Heath Mash

Nationwide reconnaissance of contaminants of emerging concern in source and treated drinking waters of the United States

When chemical or microbial contaminants are assessed for potential effect or possible regulation in ambient and drinking waters, a critical first step is determining if the contaminants occur and if they are at concentrations that may cause human or ecological health concerns. To this end, source and treated drinking water samples from29 drinking water treatment plants (DWTPs) were analyzed as part of a two-phase study to determine whether chemical and microbial constituents, many of which are considered contaminants of emerging concern, were detectable in the waters. Of the 84 chemicals monitored in the 9 Phase I DWTPs, 27 were detected at least once in the source water, and 21 were detected at least once in treated drinking water. In Phase II, which was a broader and more comprehensive assessment, 247 chemical and microbial analytes were measured in 25 DWTPs, with 148 detected at least once in the source water, and 121 detected at least once in the treated drinking water. The frequency of detection was often related to the analyte’s contaminant class, as pharmaceuticals and anthropogenic waste indicators tended to be infrequently detected and more easily removed during treatment, while per and polyfluoroalkyl substances and inorganic constituents were both more frequently detected and, overall, more resistant to treatment. The data collected as part of this project will be used to help inform evaluation of unregulated contaminants in surface water, groundwater, and drinking water.

Comparison of in vitro estrogenic activity and estrogen concentrations in source and treated waters from 25 U.S. drinking water treatment plants

In vitro bioassays have been successfully used to screen for estrogenic activity in wastewater and surface water, however, few have been applied to treated drinking water. Here, extracts of source and treated water samples were assayed for estrogenic activity using T47D-KBluc cells and analyzed by liquid chromatography-Fourier transform mass spectrometry (LC-FTMS) for natural and synthetic estrogens (including estrone, 17β-estradiol, estriol, and ethinyl estradiol). None of the estrogens were detected above the LC-FTMS quantification limits in treated samples and only 5 source waters had quantifiable concentrations of estrone, whereas 3 treated samples and 16 source samples displayed in vitro estrogenicity. Estrone accounted for the majority of estrogenic activity in respective samples, however the remaining samples that displayed estrogenic activity had no quantitative detections of known estrogenic compounds by chemical analyses. Source water estrogenicity (max, 0.47ng 17β-estradiol equivalents (E2Eq) L-1) was below levels that have been linked to adverse effects in fish and other aquatic organisms. Treated water estrogenicity (max, 0.078ngE2EqL-1) was considerably below levels that are expected to be biologically relevant to human consumers. Overall, the advantage of using in vitro techniques in addition to analytical chemical determinations was displayed by the sensitivity of the T47D-KBluc bioassay, coupled with the ability to measure cumulative effects of mixtures, specifically when unknown chemicals may be present.

Nationwide reconnaissance of contaminants of emerging concern in source and treated drinking waters of the United States: Pharmaceuticals.

Mobile and persistent chemicals that are present in urban wastewater, such as pharmaceuticals, may survive on-site or municipal wastewater treatment and post-discharge environmental processes. These pharmaceuticals have the potential to reach surface and groundwaters, essential drinking-water sources. A joint, two-phase U.S. Geological Survey-U.S. Environmental Protection Agency study examined source and treated waters from 25 drinking-water treatment plants from across the United States. Treatment plants that had probable wastewater inputs to their source waters were selected to assess the prevalence of pharmaceuticals in such source waters, and to identify which pharmaceuticals persist through drinking-water treatment. All samples were analyzed for 24 pharmaceuticals in Phase I and for 118 in Phase II. In Phase I, 11 pharmaceuticals were detected in all source-water samples, with a maximum of nine pharmaceuticals detected in any one sample. The median number of pharmaceuticals for all 25 samples was five. Quantifiable pharmaceutical detections were fewer, with a maximum of five pharmaceuticals in any one sample and a median for all samples of two. In Phase II, 47 different pharmaceuticals were detected in all source-water samples, with a maximum of 41 pharmaceuticals detected in any one sample. The median number of pharmaceuticals for all 25 samples was eight. For 37 quantifiable pharmaceuticals in Phase II, median concentrations in source water were below 113ng/L. For both Phase I and Phase II campaigns, substantially fewer pharmaceuticals were detected in treated water samples than in corresponding source-water samples. Seven different pharmaceuticals were detected in all Phase I treated water samples, with a maximum of four detections in any one sample and a median of two pharmaceuticals for all samples. In Phase II a total of 26 different pharmaceuticals were detected in all treated water samples, with a maximum of 20 pharmaceuticals detected in any one sample and a median of 2 pharmaceuticals detected for all 25 samples. Source-water type influences the presence of pharmaceuticals in source and treated water. Treatment processes appear effective in reducing concentrations of most pharmaceuticals. Pharmaceuticals more consistently persisting through treatment include carbamazepine, bupropion, cotinine, metoprolol, and lithium. Pharmaceutical concentrations and compositions from this study provide an important base data set for further sublethal, long-term exposure assessments, and for understanding potential effects of these and other contaminants of emerging concern upon human and ecosystem health.

Human health screening and public health significance of contaminants of emerging concern detected in public water supplies

The source water and treated drinking water from twenty five drinking water treatment plants (DWTPs) across the United States were sampled in 2010-2012. Samples were analyzed for 247 contaminants using 15 chemical and microbiological methods. Most of these contaminants are not regulated currently either in drinking water or in discharges to ambient water by the U. S. Environmental Protection Agency (USEPA) or other U.S. regulatory agencies. This analysis shows that there is little public health concern for most of the contaminants detected in treated water from the 25 DWTPs participating in this study. For vanadium, the calculated Margin of Exposure (MOE) was less than the screening MOE in two DWTPs. For silicon, the calculated MOE was less than the screening MOE in one DWTP. Additional study, for example a national survey may be needed to determine the number of people ingesting vanadium and silicon above a level of concern. In addition, the concentrations of lithium found in treated water from several DWTPs are within the range previous research has suggested to have a human health effect. Additional investigation of this issue is necessary. Finally, new toxicological data suggest that exposure to manganese at levels in public water supplies may present a public health concern which will require a robust assessment of this information.

The importance of quality control in validating concentrations of contaminants of emerging concern in source and treated drinking water samples

A national-scale survey of 247 contaminants of emerging concern (CECs), including organic and inorganic chemical compounds, and microbial contaminants, was conducted in source and treated drinking water samples from 25 treatment plants across the United States. Multiple methods were used to determine these CECs, including six analytical methods to measure 174 pharmaceuticals, personal care products, and pesticides. A three-component quality assurance/quality control (QA/QC) program was designed for the subset of 174 CECs which allowed us to assess and compare performances of the methods used. The three components included: 1) a common field QA/QC protocol and sample design, 2) individual investigator-developed method-specific QA/QC protocols, and 3) a suite of 46 method comparison analytes that were determined in two or more analytical methods. Overall method performance for the 174 organic chemical CECs was assessed by comparing spiked recoveries in reagent, source, and treated water over a two-year period. In addition to the 247 CECs reported in the larger drinking water study, another 48 pharmaceutical compounds measured did not consistently meet predetermined quality standards. Methodologies that did not seem suitable for these analytes are overviewed. The need to exclude analytes based on method performance demonstrates the importance of additional QA/QC protocols.

Removal of estrogens and estrogenicity through drinking water treatment.

Estrogenic compounds have been shown to be present in surface waters, leading to concerns over their possible presence in finished drinking waters. In this work, two in vitro human cell line bioassays for estrogenicity were used to evaluate the removal of estrogens through conventional drinking water treatment using a natural water. Bench-scale studies utilizing chlorine, alum coagulation, ferric chloride coagulation, and powdered activated carbon (PAC) were conducted using Ohio River water spiked with three estrogens, 17β-estradiol, 17α-ethynylestradiol, and estriol. Treatment of the estrogens with chlorine, either alone or with coagulant, resulted in approximately 98% reductions in the concentrations of the parent estrogens, accompanied by formation of by-products. The MVLN reporter gene and MCF-7 cell proliferation assays were used to characterize the estrogenic activity of the water before and after treatment. The observed estrogenic activities of the chlorinated samples showed that estrogenicity of the water was reduced commensurate with removal of the parent estrogen. Therefore, the estrogen chlorination by-products did not contribute appreciably to the estrogenic activity of the water. Coagulation alone did not result in significant removals of the estrogens. However, addition of PAC, at a typical drinking water plant dose, resulted in removals ranging from approximately 20 to 80%.

Hypochlorite oxidation of select androgenic steroids

Steroid hormones are vital for regulation of various biological functions including sexual development. Elevated concentrations of natural and synthetic androgenic steroids have been shown to adversely affect normal development in indigenous aqueous species. Androgens and their synthetic analogs released from agricultural activities and wastewater discharge may be introduced into drinking water sources. The fate of androgenic steroids during drinking water treatment, specifically the use of chlorine for biological control, has not been extensively studied. As such, this study focuses on the hypochlorite oxidation of a select number of androgenic compounds that vary in their structural composition. Where a favorable reaction is observed, we also attempt to describe the product distribution. The results show compounds that possess a ketonic functional group conjugated with a double bond inhibit oxidation by hypochlorite in the absence of biological or indirect oxidative pathways. Oxidative reactivity in the presence of hypochlorite was favorably correlated with the presence of isolated unsaturated carbon bonds and resulted in various transformation products.

Aquatic concentrations of chemical analytes compared to ecotoxicity estimates

We describe screening level estimates of potential aquatic toxicity posed by 227 chemical analytes that were measured in 25 ambient water samples collected as part of a joint USGS/USEPA drinking water plant study. Measured concentrations were compared to biological effect concentration (EC) estimates, including USEPA aquatic life criteria, effective plasma concentrations of pharmaceuticals, published toxicity data summarized in the USEPA ECOTOX database, and chemical structure-based predictions. Potential dietary exposures were estimated using a generic 3-tiered food web accumulation scenario. For many analytes, few or no measured effect data were found, and for some analytes, reporting limits exceeded EC estimates, limiting the scope of conclusions. Results suggest occasional occurrence above ECs for copper, aluminum, strontium, lead, uranium, and nitrate. Sparse effect data for manganese, antimony, and vanadium suggest that these analytes may occur above ECs, but additional effect data would be desirable to corroborate EC estimates. These conclusions were not affected by bioaccumulation estimates. No organic analyte concentrations were found to exceed EC estimates, but ten analytes had concentrations in excess of 1/10th of their respective EC: triclocarban, norverapamil, progesterone, atrazine, metolachlor, triclosan, para-nonylphenol, ibuprofen, venlafaxine, and amitriptyline, suggesting more detailed characterization of these analytes.

Effect of chlorination on the protein phosphatase inhibition activity for several microcystins.

Microcystins are of particular concern due to their toxicity to both humans and animals and may be the most prominent cyanotoxin observed in freshwater. Although a number of studies have investigated the fate of microcystins and other algal toxins through drinking water treatment facilities, measurement of their potential for toxic activity after chlorination, a popular form of treatment in the United States, has not been investigated. In this study, six microcystin variants are subjected to chlorine oxidation. The degradation of each microcystin variant is measured by liquid chromatography/mass spectrometry simultaneously with protein phosphatase inhibition (PPI) response over reaction time with chlorine. Results show that inhibition is dependent on the incorporated amino acid residues, their placement within the microcystin structure, as well as pH. This pH dependence may have practical implications to such activities such as drinking water treatment when the pH is usually adjusted to around 8. Namely, at this pH, even with chlorine addition for disinfection, PPI activity may not be totally eliminated even when the initial MYCs are eliminated.