Metabolomics revealed disruptions in amino acid and antioxidant biochemistry in Daphnia magna exposed to industrial effluents associated with plastic and polymer production.

Industrial wastewater effluents are a major source of chemicals in aquatic environments, and many of these chemicals may negatively impact aquatic life. In this study, the crustacean Daphnia magna, a common model organism in ecotoxicity studies, was exposed for 48 h to nine different industrial effluent samples from manufacturing facilities associated with the production of plastics, polymers, and coating products at a range of dilutions: 10, 25, 50, 100% (undiluted). A targeted metabolomic-based approach using liquid chromatography-tandem mass spectrometry (LC-MS/MS) was used to quantify polar metabolites from individual daphnids that survived the 48 h exposure. Multivariate analyses and metabolite changes revealed metabolic perturbations across all effluent samples studied, with non-monotonic responses and both up and downregulation relative to the unexposed control. Pathway analyses indicated the disruption of similar and distinct pathways, mostly connected to protein synthesis, amino acid metabolism, and antioxidant processes. Overall, we observed disruptions in Daphnia biochemistry that were similar across the effluent samples, but with unique features for each effluent sample. Additionally, non-monotonic heightened responses suggested additive and/or synergistic interactions between the chemicals within the industrial effluents. These findings demonstrate that targeted metabolomic approaches are a powerful tool for the biomonitoring of aquatic ecosystems in the context of complex mixtures, such as industrial wastewater effluents.

Comparison of sub-lethal metabolic perturbations of select legacy and novel perfluorinated alkyl substances (PFAS) in Daphnia magna.

Per- and polyfluoroalkyl substances (PFAS) are a class of pollutants of concern due to their ubiquitous presence, persistence, and toxicity in aquatic environments. Legacy PFAS pollutants such as perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) have been more widely studied in aquatic environments. However, replacement PFAS, such as ammonium perfluoro (2-methyl-3-oxahexanoate; GenX) are increasingly being detected with little known information surrounding their toxicity. Here, Daphnia magna, a model organism for freshwater ecotoxicology was used to compare the acute sub-lethal toxicity of PFOS, PFOA, GenX, and PFAS mixtures. Using liquid chromatography with tandem mass spectrometry (LC-MS/MS), the targeted polar metabolic profile extracted from single Daphnia was quantified to investigate perturbations in the exposure groups versus the unexposed organisms. Multivariate statistical analyses demonstrated significant non-monotonic separation in PFOA, GenX, and PFAS mixture exposures. Sub-lethal exposure to concentrations of PFOS did not lead to significant separation in multivariate analyses. Univariate statistics and pathway analyses were used to elucidate the mode of action of PFAS exposure. Exposure to all individual PFAS led to significant perturbations in many amino acids including cysteine, histidine, tryptophan, glycine, and serine. These perturbations are consistent with biochemical pathway disruptions in the pantothenate and Coenzyme A (CoA) biosynthesis, thiamine metabolism, histidine metabolism, and aminoacyl-tRNA biosynthesis pathways. Overall, the collected metabolomic data is consistent with disruptions in energy metabolism and protein synthesis as the primary mode of action of sub-lethal PFAS exposure. Secondary modes of action among individual pollutant exposures demonstrated that the structural properties (carboxylic acid vs. sulfonic acid group) may play a role in the metabolic perturbations observed. Sub-lethal exposure to PFAS mixtures highlighted a mixed response when compared to the individual pollutants (PFOS, PFOA, and GenX). Overall, this study emphasizes the niche capability of environmental metabolomics to differentiate secondary modes of action from metabolic perturbations in both single pollutant and pollutant mixtures within the same chemical class.

Which of the (Mixed) Halogenated n-Alkanes Are Likely To Be Persistent Organic Pollutants?

Short-chain polychlorinated n-alkanes are ubiquitous industrial chemicals widely recognized as persistent organic pollutants. They represent only a small fraction of the 184,600 elemental compositions (C10-25) and the myriad isomers of all possible (mixed) halogenated n-alkanes (PXAs). This study prioritizes the PXAs on the basis of their potential to persist, bioaccumulate, and undergo long-range transport guided by quantitative structure-property relationships (QSPRs), density functional theory (DFT), chemical fate models, and partitioning space. The QSPR results narrow the list to 966 elemental compositions, of which 352 (23 Br, 83 Cl/F, 119 Br/Cl, and 127 Br/F) are likely constituents of substances used as lubricants, plasticizers, and flame retardants. Complementary DFT calculations suggest that an additional 1367 elemental compositions characterized by a greater number of carbon and fluorine atoms but fewer chlorine and bromine atoms may also pose a risk. The results of this study underline the urgent need to identify and monitor these suspected pollutants, most appropriately using mass spectrometry. We estimate that the resolving power required to distinguish ∼74% of the prioritized elemental compositions from the most likely interferents, i.e., chlorinated alkanes, is approximately 60,000 (full width at half-maximum). This indicates that accurate identification of the PXAs is achievable using most high-resolution mass spectrometers.

Nontargeted Screening Using Gas Chromatography-Atmospheric Pressure Ionization Mass Spectrometry: Recent Trends and Emerging Potential.

Gas chromatography-high-resolution mass spectrometry (GC-HRMS) is a powerful nontargeted screening technique that promises to accelerate the identification of environmental pollutants. Currently, most GC-HRMS instruments are equipped with electron ionization (EI), but atmospheric pressure ionization (API) ion sources have attracted renewed interest because: (i) collisional cooling at atmospheric pressure minimizes fragmentation, resulting in an increased yield of molecular ions for elemental composition determination and improved detection limits; (ii) a wide range of sophisticated tandem (ion mobility) mass spectrometers can be easily adapted for operation with GC-API; and (iii) the conditions of an atmospheric pressure ion source can promote structure diagnostic ion-molecule reactions that are otherwise difficult to perform using conventional GC-MS instrumentation. This literature review addresses the merits of GC-API for nontargeted screening while summarizing recent applications using various GC-API techniques. One perceived drawback of GC-API is the paucity of spectral libraries that can be used to guide structure elucidation. Herein, novel data acquisition, deconvolution and spectral prediction tools will be reviewed. With continued development, it is anticipated that API may eventually supplant EI as the de facto GC-MS ion source used to identify unknowns.

Characterization of Polycyclic Aromatic Compounds in Commercial Pavement Sealcoat Products for Enhanced Source Apportionment.

Coal tar-based sealcoat (CTSC) products are an urban source of polycyclic aromatic compounds (PACs) to the environment. However, efforts to assess the environmental fate and impacts of CTSC-derived PACs are hindered by the ubiquity of (routinely monitored) PACs released from other environmental sources. To advance source identification of CTSC-derived PACs, we use comprehensive two-dimensional gas chromatography-high resolution mass spectrometry (GC × GC/HRMS) to characterize the major and minor components of CTSC products in comparison to those in other sources of PACs, viz., asphalt-based sealcoat products, diesel particulate, diesel fuel, used motor oil and roofing shingles. GC × GC/HRMS analyses of CTSC products led to the confident assignment of compounds with 88 unique elemental compositions, which includes a set of 240 individual PACs. Visualization of the resulting profiles using Kendrick mass defect plots and hierarchical cluster analysis highlighted compositional differences between the sources. Profiles of alkylated PAHs, and heteroatomic (N, O, S) PACs enabled greater specificity in source differentiation. Isomers of specific polycyclic aromatic nitrogen heterocycles (PANHs) were diagnostic for coal tar-derived PAC sources. The compounds identified and methods used for this identification are anticipated to aid in future efforts on risk assessment and source apportionment of PACs in environmental matrices.

Silver near municipal wastewater discharges into western Lake Ontario, Canada.

Because of the widespread use of silver nanoparticles in commercial products, discharges of municipal wastewater may be a point source of silver in the aquatic environment. We monitored two sites in western Lake Ontario impacted by discharges from wastewater treatment plants serving the City of Toronto. Concentrations of silver were elevated in bottom sediments and suspended sediments collected at the two sites. We also deployed two types of passive samplers in the water column at the two sites, the newly developed Carbon Nanotube Integrative Samplers for monitoring "CNIS-labile" silver and Diffusive Gradient in Thin Film samplers for monitoring "DGT-labile" silver. Results from these passive samplers indicated that the concentrations of silver at the two sites were either below detection limits or were in the ng/L range. In laboratory experiments where the sediments were re-suspended in Milli-Q water, a small proportion of the silver (i.e., < 25%) was labile and partitioned as colloidal or dissolved silver into the liquid phase after agitation. Nanoparticles tentatively identified as silver nanoparticles were detected by single-particle ICP-MS in suspension after agitation of both suspended and bottom sediments. Therefore, there is a need to assess whether silver species, including silver nanoparticles are transported from wastewater treatment plants into sediments in the aquatic environment. This study is unique in focusing on the in situ distribution of silver in natural waters and in sediments that are potentially impacted by urban sources of nanoparticles.

Reduction of Intersex in a Wild Fish Population in Response to Major Municipal Wastewater Treatment Plant Upgrades.

Intersex in fish downstream of municipal wastewater treatment plants (MWWTPs) is a global concern. Consistent high rates of intersex in male rainbow darter (Etheostoma caeruleum) have been reported for several years in the Grand River, in southern Ontario, Canada, in close proximity to two MWWTPs. The larger MWWTP (Kitchener) recently underwent upgrades that included the conversion from a carbonaceous activated sludge to nitrifying activated sludge treatment process. This created a unique opportunity to assess whether upgrades designed to improve effluent quality could also remediate the intersex previously observed in wild fish. Multiple years (2007-2012) of intersex data on male rainbow darter collected before the upgrades at sites associated with the MWWTP outfall were compared with intersex data collected in postupgrade years (2013-2015). These upgrades resulted in a reduction from 70 to 100% intersex incidence (preupgrade) to <10% in postupgrade years. Although the cause of intersex remains unknown, indicators of effluent quality including nutrients, pharmaceuticals, and estrogenicity improved in the effluent after the upgrades. This study demonstrated that investment in MWWTP upgrades improved effluent quality and was associated with an immediate change in biological responses in the receiving environment. This is an important finding considering the tremendous cost of wastewater infrastructure.

Occurrence and Fate of Trace Contaminants during Aerobic and Anaerobic Sludge Digestion and Dewatering.

Digestion of municipal wastewater biosolids is a necessary prerequisite to their beneficial use in land application, in order to protect public health and the receiving environment. In this study, 13 pharmaceuticals and personal care products (PPCPs), 11 musks, and 17 polybrominated diphenyl ethers were analyzed in 84 samples including primary sludge, waste activated sludge, digested biosolids, dewatered biosolids, and dewatering centrate or filtrate collected from five wastewater treatment plants with aerobic or anaerobic digestion. Aerobic digestion processes were sampled during both warm and cold temperatures to analyze seasonal differences. Among the studied compounds, triclosan, triclocarban, galaxolide, and BDE-209 were the substances most frequently detected under different treatment processes at levels up to 30,000 ng/g dry weight. Comparing aerobic and anaerobic digestion, it was observed that the levels of certain PPCPs and musks were significantly higher in anaerobically digested biosolids, relative to the residues from aerobic digestion. Therefore, aerobic digestion has the potential advantage of reducing levels of PPCPs and musks. On the other hand, anaerobic digestion has the advantage of recovering energy from the biosolids in the form of combustible gases while retaining the nutrient and soil conditioning value of this resource.

Industrial sources of per- and polyfluoroalkyl substances (PFAS) to a sewershed in Ontario, Canada.

Per- and polyfluoroalkyl substances (PFAS) are ubiquitous in the environment despite global regulatory action to restrict their use in industrial processes and products. The objective of this reconnaissance sampling was to understand current industrial use and ongoing sources of PFAS in Ontario. Fourteen PFAS were analyzed in effluents from four sectors: electroplaters, laundry and carpet cleaners, landfills, and circuit board manufacturers that discharge to sewersheds connected to wastewater treatment plants. Maximum concentrations were detected in carpet cleaning wastewater: 79,000 ng/L for perfluorohexane sulfonate (PFHxS), 26,000 ng/L perfluorooctane sulfate (PFOS), and 9400 ng/L perfluorooctanoic acid (PFOA). Total summed PFAS (∑PFAS14) concentrations were highest in laundry and carpet cleaners > electroplaters > landfill leachate > circuit boarders. These results indicate that PFAS continue to be used in select manufacturing and processing facilities and that the elevated levels are associated with past and current uses in commercial products.

Sublethal Exposure of Per- and Polyfluoroalkyl Substances of Varying Chain Length and Polar Functionality Results in Distinct Metabolic Responses in Daphnia magna.

Per- and polyfluoroalkyl substances (PFAS) are a class of persistent organic pollutants used in industrial applications because of their physicochemical properties, which results in their ubiquitous presence across environmental matrices. To date, legacy PFAS have been well studied; however, the concentration of alternative PFAS may exceed the concentration of legacy pollutants, and more information is needed regarding the sublethal toxicity at the molecular level of aquatic model organisms, such as Daphnia magna. Perfluorobutanoic acid (PFBA), perfluorohexanoic acid (PFHxA), perfluorohexanesulfonic acid (PFHxS), and perfluorononanoic acid (PFNA) are four widely detected PFAS alternatives of varying chain length and polar functionality that are quantified in aquatic environments. The present study examines the metabolic perturbations of PFAS with varying chemistries to D. magna using targeted mass spectrometry-based metabolomics. Daphnia were acutely exposed to sublethal concentrations of PFBA, PFHxA, PFHxS, and PFNA before the polar metabolite profile was extracted from single organisms. Multivariate analysis demonstrated significant separation between the sublethal concentrations of PFHxA, PFHxS, and PFNA relative to the controls; in sum, longer chain lengths demonstrated greater overall perturbations to the extracted metabolic profiles. Univariate statistics revealed significant perturbations in the concentrations of several amino acids, nucleotides/nucleosides, and neurotransmitters with exposure to PFAS. These metabolic perturbations are consistent with disruptions in energy metabolism (pantothenate and coenzyme A metabolism, histidine metabolism) and protein synthesis (aminoacyl-transfer RNA biosynthesis and amino acid metabolism), which were identified through biochemical pathway analysis. These results provide evidence that although PFAS chemistry (chain length and polar functional group) invokes unique metabolic responses, there is also an underlying toxic mode of action that is common with select PFAS exposure. Overall, the present study highlights the capabilities of environmental metabolomics to elucidate the molecular-level perturbations of pollutants within the same chemical class to model aquatic organisms, which can be used to prioritize risk assessment of substituted PFAS alternatives. Environ Toxicol Chem 2023;42:242-256. © 2022 SETAC.

Daphnia magna sub-lethal exposure to phthalate pollutants elicits disruptions in amino acid and energy metabolism.

Phthalic acid esters (PAEs) are a class of chemicals that are usually incorporated as additives in the manufacturing of plastics. PAEs are not covalently bound to the material matrix and can, consequently, be leached into the environment. PAEs have been reported to act as endocrine disruptors, neurotoxins, metabolic stressors, and immunotoxins to aquatic organisms but there is a lack of information regarding the impact of sub-lethal concentrations to target organisms. The freshwater crustacean Daphnia magna, a commonly used model organism in aquatic toxicity, was exposed to four phthalate pollutants: dimethyl phthalate (DMP), diethyl phthalate (DEP), monomethyl phthalate (MMP), and monoethyl phthalate (MEP). Liquid chromatography-tandem mass spectrometry (LC-MS/MS) was employed in a targeted metabolomic approach to quantify polar metabolites extracted from a single Daphnia body. Individual metabolite percent changes and hierarchical clustering heatmap analysis showed unique metabolic profiles for each phthalate pollutant. Metabolite percent changes were mostly downregulated or presented opposing responses for the low and high concentrations tested. Meanwhile, pathway analyses suggest the disruption of related and unique pathways, mostly connected with amino acid and energy metabolism. The pathways aminoacyl-tRNA biosynthesis, arginine biosynthesis, and glutathione metabolism were disrupted by most selected PAEs. Overall, this study indicates that although phthalate pollutants can elicit distinct metabolic perturbations to each PAE, they still impacted related biochemical pathways. These chemical-class based responses could be associated with a common toxic mechanism of action. The reported findings show how targeted metabolomic approaches can lead to a better understanding of sub-lethal exposure to pollutants, revealing metabolomic endpoints do not hold a close relationship with traditional acute toxicity endpoints.

Nontargeted screening reveals fluorotelomer ethoxylates in indoor dust and industrial wastewater.

Concerns regarding the persistence, bioaccumulation behaviour, and toxicity of perfluorooctanoic acid and perfluorooctane sulfonic acid have resulted in the creation of thousands of replacement perfluoroalkyl substances (PFAS). This study reports on the discovery of fluorotelomer ethoxylates (FTEO) in indoor dust (9/15 samples), and industrial effluents (14/37 samples) using gas chromatographic cyclic ion mobility mass spectrometry (GC-cIMS). By filtering the detected unknowns by mass and collision-cross section, a series of FTEO homologues were revealed with the formula F-(CF2)n(C2H4O)xH, where n = 6,8,10, and x = 4-12. The highest concentrations were observed in samples collected from healthcare facilities, consistent with the potential use of these compounds in anti-fog products, sprays used to prevent condensation on eyeglasses. FTEOs were also detected in c. 40 % of industrial effluent samples, with the highest concentrations in electroplating facilities, manufacturers of cosmetics and personal care products, and linen cleaning services for healthcare and work uniforms. These results suggest that FTEOs may well be widespread pollutants that are more persistent than previously thought, underlining the need for further study of their occurrence and potential impact to human health and the environment.

Wild fish responses to wastewater treatment plant upgrades in the Grand River, Ontario.

Municipal wastewater treatment plant (WWTP) effluent is one of several point sources of contaminants (nutrients, pharmaceuticals, estrogens, etc.) which can lead to adverse responses in aquatic life. Studies of WWTP effluent impacts on rainbow darter (Etheostoma caeruleum) collected downstream of WWTPs in the Grand River, Ontario have reported disruption at multiple levels of biological organization, including altered vitellogenin gene expression, lower levels of in vitro steroid production, and high frequency of intersex. However, major upgrades have occurred at treatment plants in the central Grand River over the last decade. Treatment upgrades to the Waterloo WWTP were initiated in 2009 but due to construction delays, the upgrades came fully on-line in 2017/2018. Responses in rainbow darter have been followed at sites associated with the outfall consistently over this entire time period. The treatment plant upgrade resulted in nitrification of effluent, and once complete there was a major reduction in effluent ammonia, selected pharmaceuticals, and estrogenicity. This study compared several key responses in rainbow darter associated with the Waterloo WWTP outfall prior to and post upgrades. Stable isotopes signatures in fish were used to track exposure to effluent and changed dramatically over time, corresponding to the effluent quality. Disruptions in in vitro steroid production and intersex in the darters that had been identified prior to the upgrades were no longer statistically different from the upstream reference sites after the upgrades. Although annual variations in water temperature and flow can potentially mask or exacerbate the effects of the WWTP effluent, major capital investments in wastewater treatment targeted at improving effluent quality have corresponded with the reduction of adverse responses in fish in the receiving environment.

Metabolomics Reveals That Bisphenol Pollutants Impair Protein Synthesis-Related Pathways in Daphnia magna.

Bisphenols are used in the production of polycarbonate plastics and epoxy resins. Bisphenol A (BPA) has been widely studied and is believed to act as an endocrine disruptor. Bisphenol F (BPF) and bisphenol S (BPS) have increasingly been employed as replacements for BPA, although previous studies suggested that they yield similar physiological responses to several organisms. Daphnia magna is a common model organism for ecotoxicology and was exposed to sub-lethal concentrations of BPA, BPF, and BPS to investigate disruption to metabolic profiles. Targeted metabolite analysis by liquid chromatography-tandem mass spectrometry (LC-MS/MS) was used to measure polar metabolites extracted from D. magna, which are linked to a range of biochemical pathways. Multivariate analyses and individual metabolite changes showed similar non-monotonic concentration responses for all three bisphenols (BPA, BPF, and BPS). Pathway analyses indicated the perturbation of similar and distinct pathways, mostly associated with protein synthesis, amino acid metabolism, and energy metabolism. Overall, we observed responses that can be linked to a chemical class (bisphenols) as well as distinct responses that can be related to each individual bisphenol type (A, F, and S). These findings further demonstrate the need for using metabolomic analyses in exposure assessment, especially for chemicals within the same class which may disrupt the biochemistry uniquely at the molecular-level.

NMR spectroscopy of wastewater: A review, case study, and future potential.

NMR spectroscopy is arguably the most powerful tool for the study of molecular structures and interactions, and is increasingly being applied to environmental research, such as the study of wastewater. With over 97% of the planet's water being saltwater, and two thirds of freshwater being frozen in the ice caps and glaciers, there is a significant need to maintain and reuse the remaining 1%, which is a precious resource, critical to the sustainability of most life on Earth. Sanitation and reutilization of wastewater is an important method of water conservation, especially in arid regions, making the understanding of wastewater itself, and of its treatment processes, a highly relevant area of environmental research. Here, the benefits, challenges and subtleties of using NMR spectroscopy for the analysis of wastewater are considered. First, the techniques available to overcome the specific challenges arising from the nature of wastewater (which is a complex and dilute matrix), including an examination of sample preparation and NMR techniques (such as solvent suppression), in both the solid and solution states, are discussed. Then, the arsenal of available NMR techniques for both structure elucidation (e.g., heteronuclear, multidimensional NMR, homonuclear scalar coupling-based experiments) and the study of intermolecular interactions (e.g., diffusion, nuclear Overhauser and saturation transfer-based techniques) in wastewater are examined. Examples of wastewater NMR studies from the literature are reviewed and potential areas for future research are identified. Organized by nucleus, this review includes the common heteronuclei (13C, 15N, 19F, 31P, 29Si) as well as other environmentally relevant nuclei and metals such as 27Al, 51V, 207Pb and 113Cd, among others. Further, the potential of additional NMR methods such as comprehensive multiphase NMR, NMR microscopy and hyphenated techniques (for example, LC-SPE-NMR-MS) for advancing the current understanding of wastewater are discussed. In addition, a case study that combines natural abundance (i.e. non-concentrated), targeted and non-targeted NMR to characterize wastewater, along with in vivo based NMR to understand its toxicity, is included. The study demonstrates that, when applied comprehensively, NMR can provide unique insights into not just the structure, but also potential impacts, of wastewater and wastewater treatment processes. Finally, low-field NMR, which holds considerable future potential for on-site wastewater monitoring, is briefly discussed. In summary, NMR spectroscopy is one of the most versatile tools in modern science, with abilities to study all phases (gases, liquids, gels and solids), chemical structures, interactions, interfaces, toxicity and much more. The authors hope this review will inspire more scientists to embrace NMR, given its huge potential for both wastewater analysis in particular and environmental research in general.

The impact of risk management measures on the concentrations of per- and polyfluoroalkyl substances in source and treated drinking waters in Ontario, Canada.

Risk management measures (RMMs) are a broad set of tools used in global treaties and national regulations to manage, ban or restrict the use of toxic chemicals. Per- and polyfluoroalkyl substances (PFAS) are a group of chemicals that are persistent, bioaccumulate, biomagnify and are inherently toxic to the environment and human health. For these reasons global RMMs have been imposed on the manufacture and use of select PFAS. To evaluate the occurrence and potential current risk of PFAS in the Ontario environment, PFAS were quantitatively measured in source waters pre- (2005-2007) and post- (2012-2016, 2018-2019) implementation of RMMs. Source water samples were collected pre- (n = 105), and post-RMMs (n = 326) from lake, river and groundwater and analyzed for up to 14 PFAS. Pre-RMMs, the most frequently detected PFAS in source water were perfluorooctanoic acid (PFOA; 83%) and perfluorooctane sulfonate (PFOS; 76%) followed by perfluorohexane sulfonate (PFHxS; 47%) and the maximum ∑PFAS10 was 42.1 ng/L. Post-RMMs, the maximum ∑PFAS10 (which includes PFOS) was statistically significantly reduced to 15.5 ng/L, well below the Federal Environmental Quality Guidelines for PFOS. To evaluate post-RMMs risk to human health, 226 drinking water samples were collected from 25 drinking water systems with conventional and advanced treatment. All individual (or ∑PFAS) concentrations are well below current and proposed Health advisory levels or regulatory guidelines/standards for PFAS in drinking water with calculated Risk Quotients (RQ) <0.02. This survey indicates that the implementation of RMMs for select PFAS have made a significant difference to the concentrations detected in source waters in Ontario, Canada.

Environmental loadings of Active Pharmaceutical Ingredients from manufacturing facilities in Canada.

Recent evidence has revealed that cities with pharmaceutical manufacturers have elevated concentrations of Active Pharmaceutical Ingredients (APIs) in their receiving water bodies. The purpose of this study was to gather information on direct sewer discharges of APIs during their manufacturing and processing from five pharmaceutical manufacturing facilities in Ontario, Canada. Drug classes and maximum reported concentrations (ng/L) for which APIs were directly discharged included: antidepressants (paroxetine - 3380 and sertraline - 5100); mood stabilizer (carbamazepine - 575,000); antibiotics (penicillin - 14,300); analgesics (acetaminophen - 461,000; codeine - 49,200; ibuprofen - 344,000; naproxen - 253,000 and oxycodone 21,000); cardiovascular drugs (atorvastatin - 893 and metoprolol - 7,333,600) and those drugs used for blood pressure control (amlodipine - 22,900; diltiazem - 1,160,000; furosemide - 1,200,000 and verapamil - 7340). Based on flow and water usage data from the individual facilities, the maximum concentrations for acetaminophen, ibuprofen, carbamazepine, diltiazem and metoprolol correlate to approximately 200, 220, 390, 420 and 14,200 g respectively, of lost product being directly discharged to the sewers daily during active manufacturing. This survey demonstrates that direct point source discharges from pharmaceutical manufacturers represent a key source of pharmaceutical pollution to receiving sewersheds. Onsite recovery of product or treatment at pharmaceutical manufacturing or processing facilities to reduce the sewage loadings to receiving treatment plants, product loss and potential environmental loadings is strongly recommended.

The final discharge: Quantifying contaminants in embalming process effluents discharged to sewers in ontario, Canada.

The process of embalming human remains as part of the funeral home industry, entails replacing blood with embalming fluid. Typically the unused/excess fluids are disposed of directly to the sewershed or septic system. The presence of select contaminants in sewer discharges from 8 funeral homes (facilities) in York Region, Ontario during active embalming processes was studied. A wide range of contaminants including embalming fluids (formaldehyde and triclosan); metals, conventional parameters, persistent organic pollutants (polycyclic aromatic hydrocarbons, pesticides, and polychlorinated byphenyls), nonyl phenols and active pharmaceutical ingredients (APIs) were measured in the final embalming effluent and compared to regulatory sewer limits where available. Two main constituents of embalming fluids-formaldehyde and triclosan-were detected at maximum concentrations of 561,000 µg/L and 505 µg/L respectively. Other persistent organic pollutants detected in embalming effluent included banned pesticides lindane (83 ng/L) and metabolites of DDT (DDE; 2,300 ng/L). Elevated APIs found in over-the-counter drugs and products were also frequently detected at elevated concentrations (oxybenzone, hydrocortisone, lidocaine, naproxen, ibuprofen, ciprofloxacin and DEET). Most contaminants did not exceed regulatory sewer limits where available, however others including biochemical oxygen demand (cBOD5) and conventional parameters were consistently above regulatory limits. Large amounts of formaldehyde and triclosan may pose a risk to receiving sewersheds and receiving sewage treatment plants due to their antimicrobial activities.

Runoff of pharmaceuticals and personal care products following application of biosolids to an agricultural field.

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.

Neonicotinoid pesticides in drinking water in agricultural regions of southern Ontario, Canada.

Because of the persistence and solubility of neonicotinoid insecticides (NNIs), there is concern that these compounds may contaminate sources of drinking water. The objective of this project was to evaluate the distribution of NNIs in raw and treated drinking water from selected municipalities that draw their water from the lower Great Lakes in areas of southern Ontario, Canada where there is high intensity agriculture. Sites were monitored using Polar Organic Chemical Integrative Samplers (POCIS) and by collecting grab samples at six drinking water treatment plants. Thiamethoxam, clothianidin and imidacloprid were detected in both POCIS and grab samples of raw water. The frequency of detection of NNIs was much lower in treated drinking water, but some compounds were still detected at estimated concentrations in the low ng L-1 range. Thiamethoxam was detected in one grab sample of raw drinking water at a mean concentration of 0.28 µg L-1, which is above the guidelines for drinking water recommended in some jurisdictions, including the European Union directive on pesticide levels <0.1 µg L-1 in water intended for human consumption. Further work is required to determine whether contamination of sources of drinking water with this class of insecticides is a global problem in agricultural regions.