosystem. EPA Report No. EPA-600/D-82- 276. Environmental Research Laboratory, U.S. Environmental Protection Agency, Corvallis, OR Odum EP (1993) The ecosystem. Ecology and our endangered life-support systems, 2nd edn. Sinauer Associates, Sunderland, MA, pp 38–67 Pandis SN, Seinfeld JH (1989) Sensitivity analysis of a chemical mechanism for aqueous-phase atmospheric chemistry. J Geophys Res Atmos 94(D1):1105–1126 Parish SB (1910) The effect of cement dust on citrus trees. Plant World 13(12):288–291 Paulozzi LJ et al (1993) A survey of carbon monoxide and nitrogen dioxide in indoor ice arenas in Vermont. J Environ Health 56:23–25

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Abstract

Air quality has become a serious concern in mostly urban areas and covering different parts of the world. Over the last few years, there have been tremendous studies reported so far related to harmful health effects due to bad air quality in urban areas across the globe. Among all air pollutants, criteria air pollutants are specifically highlighted for critically analysing about the environmental impacts in relation to plants species, materials, health, biosphere, etc. These air pollutants are in focus due to their toxicity, reactivities and the severity of their impacts. Among them very less information has been reported on secondary criteria air pollutant. Hence, the present chapter focuses on the nature and behaviour of secondary criteria air pollutants with respect to their impacts on environment. It will also highlight the mechanisms involved in examining their impacts, toxicity and overall assimilation plus fate of their chemical reactivities. Keywords

Secondary criteria air pollutants · Health · Toxicity · Air quality and Biosphere

4.1

Introduction

Deleterious air quality is a main issue in both developed and developing countries. Rapid increase in motor vehicular emissions during peak traffic hours results in major air pollution episodes at selected hotspots (Nagpure et al. 2013; Mishra et al. 2015). The extreme air pollution episodes mostly occur during winter season, characterized by low winds, low mixing heights and temperature inversions (Nagpure et al. 2016; Martins et al. 2010). Many of the populous centres have large, major contribution by man-made pollutants in the atmosphere which is resulted into bad air quality not only at regional but at worldwide level. Among all the listed environmental issues, atmospheric pollution, and their impact on environmental health, is one of the most challenging issues (Chen et al. 2012). The impacts # Springer Nature Singapore Pte Ltd. 2019 P. Saxena, Criteria Air Pollutants and their Impact on Environmental Health, https://doi.org/10.1007/978-981-13-9992-3_4

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of different air pollutants on human health can be of various types like increased risk of lung disorders, respiratory tract problems, heart-related diseases, increase in other respiratory problems like loss of breath, coughing and increase in rate of suffering from lung disorders, impact on central nervous systems like memory loss, impacts on behavioural patterns, cancer and early-age mortality (Chen et al. 2016; Fang et al. 2003). Few sensitive people are more prone to air pollution-related disorders, for example, those suffering with already existing heart-related and lung-related diseases (such as cardiac arrest, asthma, emphysema and severe and long-lasting bronchitis), diabetes, old aged people and children. In the case of developed countries, ambient air pollutant levels decreased due to implementation of advanced and efficient management practices (Farhat et al. 2013). Nevertheless, the problem of sudden occurrence of extreme air pollution episodes still survives. Moussiopoulos et al. (2004) noticed that ambient air pollution levels at urban hotspot in 20 European cities were crossing the given NAAQS. In the UK, out of total declared air quality management areas, 33% were declared due to the increment in specified NOx, and 21% were due to exceedances of the particular PM standard (Jeong 2013). China is also facing severe air pollution problem due to inefficient emission control (Chai et al. 2014; Cheng et al. 2012). It has also been estimated that approximately 3–5 lakh people had died prematurely every year due to bad air quality in China and has achieved fourth rank in producing ill effects to the health of Chinese people after cardiac disorders, heavy smoking and stringent dieting (Pui et al. 2014). In Delhi, India, maximum hourly ozone and nitrogen dioxide concentrations of 138.4 μg/m3, 106.6 μg/m3 and 92.1 μg/m3 were found during summer, winter and autumn, respectively (Kumar et al. 2015). Moreover, Chelani (2013) has also reported that 24 h average NO2 concentration during summer as 116 μg m–3 at one of the traffic intersection site in Delhi. The air quality levels are analysed as per their criteria of composition and physicochemical properties of air pollutants. The major class of pollutants are NO2, SO2, CO, VOCs and particulate matter (PM2.5 and PM10). But, there are some air pollutants which are categorized as per their health risks, formation/ transport mechanisms and air quality perspective, called as criteria air pollutants (Gurjar et al. 2008; Hu et al. 2015; Wang et al. 2014a, b; Zhang et al. 2004). There are six criteria air pollutants, viz. NO2, SO2, CO, PM, O3 and Pb, which are designated under the Clean Air Act of 1971 and are more strongly suspected to be hazardous to human health and the environment (Ji et al. 2012). The widespread research on the criteria air pollutants along with their correlation with meteorological parameters and their impacts have been reported on a large scale (Chai et al. 2014; Guan et al. 2017; He et al. 2017; Hu et al. 2014; Huang et al. 2015; Ma and Jia 2016; Song et al. 2017; Wang et al. 2014a, b; Xie et al. 2015; Yin et al. 2017; Zhang et al. 2015; 2016; Zhao et al. 2016; Zhou et al. 2017). Among all criteria air pollutants, only one of them is formed by secondary process that is called as tropospheric ozone. Hence, this chapter focuses on the overview of secondary criteria air pollutants, i.e. tropospheric ozone and their impacts on environmental health.

4.2 Secondary Criteria Air Pollutant: Tropospheric Ozone

4.2

85

Secondary Criteria Air Pollutant: Tropospheric Ozone

Ozone is found both in the troposphere and in the stratosphere. Stratospheric ozone layer is naturally occurring jacket of O3 molecules, while most of the tropospheric ozone is formed via man-made sources (Aneja et al. 2000). Stratospheric O3 is helpful in protecting biosphere, but the tropospheric O3 is harmful for the plants and human health (Aneja et al. 1991). Ozone is heavier than air; it comes near to the earth’s surface from stratosphere by vertical winds formed during electrical storms (Kasibhatla 1993). However, the tropospheric O3 is formed when precursors like nitrogen dioxide, volatile organic compounds or carbon monoxide reacts with sunlight, and, therefore, this particular type of reaction is also called as photochemical reaction (Finlayson-Pitts and Pitts Jr. 1997). Due to high amount of oxygen present in the atmosphere, more than 90% of the air constitutes ozone. The ozone concentrations are generally high in the afternoon and comparatively less during night (Atkinson 2000). Trees are another source of VOCs. Both precursors like nitrogen dioxides and volatile organic compounds can be driven to long distances due to transboundary movements of air masses before they form ozone in the atmosphere, where it can reside for a long duration. Ozone concentrations in the atmosphere are found highest during calm and sunny days when precursors are present in urban areas. Sometimes, ozone levels are found to be high in rural areas as compared to urban areas, whereas at high altitudes ozone concentrations can be somewhat comparatively stable during the whole day and night (Seinfeld and Pandis 1998). Tropospheric O3 is a worldwide concern as its main ingredient of formation is hydroxyl radical (OH∙) (major atmospheric reactant) and acts as a greenhouse gas. Over a long period of time, a number of atmospheric models have come into picture to understand the ozone chemistry and also to draft emission control policies (NRC 1991). Such models are very much limited to produce current levels of ozone and their precursors (hydroxyl group compounds, oxides of nitrogen and carboncontaining compounds). A number of probabilities in emission inventories, vehicular activities and chemical processes may all responsible for model limitations. The impact of wet deposition on ozone is not direct and pretty marginal and highlights majorly the washout of nitric acid and hydrogen peroxide which are storehouses of NOx and HOx. According to Giorgi and Chameides (1985), a simple scavenging mechanism for HNO3 and H2O2 is enough to explain wet deposition in ozone models. Lawrence and Crutzen (1998) have reported that cirrus precipitation could be a significant sink of nitric acid in the upper troposphere.

4.2.1

Tropospheric Ozone Formation

Ozone in troposphere is produced by a series of photochemical reaction which involves its several pioneers such as CH4, CO, NOx and VOCs in the presence of sunlight. In urban areas, along with industrial and other man-made activities, vehicular activities also play majorly to emanations of ozone pioneers leading to

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ozone formation. Tropospheric ozone is not only a problem of cities and metropolitans but also a problem in rural areas. Rural areas, where wide areas of land are used for agricultural purposes, have high concentration of ground-level ozone due to transboundary movement, in spite of the fact that these areas are located far away from the original source. Two mechanisms may be blamed for higher levels of ozone in rural atmosphere. Firstly, direct ozone transportation from city areas and secondly, the transfer of its pioneers like NOX, VOCs, CO, CH4 and NMHCs backed by in situ photochemical ozone formation. Transportation of ozone from stratosphere to troposphere is also a source of ground-level ozone, but its involvement in ozone built-up is comparatively less (Royal Society 2008). Formation of ozone in the troposphere takes naturally by the oxidation of carbon monoxide catalysed by hydrogen oxide (HOx ¼ OH + H + Peroxy radicals) and nitrogen oxide (NOx ¼ NO + NO2) and by the oxidation of hydrocarbons present in the atmosphere. In the highly polluted areas, there is a higher concentration of these pollutants, and hence ozone is formed in higher concentrations in the surface air which is harmful and hazardous to human health (Finlayson-Pitts and Pitts Jr. 1997). Due to various natural and anthropogenic processes, ozone is formed in the troposphere through several sources including: • The downward movement of the stratospheric O3 sources to ground level through free troposphere. • Methane produced from marshy areas and wetlands reacts with natural NOx for the in situ production of O3. • The reactions of volatile organic compounds with NOx result in the photochemical production of O3. • Transportation of O3 over large distances from distant pollution sources (Krupa and Manning 1998; Mittal et al. 2007; Rai and Agrawal 2012). All these processes are illustrated in Fig. 4.1. Ozone is produced from carbon monoxide by the following reaction: CO þ 2CO2 þ hν ! CO2 þ O3

ð4:1Þ

Ozone can also be produced from methane by the following reaction: CH 4 þ 4O2 þ 2hν ! HCHO þ H 2 O þ 2O3

ð4:2Þ

HCHO þ hν ! H þ HCO

ð4:3Þ

HCO þ hν ! H þ CO

ð4:4Þ

CO þ 2O2 þ hν ! CO2 þ O3

ð4:5Þ

Due to the combustion of fossil fuels, the oxides of nitrogen are released into the air as NO (nitric oxide) which further gets converted to NO2 (nitrogen dioxide) on reacting with ozone already present at the surface during daytime.

Fig. 4.1 Various mechanisms of tropospheric ozone formation

4.2 Secondary Criteria Air Pollutant: Tropospheric Ozone 87

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NO þ O3 ! NO2 þ O2

ð4:6Þ

NO2 þ hν ðwavelength < 420 nmÞ ! Oð3PÞ

ð4:7Þ

O ð3PÞ þ O2 ðþM Þ ! O3 ðþM Þ

ð4:8Þ

Ozone formation also takes place using non-methane hydrocarbons RH þ 4O2 þ 2hν ! RCHO þ H 2 O þ 2O3

4.2.2

ð4:9Þ

Overall Trends of Tropospheric Ozone Levels: Present Status and Future Predicted Trends

4.2.2.1 Global Ozone Distribution Tropospheric ozone is consistently increasing at a higher rate on global scale (Mittal et al. 2007; Rai and Agrawal 2012). In and around the nineteenth century, background ozone levels in the Northern Hemisphere became twice, approximately 35–40 ppb, and have also increased by 5 ppb approaching up to 35–40 ppb level (Royal Society 2008). In most of the countries like Latin and North America, Europe and Africa, alarmingly high levels of ozone were found and crossing the permissible limit set by WHO of 50 ppb (WHO 2006). In the case of South America and Africa, the rise of 30 ppb in ozone concentrations was documented (Zeng et al. 2008). In the area around the West Coast of the USA, ozone concentrations are reported with an increase of 0.46 ppb/year during 1985–2007 (Cooper et al. 2010). In remote farmland area of the USA, the average ozone concentration was found to be in the range of 50–60 ppb (US EPA 2006). In another study, it has been reported that a significant rise in ozone with an average trend of 0.26 ppb/year in seven different rural sites in western part of the USA was reported between the periods 1987 and 2004 (Jaffe and Ray 2007). In spite of the fact that there is a decline in ozone emissions from man-made sources, a rise in past ozone concentrations in lower European troposphere was reported (Chevalier et al. 2007). According to the report published by the Royal Society (2008), earlier ozone concentrations in Europe are still crossing the permissible limits set by WHO and predicted to increase till 2030 partly because of hemispheric transport of ozone formation reactants from developing countries of the world. In all parts of Europe, periodic ozone event happened each year, showing a number of days of high ozone concentrations increasing beyond 50 ppb and sometimes more than 90 ppb (Hayes et al. 2007). In the case of Mediterranean region, from 2000 to 2010, out of 214 monitoring stations, only 62 stations of rural areas are showing an overall decline of 0.43%/year, whereas a steep rise of 0.64%/ year was observed in city areas and 0.46%/year in suburban areas with respect to ozone concentrations (Sicard et al. 2013). Monks (2005) summarized the monitoring and modelling studies together all over Europe and observed that emissions of ozone and their precursors had showed

4.2 Secondary Criteria Air Pollutant: Tropospheric Ozone

89

declined trend in Europe since the past three decades and higher significant decline was shown in Russia. In another study reported by Saitanis et al. (2015), it was reported that real-time ozone concentrations repeatedly increased by 70 ppb at Tripolis plateau in Greece. In addition to that, the highest 1 h peak ozone concentration was 240 ppb as observed in France (Pellegrini et al. 2011). An increase in average concentration of ozone was measured at an Atlantic coastal station in Ireland at the rate of 0.49 ppb/year from 1987 to 2003 (Simmonds et al. 2004) and 0.31 ppb/ year from 1987 to 2007 (Derwent et al. 2007). An overall average increase of 0.14 ppb/year was reported in 13 rural sites in the UK in the period 1990–2006 (Jenkin 2008). According to a modelling study performed by van Toumainen et al. (1996), they showed that highest hourly ozone concentration was found to be more than 50 ppb over Central Zimbabwe. Emberson et al. (2009) also showed that different parts of South Asia have reported up to 50–90 ppb average 7 h (M7) ozone concentration. Ambient air quality monitoring studies reported that average monthly ozone concentration of 50 ppb was observed generally in many parts of Asia, particularly during growth stage of various agricultural crops (EANET 2006; Xu et al. 2008). Ozone concentrations were found to be reported in various locations of the world, viz. 41.7 ppb in Xiaoji, China (Pang et al. 2009); 71 ppb in Lahore, Pakistan (Wahid 2006); and 48.1 and 47.1 ppb in Osaka and Tokyo, respectively, in Japan (Sadanaga et al. 2008). In Hong Kong too, ozone concentrations were found to be increased at the rate of 0.87 ppb/year by comparing the average during 1994–2000 and 2001–2007 (Wang et al. 2009). Yamaji et al. (2006) has showed that highest ozone levels were found between 55 and 70 ppb during May and June in the boundary layer in the region of East China and Japan by using Community Multiscale Air Quality Model. Due to high industrialization and urbanization in the last two decades, ozone concentration was found to be higher in China as compared to other countries and the average of daywise 24 h mean ozone concentration reported to be more than 50 ppb during the crop growing season in various regions (Zhao et al. 2009; Tang et al. 2013). In 2010, in Beijing, China, during summer and monsoon months, the daily average and hourly peak ozone values at urban and rural areas were 46 and 67 ppb and 181 and 209 ppb, respectively (Wan et al. 2013). Moreover, in Yangtze Delta region of China too, a decline in mean values was observed, but a rise in daily variations in diurnal ozone values has been reported. Xu et al. (2008) observed a decrease in the average concentration but an increase in the daily variations in diurnal O3 concentration.

4.2.2.2 Tropospheric Ozone: An Indian Scenario The background ozone levels have increased by a rate of more than twice in the previous century with an increase of 0.1–1 ppb per year. There has been a reduction in the emission levels of NOx and VOCs by 40% and 47%, respectively, from 1980 to 2008 due to which there has been a relative reduction in the ozone concentrations and hence an improvement in the human health (Wang et al. 2009). There have been variations in ozone levels in India since the past few decades. Table 4.1 illustrates the ozone concentrations in different monitoring stations of

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Table 4.1 Ozone concentrations at various stations in India City Mohali Agra New Delhi Allahabad Varanasi Mount Abu Ahmedabad Pune Cochin Bhubaneswar Berhampur Anantapur Anantapur Chennai Tranquebar Nagercoil

Ozone concentration (in ppb) 46.5 30.8 28–33 5.9–35.1 45.2 25.5–48.8 12–30 17.5–43 11.8 31.4 23.7 70.2 20 2–53 8.1–25 19.8

Period of observation October 2011–January 2014 September 1999–June 2001 Winters of 2009–2011 July 2002–September 2002 December 2002–March 2012 1993–2000 (except winter season) 1991–1995 2003–2004 September 1999–June 2001 September 1999–June 2001 September 1999–June 2001 Summer 2010 Monsoon 2010 Summer 2005 May 1997–October 2000 March 2007–February 2010

India. At Kannur, relatively low ozone levels have been observed in monsoon (18.4  3.5 ppbv) as compared to that in summers, winters and pre-monsoon period (Nishanth et al. 2012). At Anantapur, highest ozone levels have been recorded during summers and winters, while the lowest have been recorded during the monsoon (Sarkar and Agrawal 2010b). Similar patterns have been observed in the rural areas also as recorded by Naja and Lal (Naja and Lal 2002) at a rural site Gadanki. In Ahmedabad, the ozone concentrations have been ranging from 12 ppb in August to 30 ppb in November (Lal et al. 2000). During 1988–1991 the surface ozone concentration at Pune was increasing at the rate of 0.03% per year as observed by Tiwari and Peshin (Ali et al. 2012). Ali et al. (2012) monitored O3 concentrations from 1990 to 1999 at Pune and Delhi and found highest levels of ozone during summer and lowest during monsoon season. In Pune, ozone concentrations were found to be in the range of 17.5 to 43 ppb (Beig et al. 2008). In Delhi, despite the significant short-term trends, a seasonal change is observed in the ozone concentrations in Delhi for the whole period. The mean ozone concentration for the whole period based on daily averages was 26 ppb, and the SD was 8 ppb, giving a CRV of 32%. The maximum and minimum concentrations as calculated were observed to be 64 ppb and 7 ppb, respectively, giving a range of 57 ppb. The mean ozone concentration of daily maximum values for the whole period was 62 ppb, and the SD was 32 ppb, giving a CRV of 51%. The maximum and minimum concentrations as calculated were observed to be 129 ppb and 15 ppb, respectively, giving a range of 114 ppb (Ghude et al. 2008). Ozone concentrations were found to be alarmingly higher in summer and pre-monsoon seasons as compared to winter season.

4.3 Impact of Tropospheric Ozone on Climate

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In Delhi, the ground-level ozone concentration was found to be high and crossing the permissible limits (WHO standards) in almost all the days. This is a matter of serious concern as this level of surface ozone concentrations is considered to be a health hazard. There have been clear evidences for serious ozone pollution in New Delhi. The increased levels of surface ozone can be explained on the basis of large production of photochemical ozone. Vehicular emissions of precursor gases NOx, VOCs and hydrocarbons also serve as one of the reasons of high ozone episodes (Ghude et al. 2008). Minimum ozone levels are observed during the monsoon period, probably because of the non-availability of sufficient solar radiations as well as washout of pollutants and consumption of ozone by HOx radicals. High ozone levels are usually linked with meteorological factors such as sunny and warm weather, stationary wind pattern and low humidity. These favourable conditions are usually found in Delhi in the months of April to June (Mittal et al. 2007).

4.2.3

O3 Concentrations Predictions

On the basis of modelling studies, several scientists had predicted ozone concentrations in different regions of the world. The tropospheric ozone concentrations would be expected to increase 20 to 25% by 2050 and 40 to 60% by 2100 (Meehl et al. 2007; Morgan et al. 2008). In Europe, due to the impacts of climate change, the average concentration of ozone would be around 0.9 to 3.6 ppb for the year 2029–2040 relative to the earlier concentrations that are found during 2000–2009 (Langner et al. 2012). The above-mentioned results have depicted that with drastically increased growth in O3 concentrations, the problem of air pollution would become a global issue at the end of the middle century. Though, after the adoption of ozone precursor emission mitigation policies, high ozone concentrations are slowly decreasing in Europe, Japan and North America (Harmens 2014). Moreover, over the past 29 years, a drastic decrease in O3 emissions has been reported (US EPA 2009). But, interestingly, most of the peak hourly mean ozone concentrations during the 1980s had been declined, but background ozone concentrations have increased. With the lack of control policies and laws, ozone precursor concentrations are still rising in developing countries as compared to developed countries (Harmens 2014; Royal Society 2008). According to the 5th Intergovernmental Panel on Climate Change (IPCC) Assessment Report, the ozone concentrations may continue to remain high by 20–25% between 2015 and 2050 and can again rise by 40–60% by the end of this century (IPCC 2014).

4.3

Impact of Tropospheric Ozone on Climate

Ozone has a very significant role to absorb IR radiation having wavelength of around 10 microns. Ozone has the property to effectively absorb IR radiation as the wavelengths present in the IR do not superimpose with water vapour and carbon

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Fig. 4.2 Relationship between altitudes and variation in ambient temperature caused by rise in ozone column density (Akimoto 2006)

dioxide, and therefore, ozone plays an important role in greenhouse effect. The ozone distribution is different in different areas of atmosphere because ozone residence time in the atmosphere is short as compared with other GHGs like CO2, and also the spatial distribution of ozone is tremendously not uniform, depending on the factors like season, altitude and area (Akimoto 2003). Figure 4.2 clearly explains the rate of change of ambient temperature with high levels of ozone concentrations at different heights. As it clearly reflects from the figure, the effect of global warming is not high at ground level. As it goes upwards towards the top of troposphere, the impact becomes more effective reaching the maximum around the tropopause that demarcates the two layers, i.e. stratosphere and troposphere, approx. 10 kms above the earth. In contrast, ozone has positive greenhouse effect in the lower layer of atmosphere. Nevertheless, at a height more than 30 kms, high ozone concentrations will lower the temperature at the ground level (Andersson and Engardt 2010). In case of higher altitudes, where there is low temperature, the total infrared absorption by ozone is more which resulted in the increase of greenhouse effect at a greater extent. Likewise, next to the tropopause, there is lowest temperature present in the air; the greenhouse effect is at its maximum. While at greater heights in the stratosphere there is higher temperature, the total absorption of infrared radiation by ozone is decreased, resulting in greenhouse effect negative in the middle layer of the stratosphere. In brief, ozone present in the troposphere and lower layer of the stratosphere has a positive greenhouse effect. Among all the layers of troposphere,

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ozone has reported intense greenhouse effect in the upper troposphere (Andrey et al. 2014). Tropospheric ozone, correlated with solar and terrestrial radiation, gives rise to change in its distribution and can form radiative forcings (RF) and lead to climate change. In the 5th Assessment Report of IPCC, it was reported that variations in ozone between 1750 and 2010 had produced a worldwide average radiative forcing of +0.40 W/m2 (Myhre et al. 2013; Stevenson et al. 2013). The significant feature of the O3 radiative forcing, relative to radiative forcings from uniformly mixed GHGs, is very much spatially distinct. The notable variations in ozone since 1750 have been mostly recorded in industrial regions which are major sources of ozone precursors. High industrial emissions are not only the source of ozone but also its important precursors like methane, which allows transport to decrease heterogeneities. The area-wise distribution of the O3 radiative forcing also varies with respect to a number of factors (Song et al. 2010). The long-wave radiative forcing is the greatest where temperature changes occur between the surfaces and the tropopause attains the highest, covering the major areas of tropics and subtropics, whereas the shortwave radiative forcing is the largest over more reflective surfaces, e.g. snow or ice and desert. The existence of clouds reduces the long-wave radiative forcing and also regulates the short-wave radiative forcing. This combination of contributing factors gives rise to the net long-wave and short-wave ozone radiative forcing peaking over the southern portions of northern midlatitudes and subtropics over land and especially over Northern Africa and the Middle East (Stjernberg et al. 2012).

4.4

Impact of Tropospheric Ozone on Human Health

Inhalation and dermal exposure by ozone are the two main initial processes that are responsible for its entry in human body (Brauer et al. 2016). A number of studies have showed that routine exposure to ozone can cause DNA damage (Chang et al. 2017; Fann et al. 2012). After inhalation, ozone is accumulated in upper respiratory tract and also in intrathoracic airways (Fang et al. 2013; Fowler et al. 2009). In view of the fact that oral inhalation is responsible for less ozone removal rates than nasal inhalation, excessive physical workout leads to higher penetration into the lung. Ozone accumulation is also affected by other factors such as age and gender: greater levels of accumulation are found in children and ladies, due to the distinction in airway size (Galbally et al. 2013). Bell et al. (2014) also summarized the function of susceptibility and vulnerability factors that may affect ozone-related health effects, like gender, age, socioeconomic status and occupation. As per the opinion of scientists, age is the most significant susceptibility factor, with adults reporting major health risks with respect to ozone exposure. Scarce or constructive evidence was found for gender and occupation, with greater risks among ladies and unemployed or below poverty line people. When ozone got accumulated or absorbed in the upper respiratory tract, it is difficult to wash out all ozone due to its less solubility in water. Instead, it dissolves in the thin layer of epithelial lining fluid (ELF). ELF constitutes a mixture of

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proteins, lipids and antioxidants which play as the main protector against foreign agents. Perhaps, in the reaction of ozone with ELF components, a number of products with various reactivities are formed. According to Nazaroff (2013), exposure of children to ozone is of special significance, because such exposures might have everlasting results. It has also been found that built-up design of the body of children and adults is very much distinct in the sense that children have greater air intake per kg of mass of the body, and their airways are narrower, which makes them highly prone to air pollutants (Fischer et al. 2011). According to the US EPA (2017), chronic exposure to peak values of ozone is related to severe lung disorder. In addition to that, ozone has been related with respiratory illness, medication use, asthma and decreased respiratory functions (Cohen et al. 2017; Forouzanfar et al. 2016; Bell et al. 2014; Ainsworth et al. 2012; Anenberg et al. 2010). Simultaneously, the secondary products are also formed, when ozone reacts with ELF components, and they will cause cellular damage and disturbance in cell signalling in the respiratory system. These byproducts also cause irritations followed by exposure to ozone. There are also other important pathways which are based on the mode of action of ozone in the respiratory tract. This process is responsible for activation of neural reflexes, initiation of irritable syndromes, alteration in epithelial barrier function and sensitization of bronchial smooth muscle (Vornanen-Winqvist et al. 2018).

4.4.1

Acute Health Impacts

A number of studies are carried out on the hazardous impacts of ozone exposure. Most of the reports are well documented by WHO in recent periods (WHO 2006, 2013a, b). To represent more clearly, the degree of damage to human health and number of subjects affected are represented in Fig. 4.3. Less critical health

Fig. 4.3 Summary of ozone health impacts

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conditions are placed at the broad base in the diagram which will affect most of the patients, while most critical ones like death or hospital admission are placed in narrow blocks which are experienced by lesser people. The impacts of short-term exposure to ozone in relation to death rate have been found by two main latest studies: the Air Pollution and Health: A European and North American Approach (APHENA) study (Katsouyanni et al. 2009) and Public Health and Air Pollution in Asia (PAPA) study (HEI 2010, 2011). The mandate of APHENA project is to review wide range of researchers contributing and working for US and Canadian National Morbidity, Mortality, and Air Pollution Study (NMMAPS). This project also aims at analysing the data from various megacities of Canada, the USA and Europe in order to determine the variability of multiple realtime data series and to illustrate the estimate of the interrelationship of ozone increment and mortality. Likewise, the PAPA study also analyses the data of six major Asian cities (Bangkok, Hong Kong Special Administrative Region, Shanghai, Wuhan, Chennai and Delhi), and in Europe too, data was analysed of England and Wales (Pattenden et al. 2010), France (Lefranc et al. 2009), Italy (Stafoggia et al. 2010), Spain (Ballester et al. 2006) and Greece (Kassomenos et al. 2012). Ozone also has hazardous impact on respiratory systems. The correlation between exposure and respiratory health result was explored at different conditions, like under controlled conditions during rest or in active mode, exposures in ambient atmosphere and in relation with earlier recorded pulmonary diseases like asthma or chronic bronchitis. The stimulation of short-lived reduction in lung function is among the most well-known respiratory severe end-points. Robust dataset is available for healthy young people especially passive smokers, exposed to peak levels of ozone (40–600 ppb) during workouts in ambient atmosphere (Wheida et al. 2017; Verma et al. 2017). According to WHO air quality guidelines, a new dimension of predictive models was proposed for lung function decrements (FEV1) associated with inhaled ozone exposure, with the main target to assess risk and evaluated response thresholds (Alghamdi et al. 2014; WHO 2006; Bernard et al. 1999). Major results depict that people exposed to elevated ozone concentrations which are much lesser than applied in closed chamber studies experience extreme lung function decrements (Andrade et al. 2017; ECA 2016; Bozkurt et al. 2015; Anfossi et al. 1991). Epidemiological studies also describe about concrete, positive and important relations between variations in ambient ozone levels and increased death rate levels. The impacts of ozone were generally seen in children, elderly, asthmatics and patients with chronic obstructive pulmonary disease (COPD) (Gao et al. 2017; Glas et al. 2015). These or similar types of studies are still important as they are related to model time-related variables, such as weekend variability, seasonal impacts, air quality and weather-related parameters. Ozone exposure also have cardiovascular disorders like enhanced heartbeat and diastolic pressure, vascular oxidative stress, irritable syndrome and decreased heartbeat variability (Fisk 2015; Bako-Biro et al. 2004; Chao 2001). On the other hand, laboratory studies on artificial exposure by ozone on human are less decisive and have provided non-uniform relations with ozone (Gilliland et al. 2001; Lee et al.

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2004; Parrish et al. 2009; Manikandan et al. 2010; Kleinsorge et al. 2011; Jovanović et al. 2014; Kalimeri et al. 2016). One of the studies done by scientists in the USA in 2005 observed a 11.5% decrease in low-frequency heart rate variability (HRV) related to 2.6 μg/m3 ozone rise in the earlier 4 h and dominant impacts noted in men diagnosed with ischemic heart disease and hypertension (Park et al. 2005). Many of the experimental studies have observed that there are positive correlations between exposure to ground-level ozone and some cardiovascular disturbances like oxidative stress, inflammation, disturbance in heart rate variability, arterial pressure, control, coagulation and myocardial infarction (Lelieveld et al. 2014; Melkonyan and Wagner 2013). In Western Europe, Nuvolone et al. (2013) observed that a 6.3% increase in outside-hospital coronary deaths for a 10 μg/m3 rise in ozone indicates higher risks for females, adults and subjects earlier hospitalized for cerebrovascular and artery diseases.

4.4.2

Chronic Health Impacts

As compared to acute health impact studies, evidence for chronic impacts due to ozone exposure is less available. Lack of studies has been reported so far in case of long-term exposure assessment due to limitations in methodology with respect to epidemiological point of view. The most concrete relation studied so far is on effects of asthma and similar asthma symptoms. But still, more research is needed for better interpretation of findings made between ozone and long-term health end-points. Mortality or decline in life expectancy, impacts on lung health and atherosclerosis and the early start of asthma are the most general health outcomes while analysing the health effects of chronic exposure to ozone. In 2005, WHO announced globally the recent upgradation in air quality guidelines; researchers provided sufficient proof only for short-term impact of ozone on mortality (WHO 2006). Various studies were conducted in the USA like California, and no statistically significant correlation between long-term ozone exposure and death rate was documented (Saavedra et al. 2012; Levy et al. 2005). But in the later years such as from 2012 onwards, various group studies are conducted which provided a good correlation between long-term exposure and death rate, mainly respiratory and cardiorespiratory mortality (Mullins 2018; Stowell et al. 2017; Lyng et al. 2015; Waring and Wells 2015; Schripp et al. 2012). An important initiative by the American Cancer Society Cancer Prevention Study II (CPS II) described the statistically significant correlation between long-term exposure to ozone and total death rate. Risk estimates were high for cardiopulmonary mortality (Grøntoft and Raychaudhuri 2004). Detailed analysis confirmed that long-term exposure to ozone remains connected particularly only to respiratory mortality (Carvalho et al. 2015). Among dose exposure studies, one of the most systematic studies was the Children’s Exposure Study, which occurred in 12 groups of communities present in Southern California (Bozkurt et al. 2015). A number of researchers have reported that statistically significant correlations were found between lung function and ozone

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annual means only among children, who are more exposed to ambient environment. A study conducted by the University of California at Berkeley has reported favourable results. UCB scientists reported long-term exposure assessment of people who live in California and found that there are stable and significant correlations between reduced airway function and long-term ozone exposure (Kalimeri et al. 2016; Darling et al. 2012). Another study which was conducted in Europe depicted the data on lung function tests two times a year on school children in various towns in Austria and Germany. Authors have found a significant correlation between ozone exposure and seasonal changes in lung function growth (Ihorst et al. 2004).

4.4.3

Guidelines for Human Health: Ozone Exposure

The 2008 Ambient Air Quality Directive implemented the highest daily 8 h average threshold of 120 μg/m3 for health safety purpose. The possible output value at each sampling site cannot cross more than 25 days per year, calculated on 3-year average period starting from January 1, 2010 (EEA 2016). The directive also aims at longvision approach; at each site, no value above permissible limit of 120 μg/m3 is taken into consideration. As per the well-established evidence health impacts associated with ozone exposure, the recently updated WHO air quality guidelines set a higher strict threshold for ozone, which is a daily maximum 8 h average concentration of 100 μg/m3 (WHO 2006).

4.5

Impact of Tropospheric Ozone on Plant Health

Ozone as a phytotoxic agent is very hazardous to the survival of plants in the observed atmosphere. Foliar injury and suppressed plant growth were the first observed negative impacts on ozone which were discovered in grape. Ozone causes damage to the stomata which is responsible for production of food through photosynthesis (Mills et al. 2007). Ozone causes alteration in the membrane properties and also is responsible for inhibition of guard cell K+ channels (Feng and Kobayashi 2009). This results in phytotoxicity in the internal leaf tissue. Highly reactive oxygen species (ROS) which includes peroxides and free radicals may be responsible for inducing phytotoxicity (Ashmore 2005). This is because during the disease development in plants and under normal metabolic steady-state situations, oxygen gets activated and these “chain states” over time result in cell death (Volz and Kley 1988). The resulting ROS formed through ozone directly or by encouraging plantbased oxidative bursts is assumed to get toxified within extracellular spaces, but they can start reactions causing damage (Royal Society 2008; Cooper et al. 2004). The wild plants respond to ozone with lethargic stomatal movements along with carbon dioxide concentration, vapour pressure deficit and response to light intensity variance is of lesser amplitude (Fowler et al. 1998; Pleijel 2011). Carbon allocated to different organs may get altered due to decreased assimilate supply because of photosynthesis which leads to various growth responses of the plant organs. In the

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priority, order shoot is given a higher priority compared to the roots and other organs used for storage like seeds, for example. As a result of this, observations showed decreased root length along with shoot weight ratios or a decrease in the ratio between total biomass produced and the yield given by the seed. Observation made in the case of crop is reduction in grain or seed yield. Ozone (O3) injury can be indicated very well by features connected to the stomata. Ozone can be responded to by these functions either through a direct effect of ozone or a defensive mechanism of plants to ozone. For controlling the uptake of ozone by plants, stomatal conductance is treated as a vital feature (Biswas et al. 2008). Gaseous ozone entering through stomata causes cellular damage affecting mesophyll cells and also dissolves in water surrounding the cells. After entering the leaf, ozone reacts with components of apoplast and symplast. Reaction with water happens in the apoplast along with ozone reacting with ascorbic acid (AA), phenolics, transition metals and thiols giving rise to the ROS. In addition to this, introduction of ozone is also accountable for the hazards caused by ion regulation, promotes stress ethylene formation, stimulates antioxidant and phenylpropanoid metabolism and ultimately suppresses carboxylation activity and carbon assimilation. There is also a decoupling between stomatal conductance and photosynthesis resulting mainly because of ozone exposure for the long term (Broberg et al. 2015). Ozone mainly enters inside the leaf tissues via stomata, where reactive oxygen species (ROS) is formed in huge quantity in the present aqueous medium which ultimately causes membrane permeability loss, disruption in gene expression, damage to photosynthetic proteins, loss of chlorophyll content and disturbance in plant metabolism machinery (Booker et al. 2009; Fuhrer 2009; Singh et al. 2014a, b). Increased ROS activity is observed due to exposure to high levels of ozone which produces oxidative stress that may trigger a series of complex antioxidant defence processes that can be enzymatic or non-enzymatic (Blokhina et al. 2003). Ozone is also responsible for causing decrease in photosynthetic rate (Rai and Agrawal 2012; Ainsworth et al. 2012). Therefore, decreased photosynthetic rate, enhanced defence system and secondary metabolite activities give rise to low carbon assimilation and produce significant change in carbon partitioning and decreased biomass accumulation and yield (Singh et al. 2015). The harmful effects of ozone on growth and production of agricultural crops have been reported worldwide at a large scale and cause decline in food production rate (Ashmore 2005; Fuhrer 2009; Emberson et al. 2009; Feng et al. 2008; Feng et al. 2009; Sarkar and Agrawal 2010a, b; Singh et al. 2014a; Rai et al. 2015). After examining various results, Booker et al. (2009) found that the yield losses because of ozone lie in the range of 5–15%. At global level, yield loss of four main crops (wheat, rice, soybean and maize) because of exposure by ozone in year 2000 study was estimated to be around $14–26 billion in the USA, and $6.7 billion of crop yield loss was estimated in the case of arable crops in different parts of Europe (Van Dingenen et al. 2009). Elevated ozone concentrations are also one of the important factors in affecting the forests’ health (Royal Society 2008), its productivity and economic costs (Percy et al. 2007). For the same year, in the European Union, an estimated crop yield of $ 6.7 billion was calculated for the arable crops. The

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increasing O3 concentrations have also been implicated as one of the factors contributing in forest decline (Royal Society 2008). Simultaneously, ozone is also affecting semi-artificial ecosystems consisting of grasslands, declining the primary productivity of wild plants as well as floral biodiversity (Agathokleous et al. 2015; Ainsworth et al. 2012). Another approach on impacts of ozone consists of alterations in herbivory pattern and transformations in plant interrelationships with diseases and other pathogens (Ashmore 2005). Disease transmission due to foliar pathogen on trembling aspen enhanced under high ozone concentrations in the Aspen Free Air CO2 Enrichment (FACE) experiment resulted in the variations in leaf surface properties (Karnosky et al. 2002). In the case of similar experiment, high ozone concentrations are also responsible for affecting the performance of forest pests that are associated with variations in plant biochemistry or caused higher risk of increasing natural enemies. Long-term exposure to ozone enhances the carbon fluxes from the primary to secondary metabolic mechanisms, resulting in the formation of secondary products (Iriti and Faoro 2009), which can be responsible for causing variation in forage nutritive value, plant pathology/phytopathology, natural pest interrelationship and sometimes promoting production of invasive species (Booker et al. 2009). Ozone also plays an important role in producing disturbance in competitive ability of various plant species that after a long period of time results in alterations in the species and hereditary composition as well as functioning of semi-artificial floral ecosystems having impacts on biogeochemical cycles and carbon sequestration (Fuhrer et al. 2003; US EPA 2006; Harmens 2014; IPCC 2014). A large number of research reports on natural and non-natural communities have stated that ozone can affect the series of changes taken place in competition process and species composition (Bender et al. 2006) and the quality of more sensitive species that tends to decrease further by ozone in the whole populations because of competition relative to monoculture (Fuhrer et al. 2003). Elevated ozone concentrations are also a big reason for declining forest growth and species composition (Ashmore 2005; Wittig et al. 2009; Paoletti et al. 2010). Nevertheless, the susceptibility to natural ecosystems like forests and grasslands to high levels of ozone is already established; research on these cases are very less.

4.5.1

Ozone Relationship with Oxidative Stress and Other Physiological Responses

4.5.1.1 Ozone Generated ROS Formation and Signal Transduction The major pathway for ozone entry into leaves is by stoma that is majorly dominated by stomatal conductance (Ainsworth et al. 2012). After ozone made its passage into the substomatal chamber, it does not reside in the apoplast for more time and instantly breaks down or reacts with the compounds existing in cell wall or apoplastic fluid to produce ROS like superoxide radicals (O2.), hydrogen peroxide (H2O2) and hydroxyl radicals (OH.) (Laisk et al. 1989). Staining by CeCl3 depicts that extracellular hydrogen peroxide accumulation was one of the oldest detectable

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responses to O3 in poplar leaves exposed to 150 ppb O3 after 1 h exposure (Diara et al. 2005). Among the ROS, hydroxyl radical is the most reactive of oxygen species producing hazardous damages (Iqbal et al. 1996). These ROS act as early messenger molecules in signalling mechanisms, therefore choosing the downstream signalling and also triggering defence reactions in apoplast (Vainonen and Kangasjärvi 2014). These signalling molecules consists of ethylene (ET), salicylic acid (SA), jasmonic acid (JA), nitric oxide as well as mitogen-activated protein kinases (MAP kinases) (Matyssek et al. 2008). Ozone is also responsible for generation of Ca2+ influx within very short period of time, required for the activation of MAP kinase and NADPH oxidase. The MAPK mechanism is one of the main routes through which extracellular stimuli such as O3 stress are embedded into intracellular cell responses. The energetic MAPK mechanism is involved in upregulation of ET synthesis. In addition to ET, biological synthesis of salicylic acid is also produced which together with ET is essential for the development of foliar injury due to exposure to high levels of ozone (Vainonen and Kangasjärvi 2014). ET and NADPH oxidase originate the transmission of oxidative energy from the region of lesion initiation to the nearby cells and resulted in cell death. After the cell death, products of lipid peroxidation act as substrate for production of jasmonic acid, which serves destructively and reduces ET-dependent lesion generation and is therefore responsible for cell death (Vainonen and Kangasjärvi 2014). An exclusive rise in ET evolution was noted in in the poplar clone “Eridana”, which showed sensitivity towards O3 (Diara et al. 2005; Vainonen and Kangasjärvi 2014). The stimulatory roles of SA and ET and the prevention of lesion expansion by JA have been explicitly characterized by the deployment of mutants of Arabidopsis thaliana (Vainonen and Kangasjärvi 2014). ROS is also responsible to regulate abscisic acid (ABA) that produces stomatal closure response. In the guard cells of Arabidopsis, ROS generated ABA synthesis and produces stomatal closure via activation of plasma membrane calcium channels (Apel and Hirt 2004). Ethylene-dependent reductions in stomatal sensitivity to ABA have also been reported by Wilkinson and Davies (2010).

4.5.1.2 ROS Defence Mechanisms: Role of Antioxidants The abiotic stress created by ozone gives rise to oxidative damage resulted from increased production of ROS that is responsible for causing harmful impacts on cell metabolism and ultimately leads to the damage to lipids, proteins, carbohydrates and nucleic acids (Blokhina et al. 2003). To avoid stress produced by ROS, a series of antioxidant molecules are generated by (Ashmore 2005; Caregnato et al. 2013) non-enzymatic antioxidants like ascorbic acid (AA), flavonoids, phenolics, vitamin E (tocopherol), peptides (glutathiones), carotenoids, polyamines and organic buffering systems or through enzymatic antioxidants (Blokhina et al. 2003), viz. superoxide dismutase (SOD), ascorbate peroxidase (APX), glutathione reductase (GR), catalase (CAT) and different kinds of peroxidases (POD) (Caregnato et al. 2013). Among non-enzymatic antioxidants, ascorbic acid (AA) protects complex macromolecules from oxidative bursts by directly reacting with O2•, H2O2, to give rise to α-tocopherol from tocopheroxyl and eliminate H2O2 by AA-GSH

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cycle (Pinto et al. 2003). Enhanced ascorbic acid concentrations in different crops and tree species after O3 exposure have been reported (Lu et al. 2009; Singh et al. 2010; Yan et al. 2010; Rai and Agrawal 2014). Rai et al. (2007) documented that ascorbic acid content in wheat leaves has been increasing at the rate of 11.2% under outdoor ozone pollution. Elevated mean concentrations of ascorbic acid have been increased by 40% in 20 wheat cultivars grown in controlled chambers having exposed with 82 ppb O3 for 7 h/day (Biswas et al. 2008). After exposed by high ozone concentrations, the variations in total ascorbic acid concentrations were found in Psidium guajava on the basis of leaf as an indicator and were found by Pina and Moraes (2010). Increased ascorbic acid content was noticed in tolerant soybean cultivar PK 472 relative to sensitive cultivar Bragg at 70 and 100 ppb O3 for 4 h from germination to growth stage (Singh et al. 2010). Ozone-sensitive (NC-S) and ozone-resistant (NC-R) plants of Trifolium repens and Centaurea jacea exposed to medium O3 concentration in open atmosphere are reported to have 50–70% more ascorbic acid in NC-R as compared to NC-S (Severino et al. 2007). The concentration of whole apoplastic ascorbic acid correlates directly with ozone tolerance in various floral species (Castagna and Ranieri 2009). However, higher ascorbic acid pool in sensitive varieties has also been shown in rice (Rai and Agrawal 2008) and wheat (Sarkar et al. 2010; Feng et al. 2010). D’Haese et al. (2005) reported that apoplastic ascorbic acid is not an important factor for differential O3 tolerance of Trifolium clones. Padu et al. (2005) showed that ascorbate concentration in Betula pendula did not rise significantly after got exposed by ozone even when stomata were fully open and O3 flux to the mesophyll cells was showing higher increments. Statistically insignificant observations were noted for the total ascorbate and total dehydroascorbate level when Pinus canariensis was exposed to double the level of outdoor O3 concentration (67 ppb). Hofer et al. (2008) observed that ascorbate content was reduced in needle extract of Picea abies in the presence of twice the level of ambient O3 concentrations. Poa plants in monoculture as compared to Vernonia noticed a reduction in ascorbic acid content by 21.3 and 12.4%, respectively (Scebba et al. 2006). Iglesias et al. (2006) exposed Clementina mandarin cv. Marisol for 12 months under the presence of 30 and 65 ppb O3 concentrations and found a decrease in foliar ascorbate pool. Exposure to high levels of ozone results in increase in concentrations of SOD, APX, CAT, POD and GR in wheat (Chen and Gallie 2005; Sarkar et al. 2010), rice (Rai and Agrawal 2008; Wang et al. 2013; Sarkar et al. 2015), maize (Singh et al. 2014b) and mung bean (Mishra and Agrawal 2015). Tree species have also shown alterations in their enzymatic activities after exposing them with high levels of ozone concentrations. Activities of POD, CAT, APX and MDHAR were found to be elevated in Liriodendron tulipifera under high exposure to ozone (Ryang et al. 2009). Significant high values were reported in the activities of various defence enzymes like SOD, CAT, APX, DHAR, MDHAR and GR, in case of Ginkgo biloba (Lu et al. 2009; Feng et al. 2011). Sensitive variety of rice also reported less concentration in SOD activity relative to tolerant variety under elevated O3 (Rai and Agrawal 2008), but it did not differ

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between the filtered air and O3-polluted environment in Psidium guajava (Pina and Moraes 2010). SOD levels rise significantly due to O3 exposure in Quercus mongolica (Yan et al. 2010) and a sensitive birch clone (Toumainen et al. 1996). Biswas et al. (2008) claimed that there was a mean increase of 46% in POD activity in 20 wheat varieties at 85 ppb O3 levels exposed for 7 h day1 for 21 days relative to filtered air. Rai et al. (2007) and Rai and Agrawal (2014) also observed elevated POD activity in wheat species in the presence of natural ozone in the atmosphere relative to filtered air. POD activity was also reported to increase by 54.4 and 11.6% in Achillea and Vernonia, respectively, while it has also been reduced by 21.5 and 27.7% when grown in monoculture (Scebba et al. 2006). Progression in GR activity was very much higher in a sensitive birch clone (Toumainen et al. 1996). In Fagus sylvatica, exposed to double the atmospheric O3 concentrations, glutathione content was significantly enhanced in seedlings as well as in mature trees relative to ambient levels (Herbinger et al. 2005). Rise in total and oxidized glutathione pool was also recorded in Pinus canariensis when exposed to 67 ppb O3 levels (Then et al. 2009). Similarly, APX activity recorded in a resistant white clover clone compared to a sensitive one was found to be high, indicating its possible role in producing higher tolerance towards O3 stress (Nali et al. 2005). Significant variations in the antioxidant activity are very much connected with the differential O3 sensitivity in various plants. Caregnato et al. (2013) have observed that changes in O3 sensitivity between the two varieties of Phaseolus vulgaris depended on the variations reported in maintenance of intracellular redox homeostasis. SoyFACE study performed by Betzelberger et al. (2010) showed cultivar variations in the antioxidant activities of 10 soybean cultivars and suggested that antioxidant activity negatively correlated with photosynthesis and seed yield, therefore suggesting a trade-off between antioxidant system and carbon accumulation. Zhang et al. (2012) also observed variations in the total antioxidant activity of two deciduous (Liriodendron chinense and Liquidambar formosana) and six evergreen tree species (Cinnamomum camphora, Cyclobalanopsis glauca, Schima superb, Ilex integra, Photinia  fraseri, Neolitsea sericea) and observed lowest value in Liriodendron chinense and highest in Schima superb contributing to their difference in susceptibility towards O3.

4.5.2

Characterization of Ozone Exposure

To summarize relation of ozone exposure to its impacts, it is mandatory to analyse concentrations averaged over 1 h intervals in a systematic and logical way. This acts as a substitute for dose (Aamlid et al. 2000). In specific, the exposure index is interrelated with the concept of effective dose (Alscher and Amthor 1988), i.e. it must collect and analyse the characteristics of exposure that is mostly connected with the amount of ozone absorbed by vegetation. Ozone uptake could be determined by multiplying the concentration near the leaf surface by the leaf conductance for ozone, and the absorbed dose would then be the main component of the flux rate over time (Bassin et al. 2007). This concept can be taken into consideration while

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analysing conductivity of the atmosphere (Feng et al. 2008a). Under controlled conditions of uniform air mixing, the diurnal pattern of ozone flux is analysed by leaf conductance and ozone concentration. Due to the lack of leaf conductance observations, radiation can be used as a substitute for leaf conductance which is presently used in agricultural farms/fields (Forster et al. 2007), and the most easy way is to use the measured ozone concentrations during daylight hours (e.g. >50 W/ m2 global radiation) to characterize exposure. In the case of those plant species which are having considerable leaf conductance during night, nevertheless, no such distinction could be made. The factors like atmospheric humidity, soil water availability and temperature are also responsible for affecting leaf conductance; however, these factors have not been taken into account to identify ozone uptake mechanism or chronic dose-related experiments. Chronic exposure to ozone can give rise to growth and yield loss. Consequently, the most appropriate exposure indices are related to chronic effects, and they are cumulative, i.e. they integrate exposure over time. Chronic impacts signify the arithmetic mean over the growing season of the daily average concentrations during specific time period, i.e. 7 h on daily basis (usually 09.00–16.00 h). The application of average concentration in a specific period of time implies equal weight to all concentrations. Nevertheless, controlled chamber dose-response studies of ozone suggests that only the intermittent exposure due to higher concentrations are responsible for causing chronic impacts (Heagle et al. 1999). This can be supported by the fact that more tolerant plant could able to detoxify ozone and other oxidants; if the concentration or the flux of ozone crosses the permissible limit, then harmful effect can occur. In order to calculate the cumulative exposure index, the significant variations between the actual hourly average concentration and the threshold concentration are then summed for the total exposure period (Karlsson et al. 2003). Ozone is known for producing deleterious impact on plant species, and this concept was adopted at the United Nations Economic Commission for Europe workshop at Egham in 1992, when a permissible limit concentration of 40 ppb was suggested (UNECE 2010). Such exposure index is called AOT40, i.e. accumulated ozone exposure above a permissible limit concentration of 40 ppb, expressed in units of ppb/hour or ppm/hour. Statistical analysis of crop production data from European open-top chamber experiments has clearly noted that the use of this permissible limit normally provides better linear fits to exposureresponse data as compared to the use of higher permissible limits (2005). A linear exposure-response relationship showed a better statistical basis for introducing critical levels adjacent to a specific effect as compared to other types of exposureresponse relationship (Utriainen and Holopainen 2001). The application of threshold value of 40 ppb has been dominated over lower threshold concentrations because, in Europe, it widely corresponds to the boundary between average concentrations at those sites that possess low and high frequencies of photochemical events. However, the selection of this threshold does not involve the values less than 40 ppb, and those are having no effect on plant metabolism (Paoletti et al. 2010). Therefore, threshold values do not show a threshold for impacts, instead serve as marginal concentration. As the overall concentrations of ozone get increased with increased height in the

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atmosphere, the application of marginal concentration of 40 ppb does not suit for higher elevations. This index would be estimated by determination of concentrations during daylight hours only because only less rates of ozone deposition were measured over agricultural crops and forests during night hours (Lefohn et al. 1997). Though, it should be reported that in well-mixed fumigation chambers, extensive O3 accumulation in trees can occur. Based on a typical exposure duration, the AOT40 is calculated for crops over 3 months (e.g. May–July) and for forest trees over 6 months (April–September).

4.5.3

Ozone Deposition Mechanism

Ozone deposition constitutes various mechanisms which can be described at different levels of resolution (Jonson et al. 2006). One aspect solely focuses on atmospheric mechanisms above the plant canopy, which are affected by wind turbulence and the unsymmetrical terrestrial landscape, including altitude and kind of vegetation. The another aspect that is very much common in ozone dose-response studies focuses on the role of individual leaf; ozone is deposited to vegetation canopies through uptake by leaves, majorly by stomata. The finest scale of resolution is noted by the reactions taking place inside the leaf. In forests, accumulation sites other than the stomata may also play a significant role in ozone deposition, for example, cuticles, bark, litter, soil and canopy air space, where ozone can be reduced by biogenic hydrocarbons or oxides of nitrogen released from organic decomposition in the soil or by the foliage (Grini et al. 2005). The degree of gas exchange occurs through the stomatal pores, i.e. the ozone flux, related to the total pore area per unit leaf area, and pore density. Mostly plants possess pore area which consists of 0.5–1.5% of the leaf surface (Islam et al. 2000). The extent of pore opening and also the stomatal diffusion resistance depends on the internal environment of the plant. The main external factors are light, temperature, humidity, water supply, wind speed and altitude, whereas the internal factors consists of the partial pressure of carbon dioxide in the intercellular system, the content of water and ions in the tissues and plant growth regulators (gibberellic acid and cytokinin responsible for opening and abscisic acid promotes closing). Ozone uptake by crops in highly extreme environments is very much connected with stomatal conductance and also follows the diurnal pattern of radiation (Gravano et al. 2004), whereas, under less extreme environment, the canopy can be decoupled from the atmosphere, and ozone deposition depends mainly on air mass movement over less control exerted by stomata. Due to difference in canopy structure and different atmospheric conditions, the flux or deposition of ozone mainly depends on leaf conductance (Fiala et al. 2003). In case of ozone uptake, the particular leaf area is measured on the basis of dry weight of the leaf (i.e. the area of assimilatory leaf material per unit dry weight), and this has been reported as the major determining factor. Monitoring at different levels using branch cuvettes on spruce trees reported that the extent of ozone deposition velocity varies between high- and low-elevation sites (Duenas et al. 2002; Bartholomay et al. 1997). Approximately during afternoon

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time, conductance increases with increasing altitude. Interestingly, it has been found that stomatal uptake of ozone may also occur at night in various coniferous tree species (Ashmore 2005). Nevertheless, due to lack of a considerable rate of ozone deposition in forests at night, accumulated exposure index (AOYT40) should be used. In the case of crops, AOT40 can only be applied during daylight hours.

4.5.4

Effects of Ozone on Physiology and Biochemistry of Plants

Ozone may affect the cell metabolism, individual organs, plant species, communities and ecosystems (Bytnerowicz et al. 2007). After making passage through the stomatal pore, O3 can react with organic molecules (e.g. ethylene, isoprene) in the intercellular air space or with components of the extracellular fluid. While considering both the cases, secondary oxidants (e.g. primary ozonides, hydroxyhydroperoxides) may be formed, which in turn could react with the protein component of the cell membrane (Calatayud et al. 2011). This reaction is prohibited to some extent due to the presence of radical scavengers, such as ascorbic acid and polyamines (Coyle et al. 2002). Formaldehyde, formate and acetate are deposited in affected tissue, probably as a result of the reaction between ozone and ethylene or between O3 and the phenylpropanoid residues of lignin. There are various reports which confirmed that ethylene formation determines the sensitivity of plants to O3 (Eckmullner and Sterba 2000). Elevated concentrations of O3 cause target cells to collapse, resulting into local visible tissue destruction. The effect on the plasma membrane can cause alterations in membrane functions which may affect the internal concentrations of ions (e.g. Ca2+) (Larsen et al. 1990). Consequently, this causes the changes in the osmotic potential of the cytoplasm that will produce reduction in photosynthetic processes present in the chloroplasts. Decline in carbon dioxide fixation by the enzyme ribulosebisphosphate carboxylase is a special symptom found in leaves exposed to ozone over longer periods of time (Matyssek et al. 2008). Further, inhibition of carbon dioxide assimilation gives rise to direct or indirect inhibition of stomatal opening that reduces uptake (Nali et al., 2005). Stimulated dark respiration generally occurs together with reduced photosynthesis (Oksanen et al. 2004), most likely due to increased respiration linked with maintenance and repair (Peterson et al. 1999). The combined impacts of decreased assimilation and increased respiratory loss of carbon dioxide include a total reduction of assimilate production and export from the source leaves. In crop plants which are exposed with high levels of ozone for a longer duration, the phenomena of senescence get initiated, and enhanced catalysis results in rapid loss of protein and chlorophyll (Repo et al. 2004). As a consequence, the duration of positive net assimilation of carbon dioxide is lost, and the overall production of assimilates declines. Under conditions of decreased assimilate supply through photosynthesis, transfer of carbon to different organs may vary, leading to altered growth responses of these organs. Typically, higher priority is given to the shoot relative to roots and/or other storage organs (e.g. seeds). This results in reduced root-shoot weight ratios or in a reduction of the ratio between seed yield and total biomass production.

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In agricultural crops, this results in reduced grain or seed yield (Ro-Poulsen et al. 1998).

4.5.4.1 Impact of Tropospheric Ozone on Pigment Content Chronic exposures to low concentration of ozone which accommodates variation in pigmentation or bronzing, chlorosis and premature senescence result in visible injury. Visible foliar injury serves as a major evidence of the hazards faced by the plants due to ozone exposure. Thus, when visible foliar injury can be observed, damage has surely been caused to the plants. Acute exposures to higher ozone concentrations may result in flecking and stippling. In certain species a correlation is observed between visible injury and reduction in growth, for example, yellow poplar, loblolly pine and white pine, whereas according to many studies for a wide range of species, there does not appear to be a correlation. Some of the physiological impacts of ozone contact consist of reduced photosynthesis, amplified turnover of antioxidant system, injury to reproductive procedures, increased dark respiration, dropped carbon transport to roots, reduced decay of early successional communities and reduced forage eminence of C4 grasses. Reactions to ozone are considerably varied in species, but in certain cases results even varied for the same species. Other important variables that affect ozone, like visible injury, are photosynthesis (Duenas et al. 2002) and stomatal conductance (Eckmullner and Sterba 2000). Even if visible injury is not observed, it is not necessary that vital damage has not occurred in the plant due to contact with ozone. An example for this can be Scots pine which showed no sign of visible injury when it was grown in an environment exposed to ozone (Fowler et al. 1998). Also, studies have shown that in certain plants net carbon assimilation rate reduced along with the transpiration in the region of higher concentration without any damage to the leaves visible to the eye (Pleijel 2011). Studies have also shown that continuous ozone exposure resulted in reduction in total chlorophyll content, even though this phenomenon could not be detected by the naked eye. Thus, even in the presence of visible foliar damage, the plants are affected with regard to other variables too even if the naked eye cannot detect the symptoms. 4.5.4.2 Impact of Tropospheric Ozone on Starch Content According to studies and various experiments, ozone is responsible for significantly reducing concentration of starch in stems, coarse roots and fine roots of nongrowing seedlings (Fowler et al. 1998; Pleijel 2011; Biswas et al. 2008; Broberg et al. 2015; Jonson et al. 2006; Grini et al. 2005; Islam et al. 2000; Gravano et al. 2004). The experimental observations have shown a reduction of 72% in fine starch in roots which decreased during the 4-week regrowth period which was not the case with concentrations found in the needles as they remained almost same. During the regrowth period, stem starch concentration was decreased by 65% in seedlings that were exposed to ozone, while the control seedlings saw a decrease of just 25%. Concentrations of glucose showed a little variation by tissue type and growth status in the nongrowing and growing seedlings. In the case of nongrowing seedlings, concentration of glucose was higher in the stems of seedlings that had been in contact with the ozone than the control seedlings. In the case of coarse roots,

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there was a significant reduction in glucose concentration due to ozone exposure, while the overall concentration came out to be low in the experimental results. In the case of growing seedlings, glucose concentration saw significant reduction in glucose concentration in coarse, fine and new roots. According to the experiments, this can be inferred seedlings having new roots had glucose concentration 21% of those of control seedlings as a result of exposure to the highest ozone regime. Experiments also showed that the needles had a high concentration of fructose and it was higher compared to any other part (Ro-Poulsen et al. 1998). Nongrowing seedlings showed greater concentration of stem fructose than the control seedlings. Fructose concentration underwent a decrease in fine roots and new roots in seedlings exposed to higher ozone regime compared to the control seedlings. In the case of sucrose, concentration showed wide variations in nongrowing ozone in presence of all levels of ozone and showed marginal significant ozone impacts in seedlings of the highest regime. Experiments showed that sucrose content was significantly lower in stems, coarse and fine roots of ozone-exposed seedlings compared to controls. Concentration of sucrose was lower in new roots of seedlings treated with ozone than the new roots of the control seedlings, even though the erraticism was very high and the significance of the results in the highest ozone treatment was marginal. Monosaccharides saw significant reduction in roots of growing seedlings due to past contact with ozone. In the case of nongrowing seedlings, ozone-treated plants saw higher stem concentration than the control plants. The new roots of growing seedlings experienced the greatest reduction in monosaccharides induced because of exposure to ozone as observed in the experiments (Bytnerowicz et al. 2007; Calatayud et al. 2011).

4.5.4.3 Impact on Proline Content Proline is derived from various proteins and enzymes and has been significant in providing a source of energy and behaves as an osmoprotectant under stressed conditions. High proline concentrations under stressed conditions reduce the breakdown of other proteins (Oksanen et al. 2004). High rate of proline concentration imparts increase of tolerance against salinity and drought stress in various plant species (Pleijel 2011). Proline has the property to act as free radical scavenger which can protect plants against several damages because of oxidative stresses. Increased exposure of ozone to plant species makes chloroplasts highly susceptible to generate ROS and creates oxidative stress (IPCC 2014). Environmental stress can cause extra ROS which are cytotoxic to all organisms (Biswas et al. 2008). The harmful impacts of pollutants are caused by generation of ROS in plants, which produce peroxidative destruction of cellular constituents (Bytnerowicz et al. 2007). Therefore, increased proline in plants is regarded as an indicator of higher stress such as osmotic stress (Calatayud et al. 2011; Matyssek et al. 2008; Ro-Poulsen et al. 1998). 4.5.4.4 Enzymatic Profiles and Role of Antioxidants (a) Superoxide dismutase: Signs of visible injury came to prominence after two or three pretreatments of the plants that were found to be in contact with high-level

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ozone. The visible symptoms that were observed included small areas of localized chlorosis and necrosis which in turn resulted in spots or flecked appearance to the adaxial surface of the leaf (Mills et al. 2007). With the inception of visible symptoms, the SOD levels saw a significant increase above the control values. Continuous low-level treatments have given results of chronic injury symptoms which can be related to the cumulative SOD activity in damaged plants over some time (Ali et al. 2012). Experiments (with 9-day-old plants) have shown an increase in SOD activity by 21% in plants treated with ozone as compared to the control plants. On comparing the SOD activities in plants that were undergoing acute fumigation after emergence to those that remained in ozone-free air, it was observed that there were clear indications of enzyme induction after visible injury that became clearly noticeable. The small but significant increase in SOD activity after little exposure was not followed by significant injury, but this inconsistency can be credited to the absence of sensitivity of %LAN assessment at lower injury levels (Zhao et al. 2009; Tang et al. 2013; Wang et al. 2013). In the case when experiments were conducted using 2-day-old plants, no changes in levels of minor injury or SOD activity was observed until the third day of experiment. These results signified that injury was responsible for enzyme induction and not the ozone (Calatayud et al. 2011; Matyssek et al. 2008; Oksanen et al. 2004; Ro-Poulsen et al. 1998; Creissen et al. 1999; Zheng et al. 2000). Considering the case of kidney beans, manganese SOD activity is accountable for 25% to 37% of the total activity, and this is largely related to mitochondria 1 fraction. On the basis of sensitivity to cyanide, this type of SOD and cuprozinc type can be distinguished. Thus, while considering the experiments, pretreatment with low ozone showed no significant impact on total extracted SOD activity even though it was expected that exposure to ozone might cause alteration in the ratio of cuprozincmanganese SOD. Experimental observation also show that the young leaves are predominated by cuprozinc SOD and later the manganese form begins to take control. This can be now inferred from the present studies that increased levels of SOD only occur with the beginning of or just after the appearance of visible symptoms of damage, whether caused due to repetitive exposures to low levels or by small doses of ozone (Duenas et al. 2002). Hence, it can be suggested that SOD plays a secondary role in response of leaves to ozone pollution after the damage has occurred. Also, it is not sure that enhanced SOD activity is significant to protect against small ozone exposures as the experimental observation also showed that the damage continued to increase with each exposure in spite of the substantial increase in levels of SOD. Also, no evidence was found to support the observation that susceptibility of the primary leaves to small doses of ozone reduced was caused by pretreatment with subacute doses and has any relation with SOD introduction (Grini et al. 2005). (b) Ascorbic acid: Ascorbic acid resides in the apoplast and is the possible hunter of ROS that could weaken ozone injury. Ascorbic acid is transported to the

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apoplast of the leaf after being synthesized in the cell. Many authors suggest that ascorbic acid plays an important role in many cell wall processes. Ascorbic acid is known to hunt ROS and react with ozone to lessen the chance of damage caused due to ozone and also acts as a substrate in enzymatic reactions that hunt ROS (Creissen et al. 1999). Ascorbate biological synthesis and transport have been occupied in cell wall biosynthesis and signalling. Apoplastic ascorbic acid is suggested by several studies to be oxidized when in contact with the ozone, which results in formation of dehydroascorbic acid (DHA), which is then transferred back into the cytoplasm where the coupled reactions consist of DHA reductase and reduced glutathione reduces it to ascorbic acid. Involvement of extracellular AA in ozone detoxification processes is suggested by apoplastic AA concentration and change in redox status in response to ozone. Snap bean and Plantago major are found to be sensitive to ozone which can be correlated with concentration of extracellular AA (Zheng et al. 2000). Arabidopsis thaliana mutants have low foliar concentration of AA (vtc1) and exhibit hypersensitivity to ozone. Transgenic tobacco (Nicotiana tabacum L.) plants have changed expression of DHA reductase and exhibit variation in leaf AA concentrations which positively correlate with their tolerance to ozone (Chen and Gallie 2005). However certain studies have questioned the efficiency of AA in protecting the plants against damage by ozone as the apoplastic concentration are not sufficient enough for effective detoxification of ROS. Also, the differential ozone sensitivity of NC-S and NC-R clover clones was not found to be associated with apoplastic AA concentrations (D’Haese et al. 2005). So there are still quite a few mysteries that need to be solved regarding the processes involved in maintaining the plant health with relation to ozone. (c) Glutathione: Glutathione is one of the effective and essential intracellular hunters whose role as an antioxidant can only be maintained when GSSG is reduced to GSH through GR activity. Glutathione pool had a considerable effect of ozone treatment as shown by the experiments. The GSH-(GSH+GSSG) ratio dropped noticeably with an increase in the oxidized form and decrease in the reduced form. Stress conditions are actually responsible for the increase in GSSG content. Another observation that can be made from the experiment results is that it seems that the GR activity has no impact on the stable state levels of glutathione. The relative rate of synthesis and degradation is related to the growth conditions, leaf age and NADPH level that seem to be the main factors that help in calculating the total content of glutathione in leaves and is not related to recycling of GSSG via GR activity. GR activity saw a slight stimulation in mature leaves 24 h post fumigation. The increase in the GR activity is not usually more than double (Oksanen et al. 2004) under the stress conditions, sometimes no increase is observed, and at others a drop is observed (Creissen et al. 1999) which suggests that variation in GR isoform population and not changes in total activity is of primary importance. It is not necessary that GR activity is in the steady-state levels of GR protein in response to environmental stresses. The experiments have shown small changes in the GR activity, and protein levels recorded after ozone disinfection, regardless of strident fall in specific mRNA

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level, were observed. This may signify that the enzyme is more stable than other proteins (Chen and Gallie 2005). The sudden decrease in GR mRNA is shown by a higher turnover of mRNA or specific gene down instruction which is encouraged directly by active oxygen species or by messengers like jasmonic acid, salicylic acid or ethylene (Calatayud et al. 2011).

4.5.5

Impact of Tropospheric Ozone on Photosynthetic Rate, Stomatal Conductance and Photosynthetic Output Rate

High doses of ozone cause stomatal closure because of damage to epidermal cells. The passage of ozone in leaf by stomata ahead to mesophyll cells gets dissolved in the aqueous layer of apoplast to generate ROS such as H2O2, hydroxyl radical, peroxyl radical and superoxide radicals (Felzer et al. 2007). Stomatal closure due to exposure to ozone is responsible for reduction in stomatal conductance (Gravano et al. 2004; Creissen et al. 1999; Felzer et al. 2007). Reactive oxygen species cause damage to plasma membrane via lipid peroxidation by producing alterations in membrane permeability, fluidity, potassium (K+) exchange via ATPase reactions and calcium (Ca2+) exclusion (Islam et al. 2000). Free radicals resided in the guard cells damage the chloroplast membranes, and consequently the photosynthetic apparatus would be damaged. Swelling of thylakoids, rise in plastoglobuli per chloroplast and injury of membranes lead to leakage of ions and resulted in photosynthetic capacity (Plazek et al. 2001). Mesophyll cell are affected directly or indirectly by release of organic and inorganic solutes. The stomatal closure can result in decreased production of energy equivalents like ATP and NADPH and are responsible for limiting the dark reactions of the photosynthesis. Quantum yield (ΦPSII) and photochemical quenching (qP) are significantly reduced, whereas non-photochemical quenching (NPQ) rises in the leaves of plants exposed to O3 (Plazek et al. 2001). High qN with successive decrease in qP indicates non-radiative dissipation of energy. The loss of quantum yield of ET is directly related to downregulation of PET. The reduction of photochemical efficiency (Fv/ Fm) denotes damage to PSII reaction centres (Matyssek et al. 2008; Ro-Poulsen et al. 1998; Creissen et al. 1999; Zheng et al. 2000; Chen and Gallie 2005; D’Haese et al. 2005; Felzer et al. 2007). Increase in Fo indicates alteration in the transport of excitation energy from light-harvesting complexes to reaction centres. In the light reactions, the generation of electrons by the water splitting reaction in PSII is impaired, and electron transport from PSII to PSI is lost. The stomatal closure reduces the rate of CO2 assimilation but increases the diffusive resistance of CO2 in the mesophyll, thus changing the allocation of carbon to different parts of plant species (Fowler et al. 1998; Grini et al. 2005; Chen and Gallie 2005). The reduction in the carboxylation efficiency affects the light and dark reactions of photosynthesis (Pleijel 2011; Grini et al. 2005; Matyssek et al. 2008). The harmful effects on the carboxylation efficiency showed direct oxidative damage and indirect heat-related injuries to RuBisCO. Stomatal closure may be the first mechanism for plant protection against the harmful impacts of O3. On the other side,

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increased production of antioxidants has shown to curb oxidative stress induced by gaseous pollutants. A decline in RuBisCO activity majorly contributed to the degradation of photosynthetic capacity of plants (Calatayud et al. 2011; Creissen et al. 1999). Decline in chlorophyll concentrations gives rise to decline in light harvesting and total assimilation rate. The reduction in the light-harvesting capacity of chlorophyll together with a decreased efficiency of photosynthetic energy conversion results in decreased total assimilation. Potassium flux changes the guard cell volume in the stomata and regulates the stomatal aperture. Elevated ozone exposure inhibits the activity of guard cell K+ channels, which intervene stomatal opening and leads to reduced photosynthesis (Hassan and Tewfik 2006). Non-stomatal factors which impact the photosynthetic efficiency include (i) lesser RuBP regeneration from lower pools of Calvin cycle intermediates, (ii) reduced efficiency of RuBisCO because of direct enzyme oxidation and (iii) reduced carbon dioxide transport to the enzymes. Ozone induces decline at RNA transcript level for the small subunit (rbcS) and large (rbcL) subunits of RuBisCO (Zheng et al. 2000). It also decreases the expression of photosynthetic genes for RuBisCO activase (Meehl et al. 2007; Duenas et al. 2002). Pigments like zeaxanthin also intervene photoprotection in O3-exposed plant species. Antioxidant enzymes like ascorbate peroxidase cause detoxification of H2O2 by breaking up into simpler substances like water through a number of reactions in the ascorbate-glutathione cycle (Bartholomay et al. 1997). Antioxidants like hydrophilous ascorbate (vitamin C) and lipophilous α-tocopherol (vitamin E) protect the plasma membranes of plant species. Ascorbic acid acts an important role in defending against ROS in plants (Fowler et al. 1998; Pleijel 2011; Biswas et al. 2008). The biological synthesis of phenylpropanoids increases more in sensitive species as compared to the tolerant ones. The decrease in carbon assimilation of plants exposed with O3 increases the PAL activity which is meant for the production of phenylalanine and transcinnamic acid and precursor of phenylpropanoids. Polyamines protect plastids and thylakoid membranes against O3 high concentrations. Addition of external polyamines decreases damage caused by O3 in plants. These polyamines are also related with thylakoid membranes and a number of photosynthetic subcomplexes. They will further conjugate with hydroxycinnamic acids and protect the photosynthetic machinery from ROS activity (Gravano et al. 2004). A decrease in thylakoid-bound is significantly responsible for rise of antenna size of the LHCII; however, the number of reaction centres per unit area plus the maximal photosynthetic rate and the maximum yield of photochemistry (Fv/Fm) decreased. The protections by polyamines against oxidants include (i) scavenging of ROS, (ii) increasing the infiltration rate of antioxidant by SOD enzyme, (iii) protecting the membranes against oxidant damage, (iv) altering the redox state of the cells and (v) maintaining the expression of genes. Isoprene washes out ROS and provides protection against oxidative stress (Lal et al. 2000). It effectively reacts with O3 that produces hydroxymethyl hydroperoxide, hence aggravating the O3-induced damage. It reduces O3 by directly reacting with it in the intercellular spaces and, therefore, counteracts the O3 damaging impact on membranes (Creissen

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et al. 1999; Felzer et al. 2007). Rise in flavonoid content in plants treated with O3 suggests their role in washing out ROS that consists of superoxide anion, hydrogen peroxide and hydroxyl radical. They also play a role in peroxidase-mediated catabolism of H2O.

4.5.5.1 Photosynthetic Pigments Ozone-produced ROS are known to change the membrane-bound organelles, like chloroplast, that resulted in destruction of photosynthetic pigments (Grini et al. 2005; Eckmullner and Sterba 2000). Significant decline in total chlorophyll content of rice plants under ambient and elevated dose of O3 of 27 and 44%, respectively, was recorded (Gravano et al. 2004; Duenas et al. 2002; Bartholomay et al. 1997; Bytnerowicz et al. 2007; Calatayud et al. 2011; Eckmullner and Sterba 2000). Feng et al. (2008) documented that about 40% decline in chlorophyll content in wheat plants under O3 exposure was reported in their meta-analytical study. High concentrations of O3 showed decreased trend in total chlorophyll content in subtropical broad-leaved tree species like Cinnamomum camphora, Cyclobalanopis glauca (Ali et al. 2012) and Citrus clementina. Gielen et al. (2007) treated Fagus sylvatica to double the times of ambient ozone concentration and recorded 15.9% decline in total chlorophyll content. Riikonen et al. (2005) reported 5 and 19% decreased trend in total chlorophyll content in two European silver birch clones 4 and 80, respectively, upon ozone exposure. In six species of Trifolium alexandrinum cultivars, total chlorophyll showed decreased trend, ranging from 13.1 to 57.3% and carotenoids by 9.4–39.2% under ozone treatment exposed with a dose of 10ppb (Chaudhary and Agrawal 2015; Leitao et al. 2007). Pinus canariensis treated with high O3 concentration (67 ppb) showed an increment of 14.3% in photosynthetic pigments (D’Haese et al. 2005). In Vernonia also, O3 exposure increased the total chlorophyll content (Plazek et al. 2001). Carotenoids are vital photoprotective agents that prevent photooxidative chlorophyll destruction (Felzer et al. 2007; Plazek et al. 2001; Gielen et al. 2007; Riikonen et al. 2005). Variations in carotenoid content after exposing them with O3 may result in modification in their capacity to protect photosystem against photooxidation. Several studies have reported O3-induced decline (Calatayud et al. 2011; Eckmullner and Sterba 2000; Matyssek et al. 2008; Ro-Poulsen et al. 1998; Creissen et al. 1999; Zheng et al. 2000; Chen and Gallie 2005; Felzer et al. 2007) or induction (Bartholomay et al. 1997; Bytnerowicz et al. 2007; Calatayud et al. 2011) in carotenoid content. The effects of O3 on 3-year-old Clementina mandarin trees were reported at two O3 concentrations, and decline in total chlorophyll as well as carotenoid pools in leaves was recorded (Islam et al. 2000; Gravano et al. 2004; Duenas et al. 2002; Bartholomay et al. 1997). 4.5.5.2 RuBisCO Content The decrease in RuBisCO content after exposing them with O3 has a direct effect in form of significant decline in photosynthetic capacity (Leitao et al. 2007). Ozoneinduced decrease in RuBisCO quantity may probably be due to inhibition of synthesis and/or its elevated degradation (Gielen et al. 2007). Sarkar and Agrawal

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(2010a) observed that high O3 caused damage to large subunit (LSU) and small subunit (SSU) of RuBisCO in rice. Same results were obtained in wheat (Sarkar and Agrawal 2010a, b), maize (Ma et al. 2016) and mung bean (Li et al. 2014). Amount of RuBisCO increased by 10, 20 and 17% and decreased by 7% in O3 atmospheres of +20, +40, +60 and +80, respectively, compared to nonfiltered chambers (Leitao et al. 2007).

4.6

Conclusion

The present chapter focuses on the significance of secondary criteria air pollutant, i.e. tropospheric ozone both at international and national level. Relatively, developing countries are more prone to tropospheric ozone pollution due to high anthropogenic activities. As tropospheric ozone is secondary product due to reactions among precursors like NO2, VOCs and CO in the presence of sunlight, therefore its chemistry is a challenging aspect. Increasing concentrations of ozone leads to climate change due to its major role in greenhouse effect. In the case of human health, major observations show a strong relationship between short-term exposure and pulmonary dysfunctions, pulmonary inflammation and other lung disorders along with indications of pain and cough on deep inspiration, immune system energization and epithelial cell injury. Ozone exposure studies also lead to permanent damage. Epidemiological studies conducted on broad scale with respect to communities or analysing real-time series of daily environmental and health data reflects a stable and clear relation between ozone and immediate and short-term adverse health impacts, expressed in terms of death rate or morbidity indicators. In the case of plants, tropospheric ozone is the most dangerous pollutant that is why it is called as phytotoxic agent. Ozone causes visible injury, impairs photosynthesis, alters stomatal conductance, reduces yield and also disrupts the metabolic pathway of crop plant species. Ozone also increases the susceptibility of crop plants towards pest and diseases. Hence, overall, this secondary criteria air pollutant needs a stringent check on its concentrations, and there is an urgent call for agricultural scientists, policymakers and farmers to work together for the betterment of environmental safety, food security and sustainability and overall maintenance of ecological balance.

References Aamlid D, Tørseth K, Venn K, Stuanes AO, Solberg S, Hylen G et al (2000) Changes of forest health in Norwegian boreal forests during 15 years. For Ecol Manag 127(1–3):103–118 Agathokleous E, Saitanis CJ, Koike T (2015) Tropospheric O3, the nightmare of wild plants: a review study. J Agric Meteorol 71(2):142–152 Ainsworth EA, Yendrek CR, Sitch S, Collins WJ, Emberson LD (2012) The effects of tropospheric ozone on net primary productivity and implications for climate change. Annu Rev Plant Biol 63:637–661 Akimoto H (2003) Global air quality and pollution. Science 302:1716–1719

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5

Policy Regulations and Future Recommendations

Abstract

Air quality has been worsened due to increase in urbanization and industrialization both nationally and internationally. This poor air quality has affected floral and faunal diversity severely. This will affect the whole ecosystem widely. The major factors including biomass burning, high vehicular emissions, increment in industrial emissions and increase in demand for energy are responsible for increase in air pollution. Therefore, both natural and anthropogenic activities are responsible for the alarming high concentrations of criteria air pollutants. Criteria air pollutants are hazardous categories of air pollutants under Clean Air Act, 1990, and urgent step has been needed by EPA to set permissible limits for them. Hence, it is an important agenda to control and mitigate these air pollutants which are affecting plants/vegetation, human health and other environmental concerns along with their sources. Hence, this chapter aims at various control strategies designed by national as well as international agencies to combat the deleterious concentrations of criteria air pollutants. Control strategies include various norms, implementation of clean air act policies, mitigation protocols and laws and legislations. Keywords

Criteria air pollutants · Control policies · Clean Air Act · Air quality

5.1

Introduction

Air pollutants affect a quarter of the world’s population, which resulted in a large scale from anthropogenic activities like biomass burning, industrialization and vehicular activities (WHO 2012). Air pollutants also damage buildings, crops, ecosystems and wildlife populations. Lack of control technologies and policies is responsible for worsening air quality and leads to increase in concentrations of air pollutants (Burney and Ramanathan 2014). The concentrations have increased and # Springer Nature Singapore Pte Ltd. 2019 P. Saxena, Criteria Air Pollutants and their Impact on Environmental Health, https://doi.org/10.1007/978-981-13-9992-3_5

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crossed the national as well as international air quality standards (Pope et al. 2002; Lelieveld et al. 2015). Population explosion and increase in traffic fleet in cities are mainly responsible for deteriorating the air quality (Tsigaridis and Kanakidou 2007; Kinney 2008; Johnson et al. 2011; Morgan et al. 2016). The rapid increase in vehicular activities especially during high rush times is responsible for intense air pollution hazards mostly in urban areas (Anderson et al. 2004; Derwent et al. 2009). These sources are considered as large emitters of criteria air pollutants like NO2, SO2, CO, Pb, O3 and particulate matter. These pollutants would cause severe harmful impacts in the surroundings and degrade the air quality. Due to this, a number of global phenomena would take place like photochemical smog, ozone layer depleted due to ozone-depleting substances (ODS), global climate change, acid rain and damage to plant, human and material health (Gokhale and Khare 2007; Kanlindkar 2007; Tiwari et al. 2012). Climate change is a long-term change which resulted into significant change in environmental or weather conditions. The climate change is a consequence of global warming that occurs due to rise in the concentration of greenhouse gases (GHGs) like methane, carbon dioxide, black carbon, organic carbon, ozone and other light-absorbing particles and gases. As a consequence, weather circulation patterns disturbed, very low rainfall and frequent rise in floods and droughts etc. (Sharma and Dikshit 2015; Kumar et al. 2017; Dhyani et al. 2017). Criteria air pollutants are emitted from two major sources, natural and anthropogenic. Natural sources are mainly soil particles, dust particles of different sizes, sea spray, forest fire, etc., while anthropogenic sources are from transport, industrial, residential, domestic and commercial sectors. The major contribution in urban areas is from vehicular activities and biomass burning which are ultimately responsible for climate change. The problem of air pollution is rapidly increasing at a vast rate in both developed and developing countries. Tremendous increase in population rate along with urbanization and industrialization leads to the emission of various air pollutants that are causing bad air quality (Barnett et al. 2005). Since the last 10 years, the problem of high urbanization is noticed in the developing countries. Urbanization is a major factor which produces pollution and congestion in most of the developing countries (Asian, African and Latin American) (Invernizzi et al. 2011). The city population in 1960 was not more than 22% and increased to 34% in 1990, and it is depicted to be 50% of total population by 2020 in developing world (Gurjar et al. 2016). This will increase the consumption rates, scarcity of resources and non-affordability of environment-friendly technology which poses a high economic burden. Interestingly, Organization for Economic Cooperation and Development (OECD) observed that in the year 2010, the cost of air pollution in China was US$1.5 trillion and US$2.2 trillion in India (UNEP Year Book 2014). Another study by UNEP has found that one billion people are affected by bad air quality every year which resulted in 3.5 million deaths. On the basis of percentage distribution, this mortality rate has showed an increase by 4% worldwide, 5% in China and 12% in India between 2005 and 2016. As per CSE’s 2017 report, air pollution ranked fifth in causing deaths and results in 710,000 premature deaths related to lung disorders, cardiovascular disorders and respiratory disorders in India (DEFRA 2017).

5.1 Introduction

129

Fig. 5.1 Possible control methods for criteria air pollutants

As air quality has been deteriorating rapidly, therefore, reduction of these criteria air pollutants is of prime concern. These air pollutants possess transboundary movements and affect the living systems and materials; therefore, control strategies are required at a particular area (Kura et al. 2013). The preventive air pollution measures include reduction and captures of air pollutant to acquire an air quality standard. One option to reduce the concentrations of air pollutants is by creating public awareness by adopting certain simple daily life control measures like less motor vehicle and encouraging the use of public transport and use of clean fuel and change in industrial combustion process to minimize the air pollution or some other air pollution control techniques which can coexist with economic viability. These control methods include various equipments like cyclone separators, baghouses, adsorbents, wet scrubbers, etc. Figure 5.1 describes about various air pollution control basic processes like collection, measurement and treatment of pollutants. Nevertheless, control of toxic agents in air at their source level is most likely an efficient method. Hence, this chapter describes about different control methods and policy measures used to combat the deleterious concentrations of criteria air pollutants.

5.1.1

Source Emission Control

The biggest challenge nowadays is to control air pollution which will directly serve for the welfare of the society. Towards this direction, professionals have developed strategies and technologies to control air pollution and emission problem. The major challenges in control measure are their efficiency and cost-effectiveness. The air pollutant prevention depends upon the use of cleaner raw fuel material, emission control and improved process design, for reduction of the pollutant from sources

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(Maji et al. 2017). The approaches for prevention of air pollutant are described as follows.

5.1.1.1 Elimination Approach The appropriate management of fuel firing practices allowing combustion improvement along with adequate air can help in lowering incomplete combustion product. The complete burning of fuel reduces the emission of gas like carbon monoxide which is more harmful to human health (DEFRA 2016).

5.2

Choice of Fuel

Power plant is the major source of sulphur oxides (SO2) and nitrogen oxides (NO2) which are emitted through high sulphur coal-based fired combustion process. The selection of cleaner fuel is a primary step towards air pollutant reduction measures. The gas-based combustion emits negligible amounts of particulate matters compared to oil- and coal-based fired combustion process. The use of low sulphur coal and oil in power plant and transport can be considered as a control option for reduction of SO2 emission. The use of natural gas can also reduce the NOx, SO2 and volatile organic compound (VOC) emissions. However, the choice of fuel mainly depends upon economics well as environmental regulation (EEA 2011).

5.3

Fuel Cleaning

The suspended particulate matter (SPM) emitted from the coal-based power plant and oil-based transport system. The cleaning of fuel is an important step towards clean technology. This will further reduce the production of particulate matter emission. The mechanical process involves purification of coal through washing that minimized its ash and sulphur content. The alternative of coal washing is coal cofiring with higher and lower ash content. The cleaning of fuel does not only reduce the particulate emission, low ash, also increase the life of the boiler (Goodmana et al. 2009).

5.4

Selection of Technology and Methods

The advent of new advanced technologies or processes can minimize the product of incomplete combustion (PIC) emissions. High technology-based coal combustion methods, like coal gasification, enclosed coal crushers and grinders, are examples of purification processes that will slow down PICs with an estimate of 10% (Hou et al. 2010).

5.5 Particle control system

5.4.1

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Emission Control Approaches

The strategies towards controlling emission of air pollutants are important in protecting public health and welfare. The essential planning control activities include setting up an emission limit, identifying all emission sources, the scope of process modification, defining the control problem and selection of control system. But the major challenge in specifying air pollution control for air pollutant has been to set an acceptable emission level. The selection of suitable air pollution control system is based on environmental implication and economic viability. The modification of process to reduce or eliminate usually offers the most economical way to reduce emissions because it requires little capital to implement it (Fu et al. 2000; Marlier et al. 2016). The control technologies can be grouped into physical and chemical processes used to separate pollutants from the carrier gas and classified into two classes: (A) particle control system and (B) gas and vapour control system. But technology may differ on the basis of pollutant nature as well as whether it is organic or inorganic. The following are some commercially used technologies to curb air pollutant:

5.5

Particle control system

The reduction of particulate matter is an important challenge for industrial air pollutant abatement technologies. The generated particles are collected through several mechanisms; some of the available technologies are described below: a) Gravity settling chambers This particulate collection device is based on the gravity principle to settle the particulate matter in a gas stream which is going towards the long chamber. The settling chambers are highly effective for larger particulate matter greater than 50 micrometers in aerodynamic diameter (Wark et al. 1981; EPA 1998). The collection efficiency of gravity settling chambers for PM10 is very low, typically less than 10%. Despite low collection efficiency of PM10 and PM2.5, the gravity settling chamber has been used in the past at vast level in refining, power and heating plant industries to collect the larger particles (Kumar et al. 2015). In this process the initial requirement is to reduce the carrier gas velocity to settle the particulate matter at bottom chamber through the gravity action. The velocity of gas