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Several micropollutants, including caffeine, artificial sweeteners, pharmaceuticals, steroid hormones and a current-use pesticide were analyzed in water samples collected from five groundwater pumping stations in Barbados. The presence of caffeine and three artificial sweeteners (i.e. acesulfame, sucralose, saccharin) in groundwater samples indicated that groundwater was being contaminated by infiltration of wastewater into the karst aquifer. An estrogen (i.e. estrone), three pharmaceuticals (i.e. carbamazepine, trimethoprim, ibuprofen) and a transformation product of the fungicide, chlorothalonil (i.e. 4-hydroxychlorothalonil) were also detected at ng/L concentrations in groundwater collected from two or more pumping sites. The concentrations of carbamazepine and trimethoprim were correlated with the concentrations of caffeine (R2 values of 0.70 to 0.80), indicating pharmaceutical contamination of groundwater by infiltration from domestic wastewater. The concentrations of caffeine were generally higher in groundwater samples collected in June during the wet season relative to the concentrations in samples collected in February during the dry season, indicating that infiltration of contaminants is higher during periods of heavy rainfall. Rapid rates of degradation and relatively slow rates of infiltration may explain why several target analytes were not detected in groundwater. Elevated concentrations of 4-hydroxychlorothalonil > 0.1 μg/L in samples collected at two of the monitoring sites warrant further studies on the sources and the distribution of this compound and other pesticides used in agriculture and for turf-treatment (e.g. golf courses). Overall, more data are needed in order to implement mitigation strategies that are effective in reducing chemical contamination in groundwater in Barbados.

Antidepressant drugs have been detected in municipal wastewater effluents (MWWEs) at ng/L to low μg/L concentrations. We exposed fathead minnow (Pimephales promelas) over a full lifecycle to a mixture of five antidepressants at concentrations similar to a MWWE (1× AntiD Mix); venlafaxine at 2400 ng/L, citalopram at 240 ng/L, fluoxetine at 90 ng/L, sertraline at 20 ng/L, and bupropion at 90 ng/L, and 10× these concentrations (i.e. 10× AntiD Mix). Mean measured concentrations of venlafaxine, citalopram, fluoxetine, sertraline, and bupropion were 2300, 160, 110, 7 ng/L, and below detection limits, respectively, for the 1× AntiD Mix, and 33,000, 2900, 1000, 210, and 100 ng/L, respectively for the 10× AntiD Mix. During the life-cycle exposure, no significant changes were observed in survival of fathead minnows. When male fish from the exposed treatments reached maturity, their weights were increased compared to control males. There were no significant differences in condition factor, gonadosomatic index, or liver-somatic index in the exposed fish. Exposed fathead minnows produced similar numbers of eggs as control fish, and there were no changes in nest-defense behaviours of male minnows. Egg quality, % fertilization, and % hatching in F1 fry were unaffected by exposure to the antidepressants. Eggs hatched 0.5 d earlier, deformities in fry were 50% lower, and there were transient decreases in length of F1 larvae at 8 days post-hatch in offspring from the treatment with the 10× AntiD Mix. Overall, exposure to the antidepressant mixture at environmentally relevant concentrations (i.e. 1× AntiD Mix) caused no adverse effects in fathead minnows. Exposure to the 10× AntiD Mix increased the weight of adult male minnows and caused subtle effects in F1 offspring. This study is the first to assess sublethal effects in fish exposed to mixtures of antidepressants over a full lifecycle. Capsule No effects were observed in fathead minnow exposed for a lifecycle to antidepressant mixtures at environmentally-relevant concentrations.

A sewage lagoon serving the small municipality of Lakefield in Ontario, Canada was monitored in the summer, fall and winter to determine removals of carbamazepine, trimethoprim, sulfamethoxazole, ibuprofen, gemfibrozil, triclosan, sucralose, HHCB and AHTN. Concentrations of these compounds in untreated and treated wastewater were estimated by deploying POCIS and SPMD passive samplers in the sewage lagoon. Passive samplers were also deployed at several points upstream and downstream of the point of discharge from the lagoon into the Otonabee River. LC–MS/MS and GC–MS were utilized to determine the concentrations of pharmaceuticals and personal care products (PPCPs) and sucralose, an artificial sweetener. Among PPCPs sampled by POCIS, the highest estimated concentration in untreated wastewater was ibuprofen sampled during the fall, at an estimated concentration of 60.3 ng/L. The estimated average concentration of sucralose was 13.6 ng/L in the untreated wastewaters. Triclosan, HHCB and AHTN in SPMDs were highest during fall season, at 30, 1677 and 109 ng/L, respectively. For all compounds except gemfibrozil, carbamazepine and sucralose, removals were highest in the summer (83.0 to 98.8%) relative to removals in the fall (48.4 to 91.4%) and winter (14.0 to 78.3%). Finally, the estimated concentrations of carbamazepine, sulfamethoxazole, triclosan and HHCB were compared with predicted values obtained through application of the WEST® modeling tool, with a new model based on the River Water Quality Model No. 1 and extended with dynamic mass balances describing the fate of chemicals of emerging concern subject to a variety of removal pathways. The model was able to adequately predict the fate of these four compounds in the lagoon in summer and winter, but the model overestimated removals of three of the four test compounds in the fall sampling period. This lagoon was as effective at removing PPCPs as many conventional WWTPs, but removals were better during the summer.

Environmental agencies must monitor an ever increasing range of contaminants of emerging concern, including endocrine disrupting compounds (EDCs). An alternative to using ultra-trace chemical analysis of samples for EDCs is to test for biological activity using in vitro screening assays, then use these assay results to direct analytical chemistry approaches. In this study, we used both analytical approaches and in vitro bioassays to characterize the EDCs present in treated wastewater from four wastewater treatment plants (WWTPs) in Ontario, Canada. Estrogen-mediated activity was assessed using a yeast estrogenicity screening (YES) assay. An in vitro competitive binding assay was used to assess capacity to interfere with binding of the thyroid hormone, thyroxine (T4) to the recombinant human thyroid hormone transport protein, transthyretin (i.e. hTTR). An in vitro binding assay with a rat peroxisome proliferator responsive element transfected into a rainbow trout gill cell line was used to evaluate binding and subsequent gene expression via the peroxisome proliferator activated receptor (PPAR). Analyses of a suite of contaminants known to be EDCs in extracts from treated wastewater were conducted using either gas chromatography with mass spectrometry (GC-MS) or liquid chromatography with tandem mass spectrometry (LC-MS/MS). Estrogenic activity was detected in the YES assay only in those extracts that contained detectable amounts of estradiol (E2). There was a positive relationship between the degree of response in the T4-hTTR assay and the amounts of polybrominated diphenyl ether (PBDE) congeners 47 and 99, triclosan and the PBDE metabolite, 4-OH-BDE17. Several wastewater extracts gave a positive response in the PPAR assay, but these responses were not correlated with the amounts of any of the EDCs analyzed by LC-MS/MS. Overall, these data indicate that a step-wise approach is feasible using a combination of in vitro testing and instrumental analysis to monitor for EDCs in wastewater and other environmental matrixes.

Synthetic musks have been detected in sewage effluents, surface waters, and fish tissues where the polycyclic musk compound, HHCB (Galaxolide®) is the dominant compound in those matrices. In the present study, the Galaxolide® formulation was tested in the yeast estrogenicity screening (YES) assay, and also tested in in vitro and in vivo teleost systems to determine whether it interacts with the estrogen receptor as either an agonist or antagonist. In those tests, Galaxolide® did not act as an estrogen agonist, however there was strong evidence of antagonistic activity as Galaxolide® inhibited the estrogenic activity of 17β-estradiol (E2). In the YES assay based on a recombinant strain of yeast containing the human estrogen receptor (i.e. hERα), Galaxolide® inhibited the effects of E2 in a dose-dependent manner (IC50=1.63×10(-5)M). In a luciferase reporter gene assay based on the rainbow trout estrogen receptor (i.e. rtER) transfected into a rainbow trout gonadal (RTG-2) cell line, the IC50 for the antagonistic effect of Galaxolide® was 2.79×10(-9)M. In an in vivo assay based on modulation of vitellogenin in rainbow trout, Galaxolide® i.p. injected into trout at a dose of 3.64mg/kg caused inhibition of E2-induced vitellogenin production. That dose is within the range of concentrations of Galaxolide® that have been detected in tissues of fish from contaminated locations.

Municipal biosolids are a useful source of nutrients for crop production, and commonly used in agriculture. In this field study, we applied dewatered municipal biosolids at a commercial rate using broadcast application followed by incorporation. Precipitation was simulated at 1, 3, 7, 21 and 34 days following the application on 2 m(2) microplots to evaluate surface runoff of various pharmaceuticals and personal care products (PPCPs), namely atenolol, carbamazepine, cotinine, caffeine, gemfibrozil, naproxen, ibuprofen, acetaminophen, sulfamethoxazole, triclosan and triclocarban. There was little temporal coherence in the detection of PPCPs in runoff, various compounds being detected maximally on days 1, 3, 7 or 36. Maximum concentrations in runoff ranged from below detection limit (gemfibrozil) to 109.7 ng L(-1) (triclosan). Expressing the total mass exported as a percentage of that applied, some analytes revealed little transport potential (1% exported; triclocarban, triclosan, sulfamethoxazole, ibuprofen, naproxen and gemfibrozil) whereas others were readily exported (1% exported; acetaminophen, carbamazepine, caffeine, cotinine, atenolol). Those compounds with little transport potential had log K(ow) values of 3.18 or greater, whereas those that were readily mobilized had K(ow) values of 2.45 or less. Maximal concentrations of all analytes were below toxic concentrations using a variety of endpoints available in the literature. In summary, this study has quantified the transport potential in surface runoff of PPCPs from land receiving biosolids, identified that log K(ow) may be a determinant of runoff transport potential of these analytes, and found maximal concentrations of all chemicals tested to be below toxic concentrations using a variety of endpoints.

Land application of municipal biosolids (sewage) is a common farming practice in many parts of the world. There is potential for transport of pharmaceuticals and personal care products (PPCPs) from agricultural fields to adjacent surface waters via tile drainage systems. In this study, liquid municipal biosolids (LMB) (total solids=11,933 mg L(-1)), supplemented with selected PPCPs and the fluorescent dye tracer rhodamine WT (RWT), were applied to tile drained fields using two land application approaches. Objectives included evaluating the relative benefits of land application practices with respect to reducing PPCP loadings to tile drains, evaluating PPCP persistence in tile water, and determining whether rhodamine WT can be used to estimate PPCP mass loads in tile. The PPCPs examined included an antibacterial agent used in personal care products (triclosan), a metabolite of nicotine (cotinine), and a variety of drugs including two sulfonamide antimicrobials (sulfapyridine, sulfamethoxazole), a beta-blocker (atenolol), an anti-epileptic (carbamazepine), an antidepressant (fluoxetine), analgesic/anti-inflammatories (acetaminophen, naproxen, ibuprofen), and a lipid-regulator (gemfibrozil). Maximum observed PPCP concentrations in the spiked LMB were about 10(3) ng g(-1) dry weight. PPCPs were shown to move rapidly via soil macropores to tile drains within minutes of the land application. Maximum observed PPCP concentrations in tile effluent associated with the LMB application-induced tile flow event were approximately 10(1) to 10(3) ng L(-1). PPCP mass loads, for the application-induced tile-hydrograph event, were significantly (p0.1) higher for surface spreading over non-tilled soil (incorporation tillage occurring 20 h post-application), relative to aerating soil immediately prior to surface spreading using an AerWay slurry deposition system. PPCP concentrations that were detected above the limit of quantitation (LOQ) in tile water during several precipitation-induced tile flow events that occurred post-application, included: triclosan (max. approximately 1.5 x 10(2) ng L(-1)), carbamazepine (max. approximately 7 x 10(1) ng L(-1)), atenolol (max approximately 4 x 10(1) ng L(-1)), and cotinine (max approximately 2 x 10(1) ng L(-1)). In spite of their presence in biosolids, the other PPCPs were not observed above LOQ concentrations during these events. PPCP concentrations were predicted from RWT concentrations over a 40 day study period. Tile mass loads as a percent of PPCP mass applied to soil ranged from 4.2%+/-SD of 9.2% to 7.1%+/-10.9% for the AerWay system and surface spreading plus incorporation treatments, respectively.

Municipal biosolids are a source of nutrients for crop production. Beneficial Management Practices (BMPs) can be used to minimize the risk of contamination of adjacent water resources with chemical or microbial agents that are of public or environmental health concern. In this field study, we applied biosolids slurry at a commercial rate using either subsurface injection or broadcast application followed by incorporation. Precipitation was simulated at 1, 3, 7, 22, 36 and 266 days post-application on 2 m(2) microplots to evaluate surface runoff of 9 model pharmaceuticals and personal care products (PPCPs), atenolol, carbamazepine, cotinine, gemfibrozil, naproxen, ibuprofen, acetaminophen, sulfamethoxazole and triclosan. In runoff from the injected plots, concentrations of the model PPCPs were generally below the limits of quantitation. In contrast, in the broadcast application treatment, the concentrations of atenolol, carbamazepine, cotinine, gemfibrozil, naproxen, sulfamethoxazole and triclosan on the day following application ranged from 70-1477 ng L(-1) in runoff and generally declined thereafter with first order kinetics. The total mass of PPCPs mobilized in surface runoff per m(2) of the field ranged from 0.63 microg for atenolol to 21.1 microg for ibuprofen. For ibuprofen and acetaminophen, concentrations in runoff first decreased and then increased, suggesting that these drugs were initially chemically or physically sequestered in the biosolids slurry, and subsequently released in the soil. Carbamazepine and triclosan were detected at low concentrations in a runoff event 266 days after broadcast application. Overall, this study showed that injection of biosolids slurry below the soil surface could effectively eliminate surface runoff of PPCPs.

Synthetic musks are widely used as fragrance ingredients in personal care products, and they enter domestic wastewater treatment plants (WWTPs) through discharges into municipal sewage systems. Samples of aqueous sewage and biosolids collected from the Peterborough Wastewater Treatment Plant (WWTP), Ontario, Canada were analyzed for 11 synthetic musk compounds using GC/MS. The results showed that 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta[g]-2-benzopyrane (HHCB, 173.1 ± 43.4 ng/L) and 7-acetyl-1,1,3,4,4,6-hexamethyl-tetrahydronaphthalene (AHTN, 41.6 ± 15.8 ng/L) were the dominant fragrances in sewage, but other polycyclic musks and nitro musks were present at lower concentrations. The concentrations of HHCB and AHTN in the aqueous phase of the sewage were highly correlated with both BOD5 and TOC. The overall removal efficiency of synthetic musks from the aqueous sewage in the WWTP ranged from 43.3% to 56.9%, but removal occurred mainly by partitioning into the biosolids. Based on a mass balance model, the daily input and output of HHCB and AHTN in the Peterborough WWTP were 47 g and 46 g, respectively. In an agricultural field amended with biosolids from the Peterborough WWTP, HHCB and AHTN were detected in soil immediately after application at mean concentrations of 1.0 and 1.3 μg/kg, respectively, but concentrations declined relatively rapidly over the next 6 weeks, post-application.

a Agriculture and Agri-Food Canada, London, ON, Canada N5V 4T3 b Health Canada, New Substances Assessment and Control Bureau, Ottawa, Canada K1A 0K9 c Department of Biology, University of Western Ontario, London, ON, Canada N6A 5B7 d Ontario Ministry of the Environment, Toronto, ON, Canada M4V 1M2 e Agriculture and Agri-Food Canada, Ottawa, Canada K1A 0C6 f Worsfold Water Qualify Centre, Trent University, Peterborough, ON, Canada K9J 7B8 g Ontario Ministry of Food, Agriculture and Rural Affairs, Stratford, ON, Canada N5A 5T8

In order to investigate the putative association between chemical contamination in western Lake Ontario and high prevalences of fish tumors, sediments from Hamilton Harbour and Oakville Creek in Lake Ontario and reference sites in non-polluted areas of Ontario, Canada were collected and extracted for organic contaminants. Sediment extracts from Hamilton Harbour had the highest concentrations of polychlorinated biphenyls and organochlorine insecticides (ppb) and contained very high concentrations of polynuclear aromatic hydrocarbons (ppm); although the levels of these compounds varied widely with sampling location in the harbor. A sediment extract from Hamilton Harbour was mutagenic in the Ames bacterial assay, both with and without microsomal activation. High levels of aromatic DNA adducts were induced in cultured mouse C3H1OT1/2 cells after in vitro exposure to Hamilton Harbour sediment extract. In two separate carcinogenicity experiments involving a sac fry microinjection assay with rainbow trout (Oncorhynchus mykiss), Hamilton Harbour sediment extract induced hepatocellular carcinomas in fish. No hepatic neoplasms were observed in fish that had been treated with sediment extract from Oakville Creek, or with extract from a reference sediment. The significance of these results is discussed in relation to the distribution of neoplasms in feral fish within western Lake Ontario.

a Agriculture and Agri-Food Canada, Ottawa ON, Canada K1A 0C6 b Agriculture and Agri-Food Canada, London ON, Canada N5V 4T3 c Worsfold Water Quality Centre, Trent University, Peterborough, ON, Canada K9J 7B8 d University of Guelph-Kemptville, Kemptville, ON, Canada K0G 1G0 e Ontario Ministry of Agriculture, Food and Rural Affairs, Stratfold, ON, Canada N5A 5T8 f Health Canada, New Substances Assessment and Control Bureau, Ottawa ON, Canada K1A 0K9 g Ontario Ministry of the Environment, Toronto, ON, Canada M4V 1M2