Susan D. Richardson

Environmental mass spectrometry: emerging contaminants and current issues.

Introduction 747 Major Analysis Trends 748 Sampling and Extraction Trends 748 Chromatography Trends 748 Use of Nanomaterials in Analytical Methods 748 Other Trends with Emerging Contaminants 749 General Reviews 749 Sucralose and Other Artificial Sweeteners 749 Antimony 750 Nanomaterials 751 General Reviews 751 Nanosilver and Nanogold 751 Fullerenes and Other Carbon-Based Nanomaterials 752 Nanomaterials in Foods, Plants, and Biota 752 PFOA, PFOS, and Other Perfluorinated Compounds 752 Measurements in Biota 753 Paper Coatings for Food Packaging 754 Drinking Water 754 Landfill Leachates 754 Seawater and Sediments 755 Air and Soils around a Fluorochemical Manufacturing Plant 755 Sewage Sludge 755 New PFC Substitutes 755 Fate and Sources 755 New Methods 756 Pharmaceuticals and Hormones 756 Environmental Impacts of Pharmaceuticals 756 General Reviews 757 New Methods 757 Illicit Drug Methods 758 Marine Sample Methods 758 Biota Methods 758 Direct Analysis and Novel Approaches 759 Occurrence Studies 759 Fate of Pharmaceuticals: Wastewater Treatment, Drinking Water Treatment, and Photolysis 760 Hormones 762 Drinking Water and Swimming Pool Disinfection Byproducts 762 Drinking Water DBPs 762 Combining Chemistry with Toxicology 763 Discovery of New DBPs 763 N-DBPs 763 Nitrosamines 764 Alternative Disinfection Technologies Using Iodine, UV, and Other Treatments 765 Other Formation/Fate Studies 765 DBPs of Pollutants 765 New Swimming Pool Research 766 Sunscreens/UV Filters 767 Brominated Flame Retardants 767 Benzotriazoles 769 Dioxane 769 Siloxanes 769 Naphthenic Acids 769 Musks 770 Pesticide Transformation Products 770 Perchlorate 771 Algal Toxins 772 Microorganisms 773 Biography 773 Acknowledgment 773 References 774

What's in the pool? A comprehensive identification of disinfection by-products and assessment of mutagenicity of chlorinated and brominated swimming pool water

Background Swimming pool disinfectants and disinfection by-products (DBPs) have been linked to human health effects, including asthma and bladder cancer, but no studies have provided a comprehensive identification of DBPs in the water and related that to mutagenicity. Objectives We performed a comprehensive identification of DBPs and disinfectant species in waters from public swimming pools in Barcelona, Catalonia, Spain, that disinfect with either chlorine or bromine and we determined the mutagenicity of the waters to compare with the analytical results. Methods We used gas chromatography/mass spectrometry (GC/MS) to measure trihalomethanes in water, GC with electron capture detection for air, low- and high-resolution GC/MS to comprehensively identify DBPs, photometry to measure disinfectant species (free chlorine, monochloroamine, dichloramine, and trichloramine) in the waters, and an ion chromatography method to measure trichloramine in air. We assessed mutagenicity with the Salmonella mutagenicity assay. Results We identified > 100 DBPs, including many nitrogen-containing DBPs that were likely formed from nitrogen-containing precursors from human inputs, such as urine, sweat, and skin cells. Many DBPs were new and have not been reported previously in either swimming pool or drinking waters. Bromoform levels were greater in brominated than in chlorinated pool waters, but we also identified many brominated DBPs in the chlorinated waters. The pool waters were mutagenic at levels similar to that of drinking water (~ 1,200 revertants/L-equivalents in strain TA100–S9 mix). Conclusions This study identified many new DBPs not identified previously in swimming pool or drinking water and found that swimming pool waters are as mutagenic as typical drinking waters.

Identification of new drinking water disinfection by-products from ozone, chlorine dioxide, chloramine, and chlorine.

Many drinking water treatment plants are currently using alternative disinfectants to treat drinking water, with ozone, chlorine dioxide, and chloramine being the most popular. However, compared to chlorine, which has been much more widely studied, there is little information about the disinfection by-products (DBPs) that these alternative disinfectants produce. Thus, it is not known if the DBPs from alternative disinfectants are safer or more hazardous than those formed by chlorine. To answer this question, we have set out to comprehensively identify DBPs formed by these alternative disinfectants, as well as by chlorine. The results presented here represent a compilation of the last 8 years of our research in identifying new DBPs from ozone, chlorine dioxide, chloramine, and chlorine. We also include results from recent studies of Israel drinking water disinfected with both chlorine dioxide and chloramine. Over 200 DBPs were identified, many of which have never been reported. In comparing by-products formed by the different disinfectants, ozone, chlorine dioxide, and chloramine formed fewer halogenated DBPs than chlorine.

Mammalian cell cytotoxicity and genotoxicity of the haloacetic acids, a major class of drinking water disinfection by-products.

The haloacetic acids (HAAs) are disinfection by‐products (DBPs) that are formed during the disinfection of drinking water, wastewaters and recreational pool waters. Currently, five HAAs [bromoacetic acid (BAA), dibromoacetic acid (DBAA), chloroacetic acid (CAA), dichloroacetic acid (DCAA), and trichloroacetic acid (TCAA); designated as HAA5] are regulated by the U.S. EPA, at a maximum contaminant level of 60 μg/L for the sum of BAA, DBAA, CAA, DCAA, and TCAA. We present a comparative systematic analysis of chronic cytotoxicity and acute genomic DNA damaging capacity of 12 individual HAAs in mammalian cells. In addition to the HAA5, we analyzed iodoacetic acid (IAA), diiodoacetic acid (DiAA), bromoiodoacetic acid (BIAA), tribromoacetic acid (TBAA), chlorodibromoacetic acid (CDBAA), bromodichloroacetic acid (BDCAA), and bromochloroacetic acid (BCAA). Their rank order of chronic cytotoxicity in Chinese hamster ovary cells was IAA > BAA > TBAA > CDBAA > DIAA > DBAA > BDCAA > BCAA > CAA > BIAA > TCAA > DCAA. The rank order for genotoxicity was IAA > BAA > CAA > DBAA > DIAA > TBAA > BCAA > BIAA > CDBAA. DCAA, TCAA, and BDCAA were not genotoxic. The trend for both cytotoxicity and genotoxicity is iodinated HAAs > brominated HAAs > chlorinated HAAs. The use of alternative disinfectants other than chlorine generates new DBPs and alters their distribution. Systematic, comparative, in vitro toxicological data provides the water supply community with information to consider when employing alternatives to chlorine disinfection. In addition, these data aid in prioritizing DBPs and their related compounds for future in vivo toxicological studies and risk assessment. Environ. Mol. Mutagen., 2010.

Drinking Water Disinfection By-products

Drinking water disinfection by-products (DBPs) are an unintended consequence of using chemical disinfectants to kill harmful pathogens in water. DBPs are formed by the reaction of disinfectants with naturally occurring organic matter, bromide, and iodide, as well as from anthropogenic pollutants. Potential health risks of DBPs from drinking water include bladder cancer, early-term miscarriage, and birth defects. Risks from swimming pool DBP exposures include asthma and other respiratory effects. Several DBPs, such as trihalomethanes (THMs), haloacetic acids (HAAs), bromide, and chlorite, are regulated in the U.S. and in other countries, but other “emerging” DBPs, such as iodo-acids, halonitromethanes, haloamides, halofuranones, and nitrosamines, are not widely regulated. DBPs have been reported for the four major disinfectants: chlorine, chloramines, ozone, and chlorine dioxide (and their combinations), as well as for newer disinfectants, such as UV treatment with post-chlorination. Each disinfectant can produce its own suite of by-products. Several classes of emerging DBPs are increased in formation with the use of alternative disinfectants (e.g., chloramines), including nitrogen-containing DBPs (“N-DBPs”), which are generally more genotoxic and cytotoxic than those without nitrogen. Humans are exposed to DBPs not only through ingestion (the common route studied), but also through other routes, including bathing, showering, and swimming. Inhalation and dermal exposures are now being recognized as important contributors to the overall human health risk of DBPs. Analytical methods continue to be developed to measure known DBPs, and research continues to uncover new highly polar and high-molecular-weight DBPs that are part of the missing fraction of DBPs not yet accounted for. New studies are now combining toxicology and chemistry to better understand the health risks of DBPs and uncover which are responsible for the human health effects.

Childhood asthma and environmental exposures at swimming pools: state of the science and research recommendations.

Objectives Recent studies have explored the potential for swimming pool disinfection by-products (DBPs), which are respiratory irritants, to cause asthma in young children. Here we describe the state of the science on methods for understanding children’s exposure to DBPs and biologics at swimming pools and associations with new-onset childhood asthma and recommend a research agenda to improve our understanding of this issue. Data sources A workshop was held in Leuven, Belgium, 21–23 August 2007, to evaluate the literature and to develop a research agenda to better understand children’s exposures in the swimming pool environment and their potential associations with new-onset asthma. Participants, including clinicians, epidemiologists, exposure scientists, pool operations experts, and chemists, reviewed the literature, prepared background summaries, and held extensive discussions on the relevant published studies, knowledge of asthma characterization and exposures at swimming pools, and epidemiologic study designs. Synthesis Childhood swimming and new-onset childhood asthma have clear implications for public health. If attendance at indoor pools increases risk of childhood asthma, then concerns are warranted and action is necessary. If there is no such relationship, these concerns could unnecessarily deter children from indoor swimming and/or compromise water disinfection. Conclusions Current evidence of an association between childhood swimming and new-onset asthma is suggestive but not conclusive. Important data gaps need to be filled, particularly in exposure assessment and characterization of asthma in the very young. Participants recommended that additional evaluations using a multidisciplinary approach are needed to determine whether a clear association exists.

The role of GC-MS and LC-MS in the discovery of drinking water disinfection by-products

Gas chromatography-mass spectrometry (GC-MS) has played a pivotal role in the discovery of disinfection by-products (DBPs) in drinking water. DBPs are formed when disinfectants, such as chlorine, ozone, chlorine dioxide or chloramine, react with natural organic matter in the water. The first DBP known--chloroform--was identified by Rook in 1974 using GC-MS. Soon thereafter, chloroform and other trihalomethanes were found to be ubiquitous in chlorinated drinking water. In 1976, the National Cancer Institute published results linking chloroform to cancer in laboratory animals, and an important public health issue was born. Mass spectrometry and, specifically, GC-MS became the key tool used for measuring these DBPs in water and for discovering other DBPs that were formed. Over the last 25 years, hundreds of DBPs have been identified, mostly through the use of GC-MS, which has spawned additional health effects studies and regulations. Early on, GC with low resolution electron ionization (EI)-MS was used, together with confirmation with chemical standards, for identification work. Later, researchers utilized chemical ionization (CI)-MS to provide molecular weight information and high resolution El-MS to aid in the determination of empirical formulae for the molecular ions and fragments. More recently, liquid chromatography-mass spectrometry (LC-MS) with either electrospray ionization (ESI) or atmospheric pressure chemical ionization (APCI) has been used to try to uncover highly polar DBPs that most experts believe have been missed by earlier GC-MS studies. Despite 25 years of research in the identification of new DBPs, new ones are being discovered every year, even for chlorine which has been the most extensively studied.

Transformation of pharmaceuticals during oxidation/disinfection processes in drinking water treatment.

Pharmaceuticals are emerging contaminants of concern and are widespread in the environment. While the levels of these substances in finished drinking waters are generally considered too low for human health concern, there are now concerns about their disinfection by-products (DBPs) that can form during drinking water treatment, which in some cases have been proven to be more toxic than the parent compounds. The present manuscript reviews the transformation products of pharmaceuticals generated in water during different disinfection processes, i.e. chlorination, ozonation, chloramination, chlorine dioxide, UV, and UV/hydrogen peroxide, and the main reaction pathways taking place. Most of the findings considered for this review come from controlled laboratory studies involving reactions of pharmaceuticals with these oxidants used in drinking water treatment.

Identification of New Drinking Water Disinfection by-Products from Ozone, Chlorine Dioxide, Chloramine, and Chlorine

Many drinking water treatment plants are currently using alternative disinfectants to treat drinking water, with ozone, chlorine dioxide, and chloramine being the most popular. However, compared to chlorine, which has been much more widely studied, there is little information about the disinfection by-products (DBPs) that these alternative disinfectants produce. Thus, it is not known if the DBPs from alternative disinfectants are safer or more hazardous than those formed by chlorine. To answer this question, we have set out to comprehensively identify DBPs formed by these alternative disinfectants, as well as by chlorine. The results presented here represent a compilation of the last 8 years of our research in identifying new DBPs from ozone, chlorine dioxide, chloramine, and chlorine. We also include results from recent studies of Israel drinking water disinfected with both chlorine dioxide and chloramine. Over 200 DBPs were identified, many of which have never been reported. In comparing by-products formed by the different disinfectants, ozone, chlorine dioxide, and chloramine formed fewer halogenated DBPs than chlorine.

Integrated Disinfection By-Products Mixtures Research: Comprehensive Characterization of Water Concentrates Prepared from Chlorinated and Ozonated/Postchlorinated Drinking Water

This article describes the disinfection by-product (DBP) characterization portion of a series of experiments designed for comprehensive chemical and toxicological evaluation of two drinking-water concentrates containing highly complex mixtures of DBPs. This project, called the Four Lab Study, involved the participation of scientists from four laboratories and centers of the U.S. Environmental Protection Agency (EPA) Office of Research and Development, along with collaborators from the water industry and academia, and addressed toxicologic effects of complex DBP mixtures, with an emphasis on reproductive and developmental effects that are associated with DBP exposures in epidemiologic studies. Complex mixtures of DBPs from two different disinfection schemes (chlorination and ozonation/postchlorination) were concentrated successfully, while maintaining a water matrix suitable for animal studies. An array of chlorinated/brominated/iodinated DBPs was created. The DBPs were relatively stable over the course of the animal experiments, and a significant portion of the halogenated DBPs formed in the drinking water was accounted for through a comprehensive qualitative and quantitative identification approach. DBPs quantified included priority DBPs that are not regulated but have been predicted to produce adverse health effects, as well as those currently regulated in the United States and those targeted during implementation of the Information Collection Rule. New by-products were also reported for the first time. These included previously undetected and unreported bromo- and chloroacids, iodinated compounds, bromo- and iodophenols, and bromoalkyltins.