Search

We describe initial development of microarray-based assays for detecting 4 pyrethroid pesticides (bifenthrin, cypermethrin, esfenvalerate, and permethrin) in water. To facilitate comparison of transcriptional responses with gross apical responses, we estimated concentration-mortality curves for these pyrethroids using flow-through exposures of newly hatched Daphnia magna, Pimephales promelas adults, and 24 h posthatch P. promelas. Median lethal concentration (LC50) estimates were below most reported values, perhaps attributable to the use of flow-through exposures or of measured rather than nominal concentrations. Microarray analysis of whole P. promelas larvae and brains from exposed P. promelas adults showed that assays using either tissue type can detect these pyrethroids at concentrations below LC50 values reported for between 72 and 96% of aquatic species, depending on the pesticide. These estimates are conservative because they correspond to the lowest concentrations tested. This suggests that the simpler and less expensive whole-larval assay provides adequate sensitivity for screening contexts where acute aquatic lethality is observed, but the responsible agent is not known. Gene set analysis (GSA) highlighted several Gene Ontology (GO) terms consistent with known pyrethroid action, but the implications of other GO terms are less clear. Exploration of the sensitivity of results to changes in data processing suggests robustness of the detection assay results, but GSA results were sensitive to methodological variations. Environ Toxicol Chem 2019;38:2436-2446. Published 2019 Wiley Periodicals, Inc. on behalf of SETAC. This article is a US government work, and as such, is in the public domain in the United States of America.

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., GRAPHICAL ABSTRACT

U.S. EPA conducted a national statistical survey of fish tissue contamination at 540 river sites (representing 82 954 river km) in 2008–2009, and analyzed samples for 50 persistent organic pollutants (POPs), including 21 PCB congeners, 8 PBDE congeners, and 21 organochlorine pesticides. The survey results were used to provide national estimates of contamination for these POPs. PCBs were the most abundant, being measured in 93.5% of samples. Summed concentrations of the 21 PCB congeners had a national weighted mean of 32.7 μg/kg and a maximum concentration of 857 μg/kg, and exceeded the human health cancer screening value of 12 μg/kg in 48% of the national sampled population of river km, and in 70% of the urban sampled population. PBDEs (92.0%), chlordane (88.5%) and DDT (98.7%) were also detected frequently, although at lower concentrations. Results were examined by subpopulations of rivers, including urban or nonurban and three defined ecoregions. PCBs, PBDEs, and DDT occur at significantly higher concentrations in fish from urban rivers versus nonurban; however, the distribution varied more among the ecoregions. Wildlife screening values previously published for bird and mammalian species were converted from whole fish to fillet screening values, and used to estimate risk for wildlife through fish consumption.

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.

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.

Omics technologies have long since promised to address a number of long standing issues related to environmental regulation. Despite considerable resource investment, there are few examples where these tools have been adopted by the regulatory community, which is in part due to a focus of most studies on discovery rather than assay development. The current work describes the initial development of an omics based assay using 48 h Pimephales promelas (FHM) larvae for identifying aquatic exposures to pyrethroid pesticides. Larval FHM were exposed to seven concentrations of each of four pyrethroids (permethrin, cypermethrin, esfenvalerate and bifenthrin) in order to establish dose response curves. Then, in three separate identical experiments, FHM were exposed to a single equitoxic concentration of each pyrethroid, corresponding to 33% of the calculated LC50. All exposures were separated by weeks and all materials were either cleaned or replaced between runs in an attempt to maintain independence among exposure experiments. Gene expression classifiers were developed using the random forest algorithm for each exposure and evaluated first by cross-validation using hold out organisms from the same exposure experiment and then against test sets of each pyrethroid from separate exposure experiments. Bifenthrin exposed organisms generated the highest quality classifier, demonstrating an empirical Area Under the Curve (eAUC) of 0.97 when tested against bifenthrin exposed organisms from other exposure experiments and 0.91 against organisms exposed to any of the pyrethroids. An eAUC of 1.0 represents perfect classification with no false positives or negatives. Additionally, the bifenthrin classifier was able to successfully classify organisms from all other pyrethroid exposures at multiple concentrations, suggesting a potential utility for detecting cumulative exposures. Considerable run-to-run variability was observed both in exposure concentrations and molecular responses of exposed fish across exposure experiments. The application of a calibration step in analysis successfully corrected this, resulting in a significantly improved classifier. Classifier evaluation suggested the importance of considering a number of aspects of experimental design when developing an expression based tool for general use in ecological monitoring and risk assessment, such as the inclusion of multiple experimental runs and high replicate numbers.

To assess the potential exposure of aquatic ecosystems to active pharmaceutical ingredients, the authors conducted a national-scale, probability-based statistical survey of the occurrence of these compounds in surface waters of the United States. The survey included 182 sampling sites and targeted rivers with close proximity to urban areas. The 46 analytes reported represent many classes of active pharmaceutical ingredients (APIs), including antibiotics, diuretics, antihypertensives, anticonvulsants, and antidepressants. Of the 46 analytes, 37 were detected in at least 1 sampling location. Sulfamethoxazole (an antibiotic) was the most frequently detected compound, being measured in 141 of the 182 surface waters surveyed at concentrations ranging up to 570 ng/L. Ten of the compounds were detected in 20% or more of the sampling sites. Weighted means of the analytical measurements are used with the statistical survey design and analysis to provide national estimates of the extent of contamination for these APIs in the nation's urban rivers. Published 2015 Wiley Periodicals, Inc. on behalf of SETAC. This article is a US Government work and as such, is in the public domain in the United States of America.

Effluents from four healthcare facilities were characterized for the concentration of 16 common active pharmaceutical ingredients. The sampled facilities included a hospital, nursing care, assisted living, and independent living facility located within a single municipal wastewater system in Texas. Eleven of the 16 monitored pharmaceuticals were detected in at least 1 healthcare facility effluent and 2 measured antibiotics (sulfamethoxazole and trimethoprim) were detected in all 4 facility effluents. Active pharmaceutical ingredient concentrations ranged from non-detectable levels for several corticosteroids in all facility effluents to 180 microg/L sulfamethoxazole in the nursing care wastewater effluent. The mass of active pharmaceutical ingredients discharged to the municipality's wastewater conveyance system was determined by combining individual facility concentration data and daily wastewater flow. The estimated daily mass loading of all 16 pharmaceuticals ranged from 0.16 g/day to 23 g/day in the assisted living facility and nursing wastewater effluents, respectively. The combined active pharmaceutical ingredient mass loading for all four facilities was 42.6 g/day. These findings provide source characterization data for 16 common pharmaceuticals in healthcare facility wastewater and provide a basis for risk assessment of pharmaceuticals present in healthcare facility wastewaters.

Nervous system active pharmaceutical ingredients (APIs), including anti-depressants and opioids, are important clinically administered pharmaceuticals within healthcare facilities. This study provides source characterization data describing the composition and magnitude of nervous system APIs present in healthcare facility wastewaters. Concentrations and mass loadings of ten nervous system APIs and three nervous system API metabolites are reported for wastewaters from a hospital, nursing, assisted living, and independent living facility within a single municipality. Concentrations of nervous system APIs ranged from non-detectable levels for alprazolam in all four facility wastewaters to a high of 290 ng/L amitriptyline in nursing facility wastewater. The summed mean concentration of all thirteen analytes ranged from 402 ng/L in independent living facility wastewater to 624 ng/L in assisted living facility wastewater. Wastewater flow rates from each facility were combined with concentration data to estimate the daily mass loading of nervous system APIs leaving each facility through wastewater discharge to the municipal sewer system. The total mass loading of all thirteen analytes for the hospital, nursing, assisted living, and independent living facility was 228, 44, 29.5, and 28.1 mg/day, respectively. The total mass loading of nervous system APIs contributed to the municipality's wastewater from all four facilities was 330 mg/day.

Potential exposure to active pharmaceutical ingredients (APIs) in the aquatic environment is a subject of ongoing concern. We recently published maximum likely exposure rates for several hundred human prescription pharmaceuticals commonly used in the US. These rates were estimated from nationally aggregated marketing data and wastewater production rates. The accuracy of these estimates is unclear, and it is unclear how to use the national-level estimates of exposure to predict local exposure rates. In this study we compare our previous predicted environmental concentrations (PECs), which were based on marketing data, with PECs based on regulatory data. We then use local dispensing rates for 12 APIs along with local wastewater production rates to estimate the distribution of local PECs relative to national averages, in order to identify an 'application factor' suitable for converting national-level PECs into reliable bounds for local concentrations. We compare the national-level PECs and the proposed application factor with measured environmental concentrations (MECs) published in 62 recent peer-reviewed publications. Regulatory data-based national average PECs are uniformly lower than marketing data-based national average PECs, corroborating the intended conservative nature of the marketing data-based PECs. Variability in local API usage and wastewater production rates suggest local PECs may occasionally exceed national averages by about 10-fold. Multiplying national average PECs by an 'application factor' of 10 and comparing the resulting predicted maximum local PECs to published MEC data for 83 APIs corroborates the usefulness of 10-fold adjusted national PECs as a reasonable ceiling for measured environmental concentrations.

A rapid and sensitive method has been developed for the analysis of 48 human prescription active pharmaceutical ingredients (APIs) and 6 metabolites of interest, utilizing selective solid-phase extraction (SPE) and ultraperformance liquid chromatography in combination with triple quadrupole mass spectrometry (UPLC-MS/MS). The single-cartridge extraction step was developed using a mixed mode reversed-phase/cation-exchange cartridge (Oasis MCX) and validated in both wastewater effluent and surface water. Recoveries for the majority of compounds ranged from 80% to 125%, with relative standard deviations generally below 15%. Analytes were quantified using a multiple injection analysis with four chromatographic runs, with a combined run time of 48 min and SPE-UPLC-MS/MS method detection limits ranging from 1.0 to 51 ng/L. The analysis of seven wastewater effluents and one surface water sample revealed at least one detection for 38 of the 54 compounds, with effluent concentrations ranging from 7 to 2950 ng/L and surface water concentrations ranging from 10 to 140 ng/L. This initial data demonstrates that a significant number of the selected target analytes are present in wastewater treatment plant discharges.

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.

Iopromide (an X-ray contrast agent) and trimethoprim (an antibacterial drug) are frequently detected pharmaceuticals in effluents of wastewater treatment plants (WWTPs) and in surface waters due to their persistence and high usage. Laboratory-scale experiments showed that a significantly higher removal rate in nitrifying activated sludge as compared to conventional activated sludge was observed for both iopromide and trimethoprim. When the activity of the nitrifying bacteria was inhibited, the percent removal of iopromide decreased from 97 to 86% while trimethoprim removal decreased from 70 to 25%. The metabolite of iopromide identified when nitrification was not inhibited was a dehydroxylated iopromide at the two side chains. However, when the nitrifying bacteria were inhibited the metabolite identified was a carboxylate, formed during the oxidation of the primary alcohol on the side chain of iopromide. These results suggest that the nitrifying bacteria are important in the observed biodegradation of iopromide in the activated sludge with higher solid retention time (SRT). Results from the laboratory-scale study were corroborated by the observed removal efficiencies in a full-scale municipal WWTP, which showed that iopromide (ranging from 0.10 to 0.27 microg/L) and trimethoprim (ranging from 0.0.08 to 0.53 microg/L) were removed more effectively in the nitrifying activate sludge which has a higher SRT (49 days) than in the conventional activated sludge (SRT of 6 days). In nitrifying activated sludge, the percent removal of iopromide in the WWTP reached 61%, while in conventional activated sludge, average removal was negligible. For trimethoprim, removal was limited to about 1% in the conventional activated sludge, while in the nitrifying activated sludge, the removal was increased to 50%.

Samples from six private wells formerly used as sources for drinking water by the residents of Washington County (Weiser, Idaho) were collected to assess the impact of a nearby confined animal feeding operation (CAFO) on the quality of the local groundwater. All six samples were found contaminated by two veterinary antimicrobials, sulfamethazine (at concentrations from 0.076 to 0.22 microg/l) and sulfadimethoxine (at concentrations from 0.046 to 0.068 microg/l). These groundwater samples also contained elevated concentrations of nitrate and ammonium. Three of the sampled wells have nitrate levels that exceeded the maximum contaminant level set by the US Environmental Protection Agency for drinking water, with nitrate concentration as high as 39.1mg/l. All but one well showed nitrate, which instead contained ammonium at 1.22 mg/l. Analysis of the nitrate and ammonium in these samples by isotopic ratio mass spectrometry indicated delta(15)N characteristic of an animal or human waste source. Results from this study underscore the role of CAFO as an important source of antibiotic contamination of groundwater.

Effluents from three wastewater treatment plants with varying wastewater treatment technologies and design were analyzed for six antibiotics and caffeine on three sampling occasions. Sulfamethoxazole, trimethoprim, ciprofloxacin, tetracycline, and clindamycin were detected in the effluents at concentrations ranging from 0.090 to 6.0 microg/L. Caffeine was detected in all effluents at concentrations ranging from 0.19 to 9.9 microg/L. These findings indicate that several conventional wastewater management practices are not effective in the complete removal of antibiotics, and their discharges have a large potential to affect the aquatic environment. To evaluate the persistence of antibiotics coming from the wastewater discharges on the surrounding surface waters, samples were collected from the receiving streams at 10-, 20- and 100-m intervals. Ciprofloxacin, sulfamethoxazole, and clindamycin (0.043 to 0.076 microg/L) were found as far as 100 m from the discharge point, which indicates the persistence of these drugs in surface waters.

Solid-phase extraction (SPE) and liquid chromatography in combination with ion trap mass spectrometry (LC/MS/MS) conditions were optimized for the simultaneous analysis of 13 antibiotics belonging to multiple classes and caffeine in 3 different water matrixes. The single-cartridge extraction step was developed using a reversed-phase cartridge, resulting in recoveries for the 14 compounds ranging from 71 to 119% with relative standard deviations of 16% or lower. The analytes were separated in one chromatographic run, and the SPE-LC/MS/MS detection limits ranged from 0.03 to 0.19 μg/L. The SPE procedure was validated in groundwater, surface water, and wastewater. The analysis of samples from each of the three water matrixes revealed clindamycin (1.1 μg/L) in surface water and multiple antibiotics in wastewater (0.10−1.3 μg/L). The use of identification points to unambiguously assign the identity of antibiotics in various water matrixes was applied to an ion trap data-dependent scanning method, which simulta...

To assess the potential exposure of aquatic ecosystems to active pharmaceutical ingredients, the authors conducted a national-scale, probability-based statistical survey of the occurrence of these compounds in surface waters of the United States. The survey included 182 sampling sites and targeted rivers with close proximity to urban areas. The 46 analytes reported represent many classes of active pharmaceutical ingredients (APIs), including antibiotics, diuretics, antihypertensives, anticonvulsants, and antidepressants. Of the 46 analytes, 37 were detected in at least 1 sampling location. Sulfamethoxazole (an antibiotic) was the most frequently detected compound, being measured in 141 of the 182 surface waters surveyed at concentrations ranging up to 570 ng/L. Ten of the compounds were detected in 20% or more of the sampling sites. Weighted means of the analytical measurements are used with the statistical survey design and analysis to provide national estimates of the extent of contamination for these APIs in the nation's urban rivers. Published 2015 Wiley Periodicals, Inc. on behalf of SETAC. This article is a US Government work and as such, is in the public domain in the United States of America.

There is a great diversity of sources of chemical contaminants and stressors over large geographic areas. Chemical contaminant inputs and magnitude can potentially exhibit wide seasonal variation over large geographic areas. Together, these factors make linking exposure to monitored chemical contaminants and effects difficult. In practice, this linkage typically relies on relatively limited chemical occurrence data loosely coupled with individual effects, and population- or community-level assessments. Increased discriminatory power may be gained by approaching watershed level assessment in a more holistic manner, drawing from a number of disciplines that target endpoints spanning levels of the biological hierarchy. Using the Sacramento River as a case study, the present study aimed to 1) evaluate the performance of new analytical and biomarker tools in a real world setting and their potential for linking occurrence and effect; 2) characterize the effects of geographic and temporal variability through the integration of suborganismal, tissue, and individual level endpoints, as well as extensive chemical analyses; 3) identify knowledge gaps and research needs that limit the implementation of this holistic approach; and 4) provide an experimental design workflow for these types of assessments. Sites were selected to target inputs into the Sacramento River as it transitions from an agricultural to a mixed but primarily urban landscape. Chemical analyses were conducted on surface water samples at each site in both the spring and fall for pesticides, hormones, and active pharmaceutical ingredients (APIs). Active pharmaceutical ingredients were more often detected across sampling events in the fall; however, at the most downstream site the number of analytes detected and their concentrations were greater in the spring, which may be due to seasonal differences in rainfall. Changes in gene and protein expression targeting endocrine and reproductive effects were observed within each sampling event; however, they were inconsistent across seasons. Larval mortality at the most downstream site was seen in both seasons; however, behavioral changes were only observed in the spring. No clear linkages of specific analyte exposure to biological response were observed, nor were linkages across biological levels of organization. This failure may have resulted from limitations of the scope of molecular endpoints used, inconsistent timing of exposure, or discordance of analytical chemistry through grab sampling and longer term, integrative exposure. Together, results indicate a complicated view of the watershed.

The U.S. EPA conducted a national statistical survey of fish fillet tissue with a sample size of 541 sites on boatable rivers =>5th order in 2008–2009. This is the first such study of mercury (Hg) in fish tissue from river sites focused on potential impacts to human health from fish consumption to also address wildlife impacts. Sample sites were identified as being urban or non-urban. All sample mercury concentrations were above the 3.33 ug kg � 1 (ppb) quantitation limit, and an estimated 25.4% (±4.4%) of the 51 663 river miles assessed exceeded the U.S. EPA 300 ug kg � 1 fish-tissue based water quality criterion for mercury, representing 13 144 ± 181.8 river miles. Estimates of river miles exceeding comparable aquatic life thresholds (translated from fillet concentrations to whole fish equivalents) in avian species were similar to the number of river miles exceeding the human health threshold, whereas some mammalian species were more at risk than human from lower mercury concentrations. A comparison of means from the non-urban and urban data and among three ecoregions did not indicate a statistically significant difference in fish tissue Hg concentrations at p < 0.05.

We measured concentrations of 56 active pharmaceutical ingredients (APIs) in effluent samples from 50 large wastewater treatment plants across the US. Hydrochlorothiazide was found in every sample. Metoprolol, atenolol, and carbamazepine were found in over 90% of the samples. Valsartan had the highest concentration (5300 ng/L), and also had the highest average concentration (1600 ng/L) across all 50 samples. Estimates of potential risks to healthy human adults were greatest for six anti-hypertensive APIs (lisinopril, hydrochlorothiazide, valsartan, atenolol, enalaprilat, and metoprolol), but nevertheless suggest risks of exposure to individual APIs as well as their mixtures are generally very low. Estimates of potential risks to aquatic life were also low for most APIs, but suggest more detailed study of potential ecological impacts from four analytes (sertraline, propranolol, desmethylsertraline, and valsartan).

Effluents from four healthcare facilities were characterized for the concentration of 16 common active pharmaceutical ingredients. The sampled facilities included a hospital, nursing care, assisted living, and independent living facility located within a single municipal wastewater system in Texas. Eleven of the 16 monitored pharmaceuticals were detected in at least 1 healthcare facility effluent and 2 measured antibiotics (sulfamethoxazole and trimethoprim) were detected in all 4 facility effluents. Active pharmaceutical ingredient concentrations ranged from non-detectable levels for several corticosteroids in all facility effluents to 180 microg/L sulfamethoxazole in the nursing care wastewater effluent. The mass of active pharmaceutical ingredients discharged to the municipality's wastewater conveyance system was determined by combining individual facility concentration data and daily wastewater flow. The estimated daily mass loading of all 16 pharmaceuticals ranged from 0.16 g/day to 23 g/day in the assisted living facility and nursing wastewater effluents, respectively. The combined active pharmaceutical ingredient mass loading for all four facilities was 42.6 g/day. These findings provide source characterization data for 16 common pharmaceuticals in healthcare facility wastewater and provide a basis for risk assessment of pharmaceuticals present in healthcare facility wastewaters.

Significant amounts of antibiotics enter the environment via point and nonpoint sources. We examined the temporal dynamics of tetracycline exposure to stream periphyton and associated organisms across a logarithmically dosed-series of experimental mesocosms, designed to mimic natural conditions. Target in-stream tetracycline exposures were based on environmentally relevant concentrations in aquatic ecosystems throughout the United States (1-100 μg L(-1)). Significant changes in the stream biotic community were observed within 7 days with in-stream tetracycline concentrations as low as 0.5 μg L(-1), including significant changes in antibiotic resistance, bacteria abundance and productivity, algae biomass, cyanobacteria, organic biomass, and nematodes. These effects were magnified with increased exposure time and dosing concentration. Recovery of the periphyton community after 28 days of exposure was dependent upon the tetracycline dose. At the highest doses, 10 and 100 μg L(-1), bacteria productivity recovered; however, bacteria, algae, and nematode abundance did not recover at the same rate and remained low even after a 28-day recovery period (of nondosing). This study demonstrates that tetracycline exposure under near-natural conditions and at concentrations currently observed in aquatic environments may have important consequences for the structure and function of stream periphyton and, potentially, public health via increasing resistance of naturally occurring bacteria.

Healthcare facilities are an under-characterized source of pharmaceuticals to municipal wastewaters. In this study, the composition and magnitude of sixteen cardiovascular active pharmaceutical ingredients (APIs) and two cardiovascular API metabolites in wastewater effluents from a hospital, nursing care, assisted living, and independent living facility are presented. Each cardiovascular API was detected in at least one facility's wastewater. The hospital's wastewater had the most detected cardiovascular APIs with thirteen of the eighteen measured compounds positively confirmed and quantified. Maximum mean analyte concentrations within each healthcare facility's wastewater were: 11.3 µg L(-1) atenolol for the independent living facility; 8.7 µg L(-1) valsartan for the assisted living facility; 2.7 µg L(-1) diltiazem for the nursing home facility; and 14.6 µg L(-1) valsartan for hospital facility. Daily wastewater flow was combined with individual concentrations to estimate the cardiovascular API mass loadings leaving each facility through wastewater discharges to the municipal sewer system. The estimated daily mass loading of all measured cardiovascular APIs ranged from 0.87 g per day at the assisted living facility to 12.5 g per day at the hospital. The combined loading for all four facilities was 16.2 g per day. This presented research informs the risk management process by providing source characterization data for healthcare facility wastewaters containing commonly prescribed cardiovascular APIs.

Some of the earliest initial reports from Europe and the United States demonstrated that a variety of pharmaceuticals and hormones could be found in surface waters, source waters, drinking water, and influents and effluents from wastewater treatment plants (WWTPs). It is unknown though, at this time, what ecotoxicological effects can be had from pharmaceuticals and hormones that are essentially designed for one purpose (e.g., treatment of human and domestic livestock for illness and disease) and their possible adverse effects on terrestrial wildlife, aquatic organisms, bacteria, and ultimately humans, through unintentional environmental exposure. One of the challenges the analytical chemistry community faces is the development of robust and standardized analytical methods and technologies that can easily be transferred to laboratories worldwide. While today's analysts can detect picograms per liter and nanograms per liter concentrations of numerous pharmaceuticals, hormones, and their metabolites, in a variety of environmental matrices, there are still analytical gaps that are necessary to fill. We hope that this article will add to the body of knowledge of environmental analytical chemistry techniques regarding pharmaceuticals and hormones, giving environmental scientists a good overview of those analytical techniques that are currently available, and where possible, of improvements and new methodologies that can be developed in support of this important, and relevant, environmental issue. Keywords: environmental chemistry; pharmaceuticals; hormones; analytical chemistry; solid-phase extraction; sampling; mass spectrometry; pressurized liquid extraction; green chemistry

Solid-phase extraction (SPE) and liquid chromatography in combination with ion trap mass spectrometry (LC/MS/MS) conditions were optimized for the simultaneous analysis of 13 antibiotics belonging to multiple classes and caffeine in 3 different water matrixes. The single-cartridge extraction step was developed using a reversed-phase cartridge, resulting in recoveries for the 14 compounds ranging from 71 to 119% with relative standard deviations of 16% or lower. The analytes were separated in one chromatographic run, and the SPE-LC/MS/MS detection limits ranged from 0.03 to 0.19 microg/L. The SPE procedure was validated in groundwater, surface water, and wastewater. The analysis of samples from each of the three water matrixes revealed clindamycin (1.1 microg/L) in surface water and multiple antibiotics in wastewater (0.10-1.3 microg/L). The use of identification points to unambiguously assign the identity of antibiotics in various water matrixes was applied to an ion trap data-dependent scanning method, which simultaneously collects full scan and full scan MS/MS data for the unequivocal identification of target analytes.