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While organic-diffusive gradients in thin films (o-DGT) passive samplers have been used to assess organic contaminants in water, the effects of biofouling on accurate analyte quantification by o-DGT are poorly understood. We evaluated the effects of biofouling on the uptake of six common perfluoroalkyl substances (PFAS) using a previously developed polyacrylamide-WAX (weak anion exchange) o-DGT without a filter membrane. Linear uptake (

Microplastics (MP) are distributed throughout ecosystems and settle into sediments where they may threaten benthic communities; however, methods for quantifying MP in sediments have not been standardized. This study compares two methods for analyzing MP in sediments, including extraction and identification, and provides recommendations for improvement. Two laboratories processed sediment samples using two methods, referred to as "core" and "augmentation", and identified particles with visual microscopy and spectroscopy. Using visual microscopy, the augmentation method yielded mean recoveries (78%) significantly greater than the core (47%) (p = 0.03), likely due to the use of separatory funnels in the former. Spectroscopic recovery of particles was lower at 42 and 54% for the core and augmentation methods, respectively. We suspect the visual identification recoveries are overestimations from erroneous identification of non-plastic materials persisting post-extraction, indicating visual identification alone is not an accurate method to identify MP, particularly in complex matrices like sediment. However, both Raman and FTIR proved highly accurate at identifying recovered MP, with 96.7% and 99.8% accuracy, respectively. Low spectroscopic recovery of spiked particles indicates that MP recovery from sediments is lower than previously assumed, and MP may be more abundant in sediments than current analyses suggest. To our knowledge, likely due to the excessive time/labor-intensity associated with MP analyses, this is the first interlaboratory study to quantify complete method performance (extraction, identification) for sediments, with regards to capabilities and limitations. This is essential as regulatory bodies move toward long-term environmental MP monitoring.

The use of recycled glass as a substrate for constructed wetlands was assessed through two studies. The first study examined the dissipation of atenolol, carbamazepine, and sulfamethoxazole in mesocosm-modeled wetlands using glass or limestone gravel as substrates, with or without cattails (Typha spp.). Following pseudo-first-order kinetics, atenolol dissipated the fastest from the water surface of the mesocosms (t1/2~1 day), followed by sulfamethoxazole (t1/2~14 days), and carbamazepine (t1/2~48 days), with no significant differences across treatments. Increased half-lives were observed at greater depth, likely due to light screening. A Monte Carlo sensitivity analysis diagnosed sunlight absorption rates and second-order hydroxyl-mediated indirect photolysis rates to be the main sources of uncertainty in our dissipation rate estimates, compared to our observed rates. The second study examined in situ pharmaceutical removal in tertiary pilot-scale subsurface filters made of crushed recycled glass or sand in a wastewater treatment facility in Manitoba, Canada. Glass and sand showed no significant differences for pharmaceutical removals; atenolol and metoprolol were removed below limits of detection, while carbamazepine and sulfamethoxazole persisted over a retention time of 24 h. Overall, recycled glass performed similarly to traditional substrates for wetland-based wastewater treatment.

Diffuse pollution in urban receiving waters often adversely impacts both humans and ecosystems. Identifying such pollution sources is challenging and limits the effectiveness of management actions intended to reduce risk. Here, we evaluated the use of nontarget analysis via high-resolution mass spectrometry (HRMS) to develop chemical fingerprints/signatures for source tracking. Specifically, we applied nontarget HRMS to characterize and differentiate two urban chemical sources: roadway runoff and wastewater influent. We isolated 112 and 598 nontarget compounds (both known and unidentified chemicals) that co-occurred in all roadway runoff and wastewater influent samples, respectively, and were unique relative to other sampled sources. For example, methamphetamine, often considered wastewater derived, was detected in all samples, implying that individual wastewater indicators may lack sufficient specificity in urban receiving waters impacted by multiple sources. Hierarchical cluster analysis differentiated source types, and normalized abundance profiling prioritized nontarget compounds with consistent relative abundance patterns across field sites for a given source. Hexa(methoxymethyl)melamine, 1,3-diphenylguanidine, and polyethylene glycols co-occurred in roadway runoff across geographic areas and traffic intensities, supporting continued development of a universal roadway runoff fingerprint based on ubiquitous compounds. This study provides a proof-of-concept for isolating nontarget source fingerprints to track diffuse contamination in urban receiving waters.

Non-steroidal anti-inflammatory drugs are recognized widely as emerging contaminants. Sulindac has received additional attention as a prodrug in cancer treatment and because of its detection in drinking water and wastewaters. Nevertheless, there is limited knowledge about its kinetic behaviour and fate in the aquatic environment. In this work, the direct photolysis of sulindac, in which photochemical reactions were monitored and phototransformation products identified, was investigated under prolonged periods using UV-A and UV-B radiation and pH conditions (2 and 7) to evaluate the effect of the protonation state and the efficiency of the photolytic process. A novel kinetic mechanism has been proposed in which sulindac exhibits a consecutive reaction pathway, with pseudo-first order kinetics for rapid and reversible Z to E isomerization. Once photoequilibrium was reached, second-order degradation of the isomers in the presence of the new photodegradation products was observed. Photochemical transformation was faster under UV-B irradiation and lower pH, which suggests greater persistence of sulindac at more relevant environmental conditions of UV-A and pH 7. Two novel and major byproducts were identified, corresponding to the oxidative cleavage of the alkene exo to the indene system. The degradation pathway is mainly photoinduced, enhanced by acidic conditions and presumes the double bond as the most reactive site for the parent compound. This research demonstrates an approach for determining kinetics of compounds under challenging conditions, including, absorption from multiple electronic transitions, photoinduced products with unknown extinction coefficients, concentration dependence, photoinduced sensitizing intermediates, and speciation effects. Our work greatly improves our understanding of the degradation process of sulindac and will contribute to exposure assessments and treatment methodologies for this compound in impacted waters.

The presence of microcystins (MCs) in waterbodies requires a simple and reliable monitoring technique to characterize better their spatiotemporal distribution and ecological risks. An organic-diffusive gradients in thin films (o-DGT) passive sampler based on polyacrylamide diffusive gel and hydrophilic-lipophilic balance (HLB) binding gel was developed for MCs in water. The mass accumulation of three MCs (MC-LR, –RR, and -YR) was linear over 10 days (R2 ≥ 0.98). Sampling rates (2.68–3.22 mL d−1) and diffusion coefficients (0.90–1.08 × 10−6 cm2 s−1) of three MCs were obtained at 20 °C. Two different passive samplers, o-DGT and the Solid Phase Adsorption Toxin Tracking device (SPATT), were co-deployed to estimate MC levels at three lakes in California, USA. Measured total MC concentrations were up to 10.9 μg L−1, with MC-LR the primary variant at a measured maximum concentration of 2.74 μg L−1. Time-weighted average MC concentrations by o-DGT were lower than grab water samples, probably because grab sampling measures both dissolved and particulate phases (i.e., MCs in cyanobacteria). Passive water samplers by design can only measure dissolved-phase MCs, which are considerably less during the cyanobacteria-laden periods observed. Both o-DGT and grab samples gave comparable results for three MC variants at low levels of MCs, e.g.

With the growth of both the pharmaceutical industry and the human population and longevity, more drugs are used and processed each day. Inevitably, these pharmaceuticals enter wastewater through human excretion and improper disposal of leftovers. One such medication, diltiazem, a calcium channel blocker, is of importance due to its widespread consumption, and prevalence in aquatic environments. To study the sub-lethal effects of diltiazem on aquatic animals, we investigated its impacts no feeding behaviour, heart rate, respiration, growth, and reproduction of a bioindicator species, Daphnia magna. When exposed to environmentally relevant concentrations, D. magna increased their heart rate by 12% and oxygen consumption by 48%. However, exposure did not have any effects on thoracic limb movement frequency or peristalsis (i.e. feeding behaviour). Individuals exposed to diltiazem for a longer duration (16 days) showed a 44% decrease in lipid reserves and produced between 17 and 28% fewer neonates which were 10–12% larger. Our study demonstrated that exposure to diltiazem creates an energy imbalance in D. magna which could, in the long run, influence their populations.

The impacts of microplastics on aquatic ecosystems and biota are gaining attention globally. Although microplastics have been widely detected in biota, there currently are few standardized detection and identification methods. The present study developed a novel one-step digestion method which was evaluated with mussel and fish samples. This method employed nitric acid and hydrogen peroxide (HNO3 :H2 O2 = 4:1 by volume) as digestion reagents, which completely digested biota samples 0.05) were observed for all tested polymers. Fourier transform infrared spectral analyses demonstrated that the method did not degrade any of the polymers except for polyethylene terephthalate. The method was demonstrated with mussel and fish samples collected from the Pearl River delta, south China, and was able to recover microplastics effectively. Overall, the present method is time-saving and easy to operate, with low procedural cross-contamination. The properties of microplastics recovered by the present method remained largely intact, greatly benefiting subsequent qualitative and quantitative analyses. Environ Toxicol Chem 2019;38:1400-1408. © 2019 SETAC.

Perfluoroalkyl substances (PFASs) are known to be toxic, bioaccumulative, and persistent. However, exposure routes and toxic effects to humans are still widely unknown. Our objectives were to evaluate potential correlations between concentrations of PFASs in maternal plasma and infant cord blood with home characteristics and developmental effects, including wheezing. The concentrations of 17 PFASs were measured in plasma from prenatal women (n = 414), postnatal women (n = 247), and cord blood (n = 50) from a subset of participants in a population-based birth cohort in Winnipeg, Manitoba, Canada, using online solid phase extraction (SPE) with liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). Multiple linear regression and principal component analysis (PCA) were used to evaluate possible associations with PFAS concentrations. Surveys were used to collect information regarding maternal characteristics (e.g. age, parity, duration of breastfeeding), infant characteristics (e.g. birth weight, birth length, head circumference, gestational age, and incidence of recurrent wheezing), and home characteristics (e.g. home age,carpet coverage in the most used room, presence of new furniture, or recent home renovations). PFASs in plasma were associated with maternal characteristics but not home characteristics or early childhood wheezing. PFASs were not associated with developmental effects, with the exception that perfluoroundecanoic acid (PFUA) was negatively associated with birth weight. Further studies investigating the potential influences of PFUA on birth weight are warranted.

California Senate Bill 1422 requires the development of State-approved standardized methods for quantifying and characterizing microplastics in drinking water. Accordingly, we led an interlaboratory microplastic method evaluation study, with 22 participating laboratories from six countries, to evaluate the performance of widely used methods: sample extraction via filtering/sieving, optical microscopy, FTIR spectroscopy, and Raman spectroscopy. Three spiked samples of simulated clean water and a laboratory blank were sent to each laboratory with a prescribed standard operating procedure for particle extraction, quantification, and characterization. The samples contained known amounts of microparticles within four size fractions (1-20 μm, 20-212 μm, 212-500 μm,500 μm), four polymer types (PE, PS, PVC, and PET), and six colors (clear, white, green, blue, red, and orange). They also included false positives (natural hair, fibers, and shells) that may be mistaken for microplastics. Among laboratories, mean particle recovery using stereomicroscopy was 76% ± 10% (SE). For particles in the three largest size fractions, mean recovery was 92% ± 12% SD. On average, laboratory contamination from blank samples was 91 particles (± 141 SD). FTIR and Raman spectroscopy accurately identified microplastics by polymer type for 95% and 91% of particles analyzed, respectively. Per particle, FTIR spectroscopy required the longest time for analysis (12 min ± 9 SD). Participants demonstrated excellent recovery and chemical identification for particles greater than 50 μm in size, with opportunity for increased accuracy and precision through training and further method refinement. This work has informed methods and QA/QC for microplastics monitoring in drinking water in the State of California.

The use of recycled glass as a substrate for constructed wetlands was assessed through two studies. The first study examined the dissipation of atenolol, carbamazepine, and sulfamethoxazole in mesocosm-modeled wetlands using glass or limestone gravel as substrates, with or without cattails (Typha spp.). Following pseudo-first-order kinetics, atenolol dissipated the fastest from the water surface of the mesocosms (t

The application of the organic-diffusive gradients in thin films (o-DGT) passive sampling technique for the monitoring of per- and polyfluoroalkyl substances (PFAS) in the environment is still limited. Six common PFAS with different chain lengths were evaluated in water by o-DGT. Measured diffusion coefficients (D) in agarose and polyacrylamide diffusive gels ranged from 4.55–8.63 × 10−6 cm2 s−1 and 3.85–7.00 × 10−6 cm2 s−1 at 23 °C, respectively. Experimental sampling rates (Rs) for both agarose- and polyacrylamide-WAX sampler configurations were within 22% relative error of D-based Rs for four of the PFAS. Larger differences for perfluorobutanesulfonic acid (PFBS) and perfluoroundecanoic acid (PFUnDA) ranged from 36% to 56%. In general, in-situ Rs can be predicted using measured D-values for perfluorinated alkyl acids. The mass accumulation of six PFAS in two o-DGT configurations was linear over 21 days (R2 ≥ 0.97). Diffusion and uptake of o-DGT depended on the gel type and specific PFAS. Field demonstrations of o-DGT with WAX and HLB binding gels and polyacrylamide diffusive gels (not prone to biodegradation) found 0.3–19.5 ng L−1 of PFAS in rivers near industrial areas around Guangzhou and Foshan, China, with no apparent differences between the two co-deployed samplers. This study demonstrates that the configurations of o-DGT tested provide a cost-effective monitoring tool for measuring perfluorinated alkyl acids in aquatic systems, in particular the four PFAS for which reasonable correlations were observed.

The chemical composition of water-soluble organics in oil sands process-affected water (OSPW) is primarily composed of natural constituents of bitumen that are solubilized and concentrated during aqueous extraction of oil sands. OSPW organics are persistent and acutely toxic, and a leading remediation strategy is long-term ageing in end-pit lakes, despite limited data available on its photochemical fate. Here, direct photolysis of whole OSPW, or of its constituent fractions, was examined at environmentally relevant wavelengths (>290 nm) in bench-top studies. Changes in the chemical profiles of whole OSPW, acid- (AEO), and base-extractable organics (BEO) were characterized by liquid chromatography with ultra-high resolution mass spectrometry in negative (-) and positive (+) ionization modes. Following 18 d of irradiation, photolysis reduced the total ion intensity in all samples in both modes. The most photo-labile species included the O2-, O3-, O4-, O2S-, and O4S- chemical classes, which were depleted in whole OSPW by 93-100% after only 5 d. In positive mode, detected species were more recalcitrant than those detected in negative mode, with an average reduction across all heteroatomic classes of 75 ± 11.0% after 18 d. Estimated environmental half-lives for heteroatomic classes ranged from 57 d (O4S-) to 545 d (O3N+), with a greater recalcitrance for classes detected in positive mode compared to negative mode. Under field conditions in end-pit lakes, natural photolysis may be an important mechanism for effective OSPW remediation, and we suggest that future end-pit lakes be shallow to maximize light penetration and natural photolysis in ageing OSPW.

Contamination in the coastal zone is closely linked to urbanization and has become a global issue. The coastal aquatic environment is the terminal sink for many chemicals; however, little is known about the occurrence and variation among habitats as well as integrative toxicity for pesticides, i.e., fipronil, and its three major degradates (-desulfinyl, -sulfide, and -sulfone, fiproles hereafter) in sediments in urban coastlines. In the present study, we report results of a random stratified survey for fiproles in surficial sediments in five embayment habitats (strata) along the Southern California Bight (SCB), USA coastline. Fiproles were present in a small areal extent (6.8%) of the SCB embayment, and detected in 14 out of 174 stations with a total concentration of the four analytes ranging from 0.50 to 17.5 μg/kg dry weight. The area-weighted mean concentrations were 3.16 ± 3.37, 0.584 ± 0.558, 0.071 ± 0.103, and 0.005 ± 0.009 μg/kg in brackish estuaries, estuaries, bays, and marinas, respectively, with the results below the detection limits in ports. Fipronil sulfone had the greatest detection frequency (8.05%) and highest mean concentration (3.24 ± 3.36 μg/kg) among the four compounds. A screening-level deterministic risk assessment for invertebrates found that, region-wide, fiproles generally posed an insignificant to low acute risk to the amphipod Eohaustorius estuarius in 7.36% of the SCB embayment area. In addition, high risk to the midge Chironomus dilutus was found in 77.5% of the fiproles-detectable area in the brackish estuary stratum that is a part of the Los Angeles River. Fipronil sulfone was identified as the major contributor of these effects. The results of this study establish a baseline of occurrence and toxicity potential for fiproles in coastal sediments of southern California.

Some pharmaceutical conjugates can be excreted into wastewaters at levels rivalling those of the parent compounds; however, little is known about this potential reservoir of pharmaceuticals to aquatic systems. We evaluated the occurrence and distribution of four different classes of pharmaceuticals and their metabolite conjugates in a wastewater treatment plant over four months. Aqueous and suspended solids fractions of primary, mixed liquor, secondary, and final effluent, along with return activated sludge, and waste activated sludge were assessed. The only conjugate not found in the final effluent was acetaminophen sulfate. Moreover, thyroxine and thyroxine glucuronide were the only compounds quantified in the suspended solids in the final effluent. Propranolol, propranolol sulfate, thyroxine, and thyroxine glucuronide all had no significant decreases in concentration going through the wastewater treatment process, from primary to final effluent. However, there were significant decreases observed for acetaminophen (99.8%), sulfamethoxazole (71%), N-acetyl sulfamethoxazole (59%), and sulfamethoxazole glucuronide (79%). The mean (±SEM) mass loadings in the aqueous fraction of the final effluent for each compound ranged from 0.84 ± 0.2 g/d for thyroxine to 45.3 ± 4.2 g/d for acetaminophen. At least as much conjugate was released into receiving waters, if not more: 1.6 ± 0.2 g/d for thyroxine glucuronide to 18.5 ± 4.5 g/d for sulfamethoxazole glucuronide, and 61.2 ± 9.6 g/d for N-acetyl sulfamethoxazole. Additionally, the mean loading of thyroxine was 0.29 ± 0.025 g/day and thyroxine glucuronide 1.8 ± 0.59 g/day in the suspended solids. This equates to 26% of total thyroxine and 53% of total thyroxine glucuronide associated with suspended particulate matter that reaches receiving waters. This study reflects the importance of including phase II conjugates in assessing overall compound load of pharmaceutical discharge from wastewaters, and also that substantial amounts of such contaminants are associated with wastewater solids when drugs are in the pg/L to μg/L range.

Although many studies have addressed the ability of subsurface filtration systems to remove emerging contaminants from wastewater at micro- and mesocosm-scale, little is known about their performance on full-scale wastewater treatment facilities. To understand better how effective these systems can be for municipal wastewater polishing, we assessed the ability of a full-scale lagoon-subsurface filter system located in Dunnottar, Manitoba, Canada, to attenuate regulatory wastewater parameters, nutrients, pharmaceuticals, and toxicity over the course of the discharge periods in 2015 and 2016 (June–October). Pharmaceuticals included β-blockers, anticonvulsant drugs, and macrolide and sulfonamide antibiotics. Out of six consistently detected pharmaceuticals, four were efficiently removed through lagoon treatment (e.g. clarithromycin, metoprolol, propranolol), while two persisted to a certain extent (e.g. carbamazepine, sulfamethoxazole), even after subsurface filtration. Attenuation was observed for nutrients with averages of 40% and 60% for ammonia and total phosphorus respectively within the filter, consistent with previous pilot-scale studies at this facility. Compliance with regulations for conventional wastewater parameters at the effluent was observed, as well as reduced acute toxicity (as determined by Microtox®) from the primary lagoon to the effluent, and little likelihood of acute toxicity in receiving waters. Our results suggest that first, the full-scale system has an overall similar performance when compared to the previously studied pilot-scale system; second, there was no apparent effect of acclimation on the attenuation of studied contaminants or toxicity; and finally, the concentrations of contaminants do not appear to pose an acute risk for aquatic species in the receiving environment.

The organic-diffusive gradients in thin-films (o-DGT) technique has emerged as a promising aquatic passive sampler that addresses many of the challenges associated with current sampling tools used for measurement of polar organic contaminants. This study represents the first comprehensive field evaluation of the o-DGT in natural surface waters, across a wide suite of polar pharmaceuticals and pesticides. We explore the utility and limitations of o-DGT as a quantitative measurement tool compared to grab sampling and the polar organic chemical integrative sampler (POCIS) across four connected agricultural and wastewater-influenced freshwater systems spanning 600 km from the U.S. border to northern Manitoba, Canada. Overall, the suite of analytes detected with o-DGT and POCIS was similar. Concentrations in water estimated using o-DGT were greater than concentrations estimated from POCIS in 71 of 80 paired observations, and on average, the estimates from o-DGT were 2.3-fold greater than estimates from POCIS. Grab sample concentrations suggested that the systematic underestimation with POCIS were largely a result of sampling rate variation related to flow rate and boundary-layer effects, an issue reported consistently in the POCIS literature. These comprehensive measurements in an agriculturally influenced fast-flowing river, long-term sampling (>40 days) in a large dilute lake system, deployments in wastewaters, and under ice at near-freezing temperatures represent effective stress testing of o-DGT under representative and challenging conditions. Overall, its strong performance and improved accuracy over POCIS supports its use as a robust, quantitative, and sensitive measurement tool for polar organic chemicals in aquatic systems.

The Red River originates in the U.S., drains into Lake Winnipeg, and is a significant pathway for nutrients. We investigate its role as a source for pesticides, pharmaceuticals, per- and polyfluoroalkyl substances (PFASs) substances (PFASs), and microbes bearing antibiotic resistance genes (ARGs). We delineate agricultural, urban, and rural land-use for organic contaminants to determine the extent of chemical transboundary riverine fluxes, and characterize levels and trends of organic contaminants and ARGs between spring and fall 2014 and 2015. The herbicide atrazine peaked at over 500 ng/L (14-day time weighted average) near the border, indicating that the U.S. represents the major source into Canada from the Red River. Neonicotinoid insecticides had relatively constant concentrations, suggesting more widespread agricultural use in both countries. Pesticide concentrations were greatest post-application in June and July. Mass loadings of pesticides over the sampling periods, from the river to Lake Winnipeg, ranged from approximately 800 kg of atrazine, to 120 kg of thiamethoxam and clothianidin, to 40 kg of imidacloprid. Exposure distributions for atrazine exceeded benchmark water quality guidelines for protection of aquatic life (0.2% probability of exceeding chronic benchmark) with no exceedances for neonicotinoids. Seven pharmaceuticals were detected, mostly at low ng/L levels downstream of the City of Winnipeg wastewater treatment plant. Carbamazepine, the only pharmaceutical detected consistently at all sites, contributed on average 20 kg each year into Lake Winnipeg. While minor inputs were observed all along the river, city inputs represented the greatest source of pharmaceuticals to the river. Both PFASs and ARGs were observed consistently and ubiquitously, indicative of an anthropogenically influenced system with no indications of any single point-source signature. While transboundary flux from the U.S. was an important source of pesticides to the Red River, especially for atrazine, observed concentrations of all measured contaminants suggest that known aquatic toxicological risk is minimal.

The treatment performance and bacterial community structure of conventional activated sludge and aerobic granules exposed to antibiotic sulfamethoxazole (SMX) was studied. For three months, two sets of sequencing batch reactors inoculated with conventional and granular biomass were fed with a synthetic municipal wastewater containing 2 μg/L SMX. The presence of SMX had no significant impacts on treatment performance of the reactors as well as stability of the granules. Results confirmed different bacterial community structure of flocs and granules. During the operation, variations in bacterial community structure of suspended and granular sludge were observed in all reactors. The variations in bacterial community composition due to the exposure to 2 μg/L SMX were found after two months in both suspended and granular biomass. Nitrosomonas, Pseudomonas, and Acinetobacter were detected as the genes capable of degrading SMX in both biomass types. Also, Rikenellaceae, Oscillospira, Rhodocyclaceae, Zoogloea, and Shewanella varied in abundance over the operation time. Rikenellaceae and Oscillospira were vulnerable to SMX and decreased in abundance the operation time; while Rhodocyclaceae, Zoogloea, Shewanella, and Aeromonas were found as SMX resistance genes.

Recent literature has demonstrated the utility of the organic-diffusive gradients in thin films (o-DGT) device as an effective passive sampler for polar organics in aquatic environments. Here, a new configuration comprising a polyacrylamide diffusive gel and Sepra™ ZT sorbent was developed and calibrated under multiple pH conditions. Linear uptake (r2 > 0.9) was observed at pH ≈ 5 for a suite of 31 pharmaceuticals and pesticides over 25 days, suitable for typical passive sampler deployments. At pH ≈ 8.5, linear uptake (r2 > 0.9) was observed for many of the same compounds. Comparisons of the uptake rates between the two pH experiments generally agreed (14% average relative error), with only 6 compounds exhibiting marked reduction with pH (e.g. sulfonamide antibiotics). These discrepancies may be explained by changes in analyte-sorbent interaction (H-bonding) due to speciation changes at varying pH. Samplers performed well in field evaluations conducted in an impacted river system, showing close agreement with the previously validated agarose/HLB o-DGT configuration deployed simultaneously. This work illustrates that polyacrylamide diffusive gels are a more robust and resistant outer-membrane material compared to agarose used in earlier o-DGT configurations. Sepra™ ZT binding gels served as an effective binding resin, offering a cost effective and commercially available sorbent.

Occurrence of microplastics (MPs) in the environment has attracted great attention as it has become a global concern. This review aims to systematically demonstrate the role of marine microplastic as a novel medium for environmental partitioning of chemicals in the ocean, which can cause toxic effects in the ecological environment. This review assimilated and analyzed available data published between 1972 and 2017 on the interaction between MPs and selected chemicals. Firstly, the review analyzes the occurrence of chemicals in MPs and outlines their distribution patterns. Then possible mechanisms of the interaction between MPs and organic chemicals and potential controlling factors were critically studied. Finally, the hazards of MPs and affiliated organic chemicals to marine organisms were shortly summarized.

An increasing number of reports have been published concerning microplastic (MP) pollution in aquatic environments. Methods used in these studies continue to be updated and lack standardization, so that an up-to-date review pertaining methods for MP research is needed. This critical review examines the analytical methods, including sampling, identification, and quantitation, for MP research. Samples are generally collected from water, sediment, and biota gastrointestinal tract. Manta nets or trawls are prevalently used in surface water sampling, while direct shoveling or box-corer grab are commonly applied in sediment sampling. Microplastics in biota are generally obtained by dissecting organisms and separating livers, gills, and guts. Density separation is frequently chosen to separate MPs from sample matrices. Chemical digestion can dissolve other organic materials and isolate MPs for further identification. Visual sorting should be combined with chemical composition analysis to better identify the polymer type. Pyrolysis or thermal decomposition gas chromatography coupled with mass spectrometry, Fourier transform infrared spectroscopy, and Raman spectroscopy are currently the main technologies for MP identification. Units prevalently used to express MP abundance in water, sediment, and biota are “particles per m3,” “particles per m2,” and “particles per individual,” respectively. As MP abundances often varied with the methods used, we recommend that analytical protocols of MPs should better be standardized and optimized. Despite the important progress in analysis of MPs, detection technologies for identifying nano-sized plastic particles are still lacking, and therefore should be developed swiftly.

This study investigates the removal of the antibiotic sulfamethoxazole (SMX) in two sets of anoxic/anaerobic/oxic sequencing batch reactors inoculated with either suspended or granular activated sludge. Continuously, for three months, 2 μg/L SMX was spiked into the reactor feeds in a synthetic municipal wastewater with COD, total nitrogen (TN) and total phosphorous (TP) of 400, 43 and 7 mg/L, respectively. The presence of SMX had no significant impact on treatment performance of the suspended and granular biomass. After 12 h of hydraulic retention time, SMX removal efficiencies of 84 and 73% were obtained for the granular and suspended biomass, respectively. Mixing without aeration did not remove SMX, confirming the insignificance of SMX removal via sorption. The pseudo-first order SMX removal rate constants in the granular and suspended biomass were 2.25 ± 0.30 and 1.34 ± 0.39 L/gVSS·d, respectively. The results suggest that granules with advantages such as elevated biomass retention and greater biomass concentration could be effective for the removal of this class of antibiotics.

Background and Purpose Systemically delivered statins can blunt airway inflammation in ovalbumin-challenged mice; however, in asthma clinical trials the beneficial effects of introducing oral statins are not compelling. We aim to reconcile this discrepancy using a clinically relevant murine model of allergic asthma, and by including a prophylactic study arm. Experimental Approach Adult mice were: 1) challenged with house dust mite (HDM) alone or with subcutaneous (s.c.) simvastatin for two weeks; or 2) also treated with simvastatin for one week prior to HDM challenge. We assayed lung function, inflammatory cell influx and cytokine profile, goblet cell abundance, and simvastatin concentration in serum, lung lavage and tissue. Key Results Ultrahigh performance liquid chromatography-tandem mass spectrometry revealed that pharmacologically active simvastatin reached peak serum concentration after 8h, but declined rapidly. Prophylactic treatment doubled peak serum simvastatin and repeated s.c. delivery established stable serum levels, but simvastatin was undetectable in the lungs. Both simvastatin treatment arms suppressed indices of HDM-induced airway inflammation and goblet cell hyperplasia, but this was significantly greater with prophylactic therapy, in particular to inhibit neutrophil and eosinophil influx, and cytokine accumulation. Conversely, neither acute nor prophylactic delivery of simvastatin prevented HDM challenge-induced airway hyperreactivity. Conclusion and Implications Systemically administered simvastatin accumulates in the blood, but not in lung tissues, and reduces leukocyte influx and associated lung inflammation. Prophylactic therapy has the greatest anti-inflammatory effects, but as observed in human clinical trials, systemic simvastatin therapy does not prevent allergic airway hyperreactivity.

Gemfibrozil, a common lipid regulator, enters aquatic environments through treated municipal wastewater effluent that fails to remove it completely from effluent streams. When exposed to gemfibrozil concentrations of 50, 500, 5,000, and 50,000 ng L−1, Daphnia magna showed increased lipid reserves by 14–21% (significant at 500 ng L−1), increased length by 9–13% (significant at 50 ng L−1), increased mass by 6–13% (significant at 50 ng L−1) and increased neonate production by 57–74% (significant at 50 ng L−1). Gemfibrozil-exposed Daphnia held under conditions where food availability was low, grew and reproduced as well as those in the control. Taken together, these results suggest that gemfibrozil exposure within environmentally relevant concentration ranges is not toxic to Daphnia magna but has the potential to be beneficial to the species under these conditions.

In the present study, we report the freezer storage stability of pharmaceuticals and pesticides for the organic-diffusive gradients in thin-films (o-DGT) passive sampler and the polar organic chemical integrative sampler (POCIS). The average change on o-DGT after approximately 18 mo was 9 ± 9% across 30 compounds. For POCIS, the average change after approximately 6 yr was 14 ± 14% for the same compounds. Our data suggest that analytes stored on these samplers are stable and appropriate for archival purposes. Environ Toxicol Chem 2018;37:762-767. © 2017 SETAC.

A solids extraction method, using sonication in combination with weak anion exchange solid phase extraction, was created to extract thyroxine (T4) and thyroxine-O-β- d -glucuronide (T4-Glc) simultaneously from wastewaters and sludges, and to quantify these compounds via reversed-phase ultra-high performance liquid chromatography-tandem mass spectrometry. The method limits of quantification were all in the low ng/g (dry weight solids) range for both T4 and T4-Glc: 2.13 and 2.63 ng/g respectively in primary wastewater, 4.3 and 28.3 ng/g for primary suspended solids, for 1.1 and 3.7 ng/g for return activated sludge. Precision for measurements of T4 and T4-Glc were 2.6 and 6.5% (intraday) and 9.6 and 5.7% (interday) respectively, while linearity was 0.9967 and 0.9943 respectively. Overall recoveries for T4 and T4-Glc in primary suspended solids were 94% and 95%, and 86 and 101% in primary wastewater, respectively. Extraction efficiency tests using primary sludge determined that one methanol aliquot was sufficient during the extraction process as opposed to 2 or 3 aliquots. Mass loadings at the North Main Wastewater Treatment Plant in Winnipeg, Canada showed 316%, 714%, and 714% greater T4-Glc than T4 associated with the suspended solids of the primary, secondary, and final effluent respectively, yet 765% more T4 than T4-Glc associated with the solids of the mixed liquor. Moreover, 26% of T4 and 49% of T4-Glc were associated with the suspended solids during the treatment process. This method demonstrates the need to assess accurately both metabolite conjugates of contaminants of emerging concern, as well as the sorbed levels of particle-reactive analytes such as T4 in the aquatic environment.

The fate of selected common pharmaceuticals and four of their major conjugates in wastewater batch bioreactors was evaluated to determine how treatment plant parameters such as addition of air, and the presence of waste activated sludge (WAS) could influence the removal of parent compounds and conjugates. Under a realistic hydraulic residence time (HRT) for each treatment sub-process of approximately 2 h, acetaminophen and its sulfate metabolite were both rapidly degraded (99%). Propranolol was sulfated and concurrently removed. Deconjugation of N-acetylsulfamethoxazole and sulfamethoxazole-glucuronide contributed to increases of the parent sulfamethoxazole. Thyroxine was resistant to degradation, while thyroxine-glucuronide was rapidly deconjugated (90% in2 h). In the absence of WAS, sorption to suspended solids was another major removal mechanism for acetaminophen, propranolol, sulfamethoxazole, and thyroxine. However, with WAS, concentrations associated with suspended solids decreased for all analytes within 24 h. These results indicate that both conjugation and back-transformation are compound-specific and dependent on parameters such as HRT, addition of microbial content, and suspended solids levels. Therefore, conjugation-deconjugation processes may strongly influence the speciation of pharmaceuticals and their fate in wastewater treatment plant effluents.

Passive sampling techniques have been widely used to determine the dissolved concentration profiles of hydrophobic organic compounds (HOCs) in sediment porewater. However, the effects of having a protection for the passive sampler on profiling HOCs concentrations in sediment porewater, especially in deep sediment, have remained unclear. To address this issue, low density polyethylene passive samplers with and without protectors, which consisted of glass fiber filter and porous stainless steel shield, were simultaneously deployed in sediment of the Dongjiang River, South China. The results showed that the protectors retarded the dissipation of performance reference compounds (PRCs) from the sampler by a factor of 2–9. The protectors seemed to exert a negligible effect on the measured concentrations of PAHs, BDE-47, and BDE-99 in surficial sediment porewater (0–14 cm depth) from both samplers. However, the sediment porewater concentration profiles of PAHs and BDE-47 from the sampler with protectors were in agreement with those normalized by dry weight in deep sediment (16–34 cm depth), indicating that a diffusion layer established by the protectors may minimize the probability of local depletion of the target analytes in deep sediment. In addition, the log Koc values of PAHs, BDE-47, and BDE-99 exhibited a slight increasing trend with sediment depth. This finding suggested that in situ passive sampling techniques could be a feasible tool in determining the site-specific log Koc values of HOCs at different sediment depths.

Aerated lagoons, typically used by small communities, often provide limited removal of wastewater nutrients. Given increasingly stringent wastewater standards, it is imperative that effective, but economical and easy-to-operate, treatment technologies be developed. The Submerged Attached Growth Reactor (SAGR®) is a treatment process developed to perform nitrification near freezing temperatures. Previous tests on full-scale installations have shown that SAGR could consistently remove ammonia to below current Canadian standards and provide additional total suspended solids and biochemical oxygen demand removal. In this study, we evaluated removal of polar chemicals of emerging concern (CECs), including pharmaceuticals, personal care products, and pesticides, at SAGR installations in two Manitoba First Nations communities (MCN and LPFN) under cold winter conditions. Both showed some removal of diclofenac, naproxen, clarithromycin, metoprolol, and trimethoprim, likely by biotransformation. Average naproxen removal was 21% (2.53 × 103 ng L−1) in MCN and 64% (1.58 × 103 ng L−1) in LPFN. Atenolol was well-removed by SAGR, by 80% on average (range of 64%–94%). Clarithromycin, metoprolol, and trimethoprim removal was similar within and between systems, ranging from 54% to 76% (30.8–3.07 × 102 ng L−1 removed). Carbamazepine was detected in nearly all samples, but was not well-removed, consistent with other treatment studies. Overall, results showed that SAGR technology could moderately remove CECs, while providing the designed treatment performance for other parameters. This work will help to improve our understanding of wastewater treatment in small and/or remote communities with limited infrastructure and challenging cold-weather conditions.

Effective removal of organic contaminants in wastewater effluent poses a challenge to small communities worldwide, particularly in the Arctic due to infrastructure challenges and harsh climates. To understand better the efficacy of current treatment options and risks posed by pharmaceuticals and pesticides on receiving waters in the Arctic, four representative human communities in Nunavut, Canada were evaluated. Per- and polyfluorinated alkyl substances (PFASs) were also investigated in one community. These communities have treatment ranging from primary lagoons, engineered wetlands, and natural lakes. Pharmaceuticals and pesticides were measured using the organic diffusive gradients in thin film (o-DGT) passive sampler in summer 2018. Of the 34 compounds studied, seven pharmaceuticals were found at least once: atenolol, carbamazepine, metoprolol, naproxen, sulfapyridine, sulfamethoxazole, and trimethoprim. With the exception of 5210 ng naproxen/L in Iqaluit, most receiving waters showed negligible amounts of contamination. Iqaluit had the poorest overall system performance while Baker Lake had the best. Measured pharmaceutical concentrations do not appear to pose a significant acute hazard to receiving waters at this time, based on known toxicological endpoints. PFAS concentrations were found to be over 100-fold greater in Cambridge Bay wastewater than previously reported Arctic seawater. Results suggest that wastewater may be an important point source of PFASs in Arctic communities. The o-DGT passive samplers performed well in marine Arctic settings. We recommend further testing of wastewater efficiencies in Arctic communities along with evaluations of seasonal variations.

Hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBPA) are legacy brominated flame retardants which are still produced and used in China. In this study, 187 surface soils from the Pearl River Delta (PRD) urban conurbation in China were collected, and the effects of urban conurbation development on the concentrations, distributions and human exposure risk of HBCDs and TBBPA were investigated. The concentration ranges of Σ3HBCD (sum of α-, β-, and γ-HBCD) and TBBPA in soil were below the limit of quantification (

Estrogenically active compounds (EACs) in surface waters can disrupt the endocrine system of biota, raising concern for aquatic species. Concentrations of EACs are generally higher in effluent-dominated aquatic systems, such as California's Santa Ana River (SAR). Addressing estrogenicity of effluent-dominated waters is increasingly important due to both increasing urbanization and climate change. To this end, water samples were collected from multiple sites downstream of wastewater treatment plants (WWTPs) and intermittent points along the SAR during 2018–2019 and cell-based bioassays were used to determine estrogen receptor activity. During baseflow conditions, the highest estradiol equivalencies (EEQs) from all SAR water between summer (August and September) and fall (November) sampling events in 2018 were from Yorba Linda (EEQ = 1.36 ± 0.38 ng/L) and Prado (1.14 ± 0.13 ng/L), respectively. Water extracts in January 2019 following a major rainfall generally had higher EEQs with the highest EEQ of 10.0 ± 0.69 ng/L observed at Yorba Linda. During low flow conditions in November 2018, male Japanese medaka (Oryzias latipes) fish were exposed to SAR water to compare to cell bioassay responses and targeted analytical chemistry for 5 steroidal estrogens. Chemical-based EEQ correlations with in vitro EEQs were statistically significant. However, vitellogenin (vtg) mRNA expression in the livers of medaka exposed to SAR water was not significantly different compared to controls. These results indicate that seasonal variation and surface water runoff events influence estrogenic activity in the SAR and may induce estrogenic effects to native fish populations in wastewater-dominated streams in general.

Recent data suggests there are non-trivial amounts of human pharmaceutical conjugates potentially entering environmental surface waters. These compounds could contribute to eliciting toxic effects on aquatic biota either directly or indirectly, via de-conjugation. The need for developing a single method for quantifying both parents and conjugates is necessary. Propranolol (PRO), sulfamethoxazole (SMX), and their respective major conjugates 4-OH-propranolol sulfate (PRO-Sul) and sulfamethoxazole-β-glucuronide (SMX-Glc) were successfully simultaneously extracted through weak anion exchange solid phase extraction cartridges from primary and secondary clarification wastewaters from the North End Winnipeg Water Pollution Treatment Plant in Winnipeg, Canada. Subsequent separation and quantification were achieved by reversed-phase C18 chromatography coupled to positive electrospray ionisation tandem mass spectrometry. Linearity for all compounds throughout the 7-point calibration range was >0.99. Recovery RSD ranges across all matrices for PRO, SMX, PRO-Sul, and SMX-Glc were 2.1–13.2%, 2.3–10.2%, 9.8–19.2%, and 2.0–10.3% respectively. Primary and secondary filtrates respectively showed a significant increase of PRO from 0.039 to 0.045 μg/L; a significant decrease for SMX from 1.56 to 0.58 μg/L; significant decrease of PRO-Sul from 0.050 to 0.020 μg/L; and a significant decrease of SMX-Glc from 0.41 to 0.019 μg/L. These observations indicate that there was removal of all compounds, except for PRO, from the aqueous phase occurring at some point between the stages of treatment. To our knowledge, this is first study that simultaneously separated and quantified two different classes of parent compounds and two different kinds of human metabolite conjugates (glucuronide and sulfate) from a major urban wastewater treatment plant.

Mass transfer of hydrophobic organic contaminants (HOCs) across the air-water interface is an important geochemical process controlling the fate and transport of HOCs at the regional and global scales. However, few studies have characterized concentration or fugacity profiles of HOCs near both sides of the air-water interface, which is the driving force for the inter-compartmental mass transfer of HOCs. Herein, we introduce a novel passive sampling device which is capable of measuring concentration (and therefore fugacity) gradients of HOCs across the air-water interface. Laboratory studies indicated that the escaping fugacity values of polycyclic aromatic hydrocarbons (PAHs) from water to air were negatively correlated to their volatilization half-lives. Results for field deployment were consistent between the passive sampler and an active method, i.e., a combination of grab sampling and liquid-liquid extraction. In general, the fugacity profiles of detected PAHs were indicative of an accumulation mechanism in the surface microlayer of the study regions (Haizhu Lake and Hailing Bay of Guangdong Province, China), while p,p'-DDD tended to volatilize from water to the atmosphere in Hailing Bay. Furthermore, the fugacity profiles of the target analytes increased towards the air-water interface, reflecting the complexity of environmental behavior of the target analytes near the air-water interface. Overall, the passive sampling device provides a novel means to better characterize the air-water diffusive transfer of HOCs, facilitating the understanding of the global cycling of HOCs.

A unique configuration of the diffusive gradients in thin films sampler for polar organics (o-DGT) without a poly(ether sulfone) membrane was developed, calibrated, and field-evaluated. Diffusion coefficients (D) through agarose diffusive gels ranged from (1.02 to 4.74) × 10–6 cm2/s for 34 pharmaceuticals and pesticides at 5, 13, and 23 °C. Analyte-specific diffusion–temperature plots produced linear (r2 > 0.85) empirical relationships whereby D could be estimated at any environmentally relevant temperature (i.e., matched to in situ water conditions). Linear uptake for all analytes was observed in a static renewal calibration experiment over 25 days except for three macrolide antibiotics, which reached saturation at 300 ng (≈15 d). Experimental sampling rates ranged from 8.8 to 16.1 mL/d and were successfully estimated with measured and modeled D within 19% and 30% average relative error, respectively. Under slow flowing (2.4 cm/s) and static conditions, the in situ diffusive boundary layer (DBL) thicknes...

Although passive sampling is widely accepted as an excellent tool for environmental monitoring, their integration with suspect or non-targeted screening by high-resolution mass spectrometry has been limited. This study describes the application of the organic-diffusive gradients in thin-films (o-DGT) passive sampler as a tool for accurate measurement of both targeted and suspect polar organic contaminants (primarily pharmaceuticals) in wastewater. First, performance of o-DGT was assessed alongside the polar organic chemical integrative sampler (POCIS) and active sampling at two wastewater treatment facilities using targeted analyses. Overall, water concentrations measured by o-DGT, POCIS, and 24-hr integrative active samples were in good agreement with each other. There were exceptions, including a systematic difference between o-DGT and POCIS at certain sites that we propose was a result of site-specific conditions and a difference in sampling rates between the two techniques. The second component of this work involved suspect screening of the o-DGT extracts using high-resolution, high mass accuracy quadrupole time-of-flight mass spectrometry (QTOF). Lamotrigine, venlafaxine, and des-methylvenlafaxine were three suspect compounds identified and selected as proof-of-concept case studies to determine the feasibility and accuracy of o-DGT for estimating water concentrations based upon predicted sampling rates using a previously validated o-DGT diffusion model. Semi-quantification of the suspect compounds was conducting using an average surrogate response factor based on the suite of compounds measured by the targeted analyses. This, combined with the modelled sampling rates provided time-weighted average wastewater concentrations of the identified suspects within a factor of 2 of the true value, confirmed by isotope dilution with mass labelled internal surrogates. To the knowledge of the authors, this work is the first to demonstrate the utility of the o-DGT passive sampler as a potential environmental screening tool that can be integrated into the rapidly advancing field of non-targeted high resolution mass spectrometry.

Organophosphate flame retardants (OPFRs) have been increasingly produced and consumed since the gradual phase-out of polybrominated diphenyl ethers. Primitive recycling of e-waste can be a significant input source of OPFRs to the environment. Thermal treatment and open burning of typical e-wastes were conducted in a closed chamber to examine the emissions and the size distribution patterns of particle-bound OPFRs from these processes. The sum emission factors of OPFRs were 3.70 × 104–3.65 × 105 ng g−1 by thermal treatment and 5.22 × 103–9.27 × 104 ng g−1 by open burning. The output-input mass ratios of OPFRs for plastic casings were 0.030–116 and 0.012–7.1 by thermal treatment and open burning, respectively, and were 0.11–40 and 0.0014–6.7 for printed circuit boards. The size distribution patterns of OPFRs were characterized by one unimodal peak (0.56–1.0 μm) for thermal treatment and bimodal peaks (0.56–1.0 or 1.0–1.8 and 10–18 μm) for open burning. Particle-bound OPFRs appeared to form in affiliation with particles rather than by adsorption or deposition from the gaseous phase to particulate organic matter. With increasing amounts of OPFRs used in a variety of consumer products, the emissions of OPFRs to the environment are expected to increase continuously in the future.

Thiamethoxam is a neonicotinoid insecticide that can reach wetlands in agro-ecosystems through runoff. The fate and effects of thiamethoxam on non-target organisms in shallow wetland ecosystems have not been well characterized. To this end, a mesocosm study was conducted with a focus on characterizing zooplankton community responses. A single pulse application of thiamethoxam (0, 25, 50, 100, 250, and 500 μg/L; n = 3) was applied to experimental systems and monitored for 8 weeks. The mean half-life of thiamethoxam among the different treatments was 3.7 days in the water column with concentrations of0.8 μg/L in the majority of mesocosms by 56 days. Principal response curve analysis did not show any significant concentration-dependent differences in the zooplankton community among treatments over the course of the study. The minimum detectable difference (MDD%) values for abundance of potentially sensitive arthropod taxa (nauplius larvae, cyclopoid copepods) allowed the detections from controls as low as 42 and 59% effect, respectively. The MDD% values for total abundance of zooplankton (including the potentially less sensitive taxonomic group of Rotifera) allowed the detection from controls as low as 41% effect. There were no statistically significant differences in zooplankton abundance or diversity between control and treated mesocosms at the end of the study. There were also no statistically significant differences for individual taxa that were sustained between sampling points, or manifested as a concentration-response. We conclude that acute exposure to thiamethoxam at environmentally relevant concentrations (typically ng/L) likely does not represent a significant adverse ecological risk to wetland zooplankton community abundance and structure.

Plastic waste is ubiquitously found in the terrestrial environment. However, little attention has been paid to the sources and environmental fate of terrestrial microplastics (MPs). Given that the terrestrial environment is home to the human race, it is essential to understand the occurrence, fate, and effects of MPs in the terrestrial environment. In addition, terrestrial MPs are a nonnegligible input of MP pollution to the oceans. This chapter provides an overview of the sources, distribution, and biological effects of terrestrial MPs and further illustrates their contribution to marine MP pollution. Because of the scarcity of literature data on MPs in the terrestrial environment, this chapter focuses on plastic particles in soil, terrestrial biota, and sewage sludge. Agricultural application of plastic products and general disposal by the general population lead to the widespread occurrence of plastic wastes in soil. Sewage sludge is also an important contributor of MPs in soil. MPs in the terrestrial environment may also act as a vector for transporting chemical contaminants such as metals (e.g., Zn) and organic pollutants (e.g., polycyclic aromatic hydrocarbons and polychlorinated biphenyl) within the terrestrial ecosystem and into the aquatic environment. Further studies are urgently needed to investigate the spatial distribution, fate, and biological effects of MPs in soil, biota, and other terrestrial matrices.

The ability of a sub-surface treatment filtration system to remove nutrients, thirty-nine organic contaminants, metals, and antibiotic resistant gene (ARG)-bearing organisms, and to attenuate acute toxicity of wastewater lagoon effluents, was assessed. Significant removal was observed for nutrients between the conventional primary and secondary sewage lagoons, with further average attenuation of 59% and 50% of ammonia and total phosphorus (TP), respectively, within the filter. Effluent concentrations of ammonia ranged from 0.4 to 2.6 mg/L and concentrations of TP from 1 to 4.1 mg/L, with decreasing acute toxicity from primary to secondary lagoons, and no toxicity observed in the filtration system based on Microtox ® assays. Most organic micropollutants were also efficiently removed between the primary and secondary lagoons (e.g., up to 98% for atenolol). However, in general, little attenuation occurred within the filter for estrogenic compounds (e.g., 17α-ethinylestradiol); β-blockers (e.g., metoprolol); antidepressants (e.g., fluoxetine-Prozac); antibacterial agents (e.g., triclosan), non-steroidal anti-inflammatory drugs (e.g., diclofenac); lipid regulators (e.g., clofibric acid); and macrolide (e.g., clarithromycin) and sulfonamide (e.g., sulfamethazine) antibiotics; or metals (Cr, Cu, Fe, Mn, Ni, and Zn). This lack of removal was likely due to a minimal hydraulic residence time within the filter (∼6 h) under current operating conditions. The lagoon treatment system effectively removed ∼99% of sulfonamide resistant bacteria, but the filter both reduced tetracycline-resistant bacteria (∼58%) in wastewater and harbored them in the biofilms, as relative abundances of sul and tet genes were greatest there. The filter also harbored nitrifying and denitrifying bacteria, respectively, contributing to N removal. These results suggest that the constructed sub-surface treatment filtration system can provide a low-cost, low-maintenance, and effective means to reduce nutrient loading and improve microbial community structure and function.

Environmental fate processes of neonicotinoid insecticides are of significant interest, given the serious threats these chemicals can pose to nontarget organisms such as pollinators (e.g., bees). Direct photolysis was investigated using a laboratory photoreactor approximating full-spectrum sunlight to predict the aquatic fate of neonicotinoids. Quantum yields (ϕc) were 0.019 ± 0.001, 0.013 ± 0.001, 0.0092 ± 0.0005, 0.0022 ± 0.0003, and 0.0013 ± 0.0002 for thiamethoxam, clothianidin, imidacloprid, acetamiprid, and thiacloprid, respectively. On the basis of these values, estimated half-lives were 0.2–1.5 days for different seasons in surface waters at temperate latitudes for thiamethoxam, consistent with the 0.98 day half-life observed experimentally outdoors at Winnipeg, Manitoba, Canada (50°N), for thiamethoxam in summer. Light attenuation through shallow clear surface waters (e.g., by natural organic matter) indicated that photolysis of thiamethoxam at depths greater than 8 cm was negligible, which may h...

A probabilistic ecological risk assessment was conducted for the transformation products (TPs) of 3 β-blockers (atenolol, metoprolol, and propranolol) and 5 selective serotonin reuptake inhibitors (SSRIs; citalopram, fluoxetine, fluvoxamine, paroxetine, and sertraline) to assess potential threats to aquatic organisms in effluent-dominated surface waters. To this end, the pharmacokinetic literature, the University of Minnesota's Biocatalysis/Biodegradation Database Pathway Prediction System aerobic microbial degradation software, and photolysis literature pertaining to β-blockers and SSRIs were used to determine their most likely TPs formed via human metabolism, aerobic biodegradation, and photolysis, respectively. Monitoring data from North American and European surface waters receiving human wastewater inputs were the basis of the exposure characterizations of the parent compounds and the TPs, where available. In most cases, where monitoring data for TPs did not exist, we assumed a conservative 1:1 parent-to-TP production ratio (i.e., 100% of parent converted). The US Environmental Protection Agency (USEPA)'s EPISuite and ECOSAR v1.11 software were used to estimate acute and chronic toxicities to aquatic organisms. Hazard quotients, which were calculated using the 95(th) percentile of the exposure distributions, ranged from 10(-11) to 10(-3) (i.e., all significantly less than 1). Based on these results, the TPs of interest would be expected to pose little to no environmental risk in surface waters receiving wastewater inputs. Overall, we recommend developing analytical methods that can isolate and quantify human metabolites and TPs at environmentally relevant concentrations to confirm these predictions. Further, we recommend identifying the major species of TPs from classes of pharmaceuticals that could elicit toxic effects via specific modes of action (e.g., norfluoxetine via the serotonin 5-hydroxytryptamine [5-HT]1A receptors) and conducting aquatic toxicity tests to confirm these findings. To our knowledge, this is the first quantitative probabilistic ecotoxicological assessment of all of the predicted and probable TPs of these pharmaceuticals, and our approach provides a framework for future such studies with other compound classes as data become available.

Analytical techniques are necessary to facilitate the accurate identification and quantification of human pharmaceutical conjugates, which have the potential to comprise a significant hidden environmental load potentially rivaling those of the parent compounds. This review reflects the current trends in the processing and analysis of human pharmaceutical conjugates. The primary focus was to outline trends in environmental analytical chemistry. However, techniques involved in analysis of bile acid conjugates associated with biological fluids were included, as these provided insight into steroid conjugate analysis that may prove potentially applicable to conjugate analysis in the aquatic environment. Currently, sample collection is typically done by grab samples, and extraction from matrices is mainly achieved by hydrophilic–lipophilic balance cartridges. Reversed-phase liquid chromatography is by far the most common form of separation. The most common column choice was C18, with some inroads being made by the zwitterionic ion chromatography–hydrophilic interaction liquid chromatographic columns to take advantage of the polar moieties of conjugates for separation. The majority of studies used a binary gradient comprised of aqueous buffer and acetonitrile, which afforded good separation and preparation for mass analysis. Quadrupole-time-of-flight mass spectrometry was most commonly used for unknown conjugate identification. There is a noted increase in linear ion traps and high mass resolution mass spectrometers (e.g., Orbitrap™) for the identification and quantification of conjugates, and as such, some hybrid technologies are emerging. However, triple quadrupole instruments remain used for the greatest sensitivity and reproducibility for conjugate quantification. Moreover, the multi-faceted combination of quadrupole-time-of-flight and triple quadrupole will be of great value.

Human and ecological risks of BDE-209 have drawn much attention, particularly with growing e-waste recycling activities in developing countries. To further address the issue of BDE-209 biotransformation, a laboratory-controlled study was conducted. Female Sprague-Dawley rats were dosed orally by gavage at a daily dose of 1 mg kg−1 body weight for 7 d and a depuration period of 22 d, to characterize absorption, distribution, metabolism, and elimination dynamics of BDE-209 during multi-dose exposures simulating short-term oral exposure of e-waste workers. The concentrations of BDE-209 in all tissues increased exponentially during the 7-d exposure period, indicating that multi-dose exposure could lead to increased accumulation of BDE-209 in rats. The liver accumulated the greatest amount of BDE-209 on a wet-weight basis, while adipose tissue had the highest concentration by the end of the 22-d depuration period. Half-lives of BDE-209, 207, and 197 during depuration were 1.1 ± 0.1, 2.7 ± 0.3, and 10.5 ± 3.1 d in serum and 0.9 ± 0.1, 2.2 ± 0.2, and 11.8 ± 2.3 d in liver, i.e., the half-life increased with decreasing level of bromination from deca- to octa-BDEs and was similar in both serum and liver. By contrast, the half-life of the debromination metabolite BDE-207 (21.7 ± 7.7 d) was longer in small intestine than in serum and liver, suggesting slower depletion of BDE-209 metabolites in small intestine. The metabolism of BDE-209 was not responsible for the occurrence of low brominated BDE congeners and OH and MeO-PBDEs in human tissues.