Contaminants of Emerging Environmental Concern

497 Pages·2008·6.149 MB·English

by  Environmental and Water Resources Instit

C E
ONTAMINANTS OF MERGING
E C
NVIRONMENTAL ONCERN

SPONSORED BY
Emerging Contaminants of Concern Task Committee of the
Environmental Council

Environmental and Water Resources Institute (EWRI)
of the American Society of Civil Engineers

EDITED BY
Alok Bhandari
Rao Y. Surampalli
Craig D. Adams
Pascale Champagne
Say Kee Ong
R. D. Tyagi
Tian C. Zhang

Published by the American Society of Civil Engineers
Library of Congress Cataloging-in-Publication Data

Contaminants of emerging environmental concern / sponsored by Emerging Contaminants
of Concern Task Committee of the Environmental Council [and] Environmental and Water
Resources Institute (EWRI) of the American Society of Civil Engineers ; edited by Alok
Bhandari … [et al.].
p. cm.
Includes bibliographical references and index.
ISBN 978-0-7844-1014-1
1. Pollutants. I. Bhandari, Alok. II. Environmental Council of the States (U.S.) Emerging
Contaminants of Concern Task Committee. III. Environmental and Water Resources
Institute (U.S.)

TD174.C66 2009
628.5'2--dc22 2008048522

American Society of Civil Engineers
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Reston, Virginia, 20191-4400

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Copyright © 2009 by the American Society of Civil Engineers. All Rights Reserved.
ISBN 978-0-7844-1014-1
Manufactured in the United States of America.
Preface
The 21st century has unfolded the widespread occurrence of a new category of
contaminants which have attracted the attention of citizens, scientists and engineers,
researchers, state and federal agencies, environmental groups, industrial and
commodity groups, and regulators. These contaminants are predominantly
unregulated anthropogenic chemicals that occur in air, soil, water, food, and,
human/animal tissues in trace concentrations, are persistent in the environment, and
are capable of perturbing the physiology of target receptors. These chemicals are
considered to be contaminants of emerging environmental concern (CoEECs).

The ASCE’s Technical Committee on Hazardous, Toxic, and Radioactive
Waste Management identified the need to collect and present the latest information on
the occurrence and fate of CoEECs in natural and engineered systems. The committee
envisioned to prepare an easy-to-read book that would serve as a reference for
practicing professionals and be equally effective as a text in undergraduate or
graduate courses.

This book report is organized by types of commonly occurring and widely
studied CoEECs. Chapter 1 introduces the topic of the book report and presents the
need to understand the characteristics and environmental occurrence of these
chemicals. Chapter 2 discusses analytical chemistry methods for sampling,
separation, purification, identification and quantification of CoEECs in environmental
samples. Chapter 3 discusses pharmaceuticals, while Chapter 4 talks about personal
care products. Chapters 5 and 6 present information about antibiotics and hormones,
respectively. Chapter 7 discusses the occurrence and fate of phthalate plasticizers and
their degradation products in natural and engineered systems. Chapters 8 and 9 focus
on surfactants and their derivatives, and fire retardants. Chapter 10 discusses
pesticides, several of which are considered to be CoEECs at trace concentrations.
Chapter 11 focuses on nanomaterials, a category of CoEECs whose health and
environmental implications are just beginning to be evaluated. Finally, Chapter 12
talks about organisms capable of degrading CoEECs and the molecular biology tools
used to study these organisms.

The editors acknowledge the hard work and patience of all authors who have
contributed to this book.

- AB, RYS, CDA, PC, SKO, RDT, TCZ

iii
Contributing Authors
Craig D. Adams, University of Kansas, Lawrence, KS
Shankha K. Banerji, University of Missouri – Columbia, MO
S. Barnabe, Pulp and Paper Center, University of Quebec at Trois-Rivières, QC
I. Beauchesne, INRS, Universite du Quebec, Quebec, QC
Alok Bhandari, Iowa State University, Ames, IA
Satinder K. Brar, INRS, Universite du Quebec, Quebec, QC
Pascale Champagne, Queens University, Kingston, ON
Supreeda Homklin, Chulalongkorn University, Bangkok
Keith C.K. Lai, University of Texas, Austin, TX
Warisara Lertpaitoonpan, Iowa State University, Ames, IA
Tawan Limpiyakorn, Chulalongkorn University, Bangkok
Say Kee Ong, Iowa State University, Ames, IA
Bala Subramanian, INRS, Universite du Quebec, Quebec, QC
Rao Y. Surampalli, U.S. Environmental Protection Agency, Kansas City, KS
R.D. Tyagi, INRS, Universite du Quebec, Quebec, QC
Mausam Verma, Dalhousie University, Halifax, NS
Kang Xia, Mississippi State University, Mississippi State, MS
Song Yan, INRS, Universite du Quebec, Quebec, QC
Tian C. Zhang, University of Nebraska-Lincoln, Omaha, NE

iv
Contents
Chapter 1 Introduction.................................................................................................1
1.1 Background1............................................................................................................1
1.2 Types of CoEECs......................................................................................................3
1.3 Future Challenges......................................................................................................3
Chapter 2 Analytical Methods for Environmental Samples.........................................7
2.1 Introduction..............................................................................................................7
2.2 Sample Handling, Preparation, Extraction, and Clean-Up........................................10
2.3 Sample Analysis......................................................................................................24
2.4 Conclusion..............................................................................................................49
Chapter 3 Pharmaceuticals........................................................................................56
3.1 Introduction............................................................................................................56
3.2 Properties................................................................................................................59
3.3 Occurrence and Behavior in Natural Systems..........................................................63
3.4 Fate and Transformation in Engineered Systems......................................................69
3.5 Conclusion..............................................................................................................79
Chapter 4 Personal Care Products.............................................................................86
4.1 Introduction............................................................................................................86
4.2 Properties................................................................................................................88
4.3 Occurrence and Behavior in Natural Systems........................................................107
4.4 Fate and Transformation in Engineered Systems....................................................118
4.5 Conclusion............................................................................................................127
Chapter 5 Antimicrobials and Antibiotics................................................................141
5.1 Introduction..........................................................................................................141
5.2 Properties of Common Antibiotics.........................................................................143
5.3 Incomplete Metabolism of Antibiotics...................................................................152
5.4 Occurrence of Antibiotics in Natural Systems........................................................153
5.5 Fate of Antibiotics in Engineered Systems..............................................................165
5.6 Antibiotic-Resistant Bacteria..................................................................................170
5.7 Conclusion............................................................................................................175
Chapter 6 Hormones................................................................................................186
6.1 Introduction..........................................................................................................186
6.2 Properties and Structure of Common Hormones....................................................187
6.3 Sources of Androgens and Estrogens.....................................................................190
6.4 Fate and Behavior in Natural Systems....................................................................195
6.5 Fate of Livestock Waste Estrogens in Engineered Systems......................................198
6.6 Fate of Estrogens in Septic Tanks and Sewer Lines................................................203
6.7 Fate of Estrogens in Municipal Sewage Treatment Systems....................................204
6.8 Conclusions...........................................................................................................222
Chapter 7 Phthalate Plasticizers and Degradation Products...................................235
7.1 Introduction..........................................................................................................235
7.2 Background..........................................................................................................236
7.3 General Health Issues............................................................................................238
7.4 Degradation of Toxic Intermediates.......................................................................242
v
7.5 Fate in the Environment.........................................................................................245
7.6 Fate in Wastewater Treatment Plants.......................................................................259
7.7 Fate in Drinking Water and Reuse Water.................................................................268
7.8 Conclusion............................................................................................................269
Chapter 8 Surfactants..............................................................................................279
8.1 Introduction..........................................................................................................279
8.2 LAS and APEO Surfactants...................................................................................280
8.3 Occurrence and Behavior in Natural Systems........................................................284
8.4 Fate and Transformation in Engineered Systems....................................................289
8.5 Regulations...........................................................................................................307
8.6 Conclusions...........................................................................................................308
Chapter 9 Brominated Fire Retardants....................................................................315
9.1 Introduction..........................................................................................................315
9.2 General Information on BFRs................................................................................316
9.3 Occurrence and Behavior in Natural Systems........................................................321
9.4 Fate and Transformation in Engineered Systems....................................................331
9.5 Issues Related to Regulation, Policy, and Future Actions........................................334
9.6 Conclusion............................................................................................................335
Chapter 10 Pesticides................................................................................................343
10.1 Introduction........................................................................................................343
10.2 Physical and Chemical Properties........................................................................346
10.3 Occurrence and Behavior in Natural Systems......................................................367
10.4 Fate and Transformation in Engineered Systems..................................................381
10.5 Considerations for Pesticide Application and Pollution Control............................395
10.6 Conclusion..........................................................................................................401
Chapter 11 Nanoparticles.........................................................................................416
11.1 Introduction........................................................................................................416
11.2 Classification of Nanomaterials............................................................................419
11.3 Fate of Nanomaterials in Air, Water, and Soil........................................................423
11.4 Health Effects......................................................................................................427
11.5 Regulations.........................................................................................................434
11.6 Socioeconomic Issues..........................................................................................436
11.7 Conclusion..........................................................................................................437
Chapter 12 Molecular Biology Techniques for CoEEC Degrading Organisms........446
12.1 Introduction........................................................................................................446
12.2 CoEEC Degrading Microbes and Their Genes.....................................................450
12.3 Molecular Biology Techniques............................................................................451
12.4 Detection of CoEEC Degraders...........................................................................456
12.5 Conclusion..........................................................................................................465
Editor Biographies.....................................................................................................481
Index..........................................................................................................................484
vi
CHAPTER 1

Introduction

Alok Bhandari

1.1 Background

Over the past century our industries have produced thousands of chemicals to
enhance our overall quality of life. These compounds have allowed us to increase
agricultural productivity, improve animal health, and boost human longevity. The
improper use and disposal of some of these chemicals, however, has also resulted in
adverse human health impacts and environmental problems. The societal need to
ensure the quality of soil and water environments was first recognized in the mid-20th
century. Soon thereafter, we began regulating our coastal waters and surface streams
for sediments and oxygen-consuming organic material. Then came Rachel Carson’s
Silent Spring which introduced the public to the environmental and human health
impacts of a wide array of persistent and toxic anthropogenic chemicals. Regulations
were reinforced and maximum contaminant levels (MCLs) were established to
minimize human exposure to chemicals characterized as acutely toxic or
carcinogenic. The National Pollutant Discharge Elimination System (NPDES)
ensured that these contaminants were not discharged into surface water from point-
sources such as industries and municipal wastewater treatment plants (WWTPs).

The late 20th century produced great advancements in trace chemical analysis
including separation and identification methods such as solid phase extraction, gas-
chromatography/mass-spectrometry (GC/MS), and liquid-chromatography/mass-
spectrometry (LC/MS). These technologies allowed scientists to separate compounds
from environmental media and identify them at unprecedented levels of parts per
trillion (ppt or ng/L) and lower. Suddenly, a broad range of previously undetected
micropollutants became apparent in media as diverse as food, tissue, breast milk, and
water samples collected from rivers, lakes, aquifers, municipal water treatment plants
and WWTPs. Thus, the dawn of the 21st century has brought with it the knowledge of
widespread, trace-level environmental occurrence of a generally unregulated group of
chemicals that have been variously termed as ‘emerging chemicals of concern’,
‘contaminants of concern’, ‘contaminants of emerging concern’, ‘micro-constituents’,
‘unregulated contaminants’, ‘persistent organic pollutants’, ‘pharmaceuticals and
1
2 CONTAMINANTS OF EMERGING ENVIRONMENTAL CONCERN
personal care products’, or ‘contaminants of emerging environmental concern
(CoEECs)’.

CoEECs are usually unregulated, but persistent anthropogenic chemicals that
are discharged into the environment or generated therein at low concentrations. These
are potentially harmful compounds whose effects on ecology and human health are
poorly understood because of their recent discovery in the environment. CoEECs
enter the environment through a variety of domestic, industrial and agricultural
activities. Some CoEECs are used by humans as pharmaceuticals or personal care
products and enter the hydrological cycle through discharges from municipal
wastewater treatment plants or on-site septic systems. Others are used in the animal
agriculture for growth promotion or disease control and enter the environment when
animal waste is applied on agricultural fields. Still others are used in industrial
surfactants, plasticizers, or flame retardants and released via industrial discharges.
These compounds are mobile and persistent in the environment and occur in air,
water, sediments, and tissues of ecological receptors at concentrations of ppt to low
parts-per-billion (ppb, μg/L).

Scientists from the U.S. Geological Survey (USGS) were among the first to
report a widespread occurrence of CoEECs at targeted sites in streams across the
United States (Kolpin et al., 2002). USGS’s Toxic Substances Hydrology Program
has since conducted other nation-wide field investigations and have recently reported
on the presence of these compounds in groundwater and sources of municipal
drinking water (Barnes et al. 2008; Focazio et al., 2008). The most frequently
detected compounds in groundwater in human and animal waste sources included
N,N-diethyltoluamide, (DEET, insect repellent), bisphenol-A (plasticizer), tri(2-
chlroethyl)phosphate (flame retardant), sulfamethoxazole (antibiotic) and 4-
octylphenol monoethoxylate (surfactant metabolite). When untreated sources of
municipal drinking water were tested, the five most frequently detected CoEECs in
surface water included cholesterol, metolachlor (herbicide), cotinine (nicotine
metabolite), (cid:2)-sitosterol (natural plant sterol), and 1,7-dimethylxanthine (caffeine
metabolite).

Robust data on ecological and human health effects of exposure to CoEECs at
environmentally relevant concentrations is still lacking. However, extensive research
is being conducted on this topic and early results appear to suggest some ecological
concern. Frogs exposed to the anti-bacterial agent, triclosan, have been found to show
reduced activity and startle response (Fraker and Smith, 2004). Residues of the anti-
inflammatory, diclofenac, have been implicated with declines in vulture populations
in South Asia (Oaks et al., 2004). Fish collected downstream from municipal
wastewater treatment plants discharging effluent containing a variety of estrogenic
chemicals have revealed signs of altered sex ratios, reduced gonad size, gonadal
intersex, disrupted ovarian and testicular histopathology and vitellogenin induction,
that are typical of exposure to estrogenic chemicals (Vajda et al., 2008). Intersex
gonads and high vitellogenin concentrations were recently reported in male fish
CONTAMINANTS OF EMERGING ENVIRONMENTAL CONCERN 3
collected from four river basins of the Southeastern United States indicating exposure
to EDCs and estrogenic chemicals (Hinck et al., 2008).

The antiepileptic drug, carbamazepine, has been shown to impact the
survivability of the non-biting midge Chironomus riparius but it had no effects on
other organisms such as the oligochaete Lumbriculus variegates and the freshwater
snail Potamopyrgus antipodarum (Oetken et al., 2005). Other researchers have found
little or no ecological impact of some CoEECs. No adverse impact of exposure of the
antidepressant, fluoxetine, was observed on zooplankton at environmentally relevant
concentrations (Laird et al., 2007). The antibiotic, tylosin, was shown to pose little or
no risk for aquatic macrophytes (Brain et al., 2005). Exposure to the surfactant
derivative, 4-nonylphenol, at or above the EPA toxicity-based chronic exposure level
produced no changes in morphological endpoints such as the gonadosomatic and
hepatosomatic indices, secondary sexual characteristics and histopathology in male
fathead minnows (Schoenfuss et al., 2008).

1.2 Types of CoEECs

Several classes of anthropogenic compounds can be classified as CoEECs. In its
national reconnaissance studies of US streams, groundwater and raw drinking water,
the USGS has focused on the subset of CoEECs summarized in Table 1.1 (USGS,
2008). These include human and veterinary antibiotics, sex and steroidal hormones,
household and industrial chemicals and other human pharmaceuticals. The latter
category includes lifestyle medicines analgesics, anti-inflammatories, stimulants,
antacids, antidepressants, antihypertensives, antidiabetics, anticoagulants, antianxiety,
antiasthmatics, antihyperlipidimics, and antianginals. This book report includes
specific chapters focusing on pharmaceuticals (chapter 3), personal care products
(chapter 4), antibiotics (chapter 5), hormones (chapter 6), plasticizers (chapter 7),
surfactants (chapter 8), fire retardants (chapter 9), pesticides (chapter 10), and
nanomaterials (chapter 11). Also discussed are analytical methods used for the
separation, clean-up, and identification of CoEECs in environmental samples (chapter
2) and molecular biology techniques for CoEEC degrading organisms (chapter 12).

1.3 Future Challenges

Modern analytical tools and techniques have allowed detection of CoEECs at
minute concentrations. Continued development and refinement of techniques for
separation and quantitation of trace level CoEECs in complex environmental matrices
is necessary to improve our understanding of factors affecting the fate and transport
of these contaminants. This knowledge will lead to the development of models that
can accurately predict the behavior of these contaminants in the soil and water
environment.