Freshwater ecosystems are threatened by multiple anthropogenic stressors, which might be differentiated into two types: those that reduce biological activity at all concentrations (toxic contaminants), and those that subsidize biological activity at low concentrations and reduce it at high concentrations (assimilable contaminants). When occurring in mixtures, these contaminants can have either antagonistic, neutral or synergistic effects; but little is known on their joint effects. We assessed the interaction effects of a mixture of assimilable and toxic contaminants on stream biofilms in a manipulative experiment using artificial streams, and following a factorial design with three nutrient levels (low, medium or high) and either presence or absence of a mixture of emerging contaminants (ciprofloxacin, erythromycin, diclofenac, methylparaben, and sulfamethoxazole). We measured biofilm biomass, basal fluorescence, gross primary production and community respiration. Our initial hypotheses were that biofilm biomass and activity would: increase with medium nutrient concentrations (subsidy effect), but decrease with high nutrient concentrations (stress effect) (i); decrease with emerging contaminants, with the minimum decrease at medium nutrient concentrations (antagonistic interaction between nutrients subsidy and stress by emerging contaminants) and the maximum decrease at high nutrient concentrations (synergistic interaction between nutrients and emerging contaminants stress) (ii). All the measured variables responded linearly to the available nutrients, with no toxic effect at high nutrient concentrations. Emerging contaminants only caused weak toxic effects in some of the measured variables, and only after 3–4 weeks of exposure. Therefore, only antagonistic interactions were observed between nutrients and emerging contaminants, as medium and high nutrient concentrations partly compensated the harmful effects of emerging contaminants during the first weeks of the experiment. Our results show that contaminants with a subsidy effect can alleviate the effects of toxic contaminants, and that long-term experiments are required to detect stress effects of emerging contaminants at environmentally relevant concentrations.

With the increasing use of treated wastewater and biosolids in agriculture, residues of pharmaceutical and personal care products (PPCPs) in these reused resources may contaminate food produce via plant uptake, constituting a route for human exposure. Although various PPCPs have been reported to be taken up by plants in laboratories or under field conditions, at present little information is available on their metabolism in plants. In this study, we applied carrot cell cultures to investigate the plant metabolism of PPCPs. Five phase I metabolites of carbamazepine were identified and the potential metabolism pathways of carbamazepine were proposed. We also used the carrot cell cultures as a rapid screening tool to initially assess the metabolism potentials of 18 PPCPs. Eleven PPCPs, including acetaminophen, caffeine, meprobamate, primidone, atenolol, trimethoprim, DEET, carbamazepine, dilantin, diazepam, and triclocarban, were found to be recalcitrant to metabolism. The other 7 PPCPs, including triclosan, naproxen, diclofenac, ibuprofen, gemfibrozil, sulfamethoxazole, and atorvastatin, displayed rapid metabolism, with 0.4–47.3% remaining in the culture at the end of the experiment. Further investigation using glycosidase hydrolysis showed that 1.3–20.6% of initially spiked naproxen, diclofenac, ibuprofen, and gemfibrozil were transformed into glycoside conjugates. Results from this study showed that plant cell cultures may be a useful tool for initially exploring the potential metabolites of PPCPs in plants as well as for rapidly screening the metabolism potentials of a variety of PPCPs or other emerging contaminants, and therefore may be used for prioritizing compounds for further comprehensive evaluations.

We evaluated three types of functionalized, graphene-based materials for activating persulfate (PS) and removing (i.e., sorption and oxidation) sulfamethoxazole (SMX) as a model emerging contaminant. Although advanced oxidative water treatment requires PS activation, activation requires energy or chemical inputs, and toxic substances are contained in many catalysts. Graphene-based materials were examined herein as an alternative to metal-based catalysts. Results show that nitrogen-doped graphene (N-GP) and aminated graphene (NH2-GP) can effectively activate PS. Overall, PS activation by graphene oxide was not observed in this study. N-GP (50 mg L−1) can rapidly activate PS (1 mM) to remove >99.9% SMX within 3 h, and NH2-GP (50 mg L−1) activated PS (1 mM) can also remove 50% SMX within 10 h. SMX sorption and total removal was greater for N-GP, which suggests oxidation was enhanced by increasing proximity to PS activation sites. Increasing pH enhanced the N-GP catalytic ability, and >99.9% SMX removal time decreased from 3 h to 1 h when pH increased from 3 to 9. However, the PS catalytic ability was inhibited at pH 9 for NH2-GP. Increases in ionic strength (100 mM NaCl or Na2SO4) and addition of radical scavengers (500 mM ethanol) both had negligible impacts on SMX removal. With bicarbonate addition (100 mM), while the catalytic ability of N-GP remained unaltered, NH2-GP catalytic ability was inhibited completely. Humic acid (250 mg L−1) was partially effective in inhibiting SMX removal in both N-GP and NH2-GP systems. These results have implications for elucidating oxidant catalysis mechanisms, and they quantify the ability of functionalization of graphene with hetero-atom doping to effectively catalyze PS for water treatment of organic pollutants including emerging contaminants.

The presence of sulfonamide antibiotics in aquatic environments poses potential risks to human health and ecosystems. In the present study, a highly porous activated carbon was prepared by KOH activation of an anthracite coal (Anth-KOH), and its adsorption properties toward two sulfonamides (sulfamethoxazole and sulfapyridine) and three smaller-sized monoaromatics (phenol, 4-nitrophenol and 1,3-dinitrobenzene) were examined in both batch and fixed-bed adsorption experiments to probe the interplay between adsorbate molecular size and adsorbent pore structure. A commercial powder microporous activated carbon (PAC) and a commercial mesoporous carbon (CMK-3) possessing distinct pore properties were included as comparative adsorbents. Among the three adsorbents Anth-KOH exhibited the largest adsorption capacities for all test adsorbates (especially the two sulfonamides) in both batch mode and fixed-bed mode. After being normalized by the adsorbent surface area, the batch adsorption isotherms of sulfonamides on PAC and Anth-KOH were displaced upward relative to the isotherms on CMK-3, likely due to the micropore-filling effect facilitated by the microporosity of adsorbents. In the fixed-bed mode, the surface area-normalized adsorption capacities of Anth-KOH for sulfonamides were close to that of CMK-3, and higher than that of PAC. The irregular, closed micropores of PAC might impede the diffusion of the relatively large-sized sulfonamide molecules and in turn led to lowered fixed-bed adsorption capacities. The overall superior adsorption of sulfonamides on Anth-KOH can be attributed to its large specific surface area (2514 m²/g), high pore volume (1.23 cm³/g) and large micropore sizes (centered at 2.0 nm). These findings imply that KOH-activated anthracite coal is a promising adsorbent for the removal of sulfonamide antibiotics from aqueous solution.

The treatment of municipal wastewater in the Arctic is challenging due to a variety of financial, operational, climatic and technical issues. To better understand the efficacy of current wastewater treatment in this region and the hazard posed to receiving waters, we assessed the occurrence of nutrients and contaminants (i.e., pharmaceuticals, antibiotic resistance genes) as they moved through a lagoon-based treatment system in Cambridge Bay, Nunavut, Canada. Wastewater treatment in this community is performed by the use of a lagoon-tundra wetland system that is discharged into the marine environment and is representative of current common practices throughout the region. In 2014, samples were collected before and during lagoon discharge from two locations in the main lagoon, one location downstream from the lagoon effluent and three locations offshore. Grab samples were collected to measure nutrients (e.g., total nitrogen and phosphorus) and the presence of antibiotic resistance gene-bearing microbes, and Polar Organic Chemical Integrative Samplers (POCIS) were deployed to collect passively organic contaminants in all locations. A total of six pharmaceuticals were detected from a screen of twenty-eight analytes during the study: atenolol, carbamazepine, clarithromycin, metoprolol, sulfamethoxazole and trimethoprim. The greatest concentrations of nutrients, antibiotic resistance genes (ARGs), and pharmaceuticals were found in sampling locations within the treatment lagoon. Offshore of the release point, we observed limited to no detection of pharmaceuticals and ARGs, but no change in total nitrogen and phosphorus from pre-release. We conclude that the current concentrations of monitored pharmaceuticals do not pose a significant hazard at this time to aquatic organisms in Cambridge Bay.

We investigated the effect of solution pH and soil structure on transport of sulfonamide antibiotics (sulfamethoxazole, sulfadimethoxine and sulfamethazine) in combination with batch sorption tests and column experiments. Sorption isotherms properly conformed to Freundlich model, and sorption potential of the antibiotics is as follows; sulfadimethoxine > sulfamethoxazole > sulfamethazine. Decreasing pH values led to increased sorption potential of the antibiotics on soil material in pH range of 4.0–8.0. This likely resulted from abundance of neutral and positive-charged sulfonamides species at low pH, which electrostatically bind to sorption sites on soil surface. Due to destruction of macropore channels, lower hydraulic conductivities of mobile zone were estimated in the disturbed soil columns than in the undisturbed soil columns, and eventually led to lower mobility of the antibiotics in disturbed column. The results suggest that knowledge of soil structure and solution condition is required to predict fate and distribution of sulfonamide antibiotics in environmental matrix.

Soils may be contaminated by human or veterinary pharmaceuticals. Their behaviour in soil environment is largely controlled by sorption of different compounds in a soil solution onto soil constituents. Here we studied the sorption affinities of 4 pharmaceuticals (atenolol, trimethoprim, carbamazepine and sulfamethoxazole) applied in solute mixtures to soils taken from different horizons of 3 soil types (Greyic Phaeozem on loess, Haplic Luvisol on loess and Haplic Cambisol on gneiss). In the case of the carbamazepine (neutral form) and sulfamethoxazole (partly negatively charged and neutral), sorption affinity of compounds decreased with soil depth, i.e. decreased with soil organic matter content. On the other hand, in the case of atenolol (positively charged) and trimethoprim (partly positively charged and neutral) compound sorption affinity was not depth dependent. Compound sorption affinities in the four-solute systems were compared with those experimentally assessed in topsoils, and were estimated using the pedotransfer rules proposed in our previous study for single-solute systems. While sorption affinities of trimethoprim and carbamazepine in topsoils decreased slightly, sorption affinity of sulfamethoxazole increased. Decreases in sorption of the two compounds could be attributed to their competition between each other and competition with atenolol. Differences between carbamazepine and atenolol behaviour in the one- and four-solute systems could also be explained by the slightly different soil properties in this and our previous study. A great increase of sulfamethoxazole sorption in the Greyic Phaeozem and Haplic Luvisol was observed, which was attributed to elimination of repulsion between negatively charged molecules and particle surfaces due to cation sorption (atenolol and trimethoprim) on soil particles. Thus, our results proved not only an antagonistic but also a synergic affect of differently charged organic molecules on their sorption to soil constituents.

Treated wastewater is expected to be increasingly used as an alternative source of irrigation water in areas facing fresh water scarcity. Understanding the behaviors of contaminants from wastewater in soil and plants following irrigation is critical to assess and manage the risks associated with wastewater irrigation. The objective of this study was to evaluate the effects of soil texture and drought stress on the uptake of antibiotics and the internalization of human pathogens into lettuce through root uptake following wastewater irrigation. Lettuce grown in three soils with variability in soil texture (loam, sandy loam, and sand) and under different levels of water stress (no drought control, mild drought, and severe drought) were irrigated with synthetic wastewater containing three antibiotics (sulfamethoxazole, lincomycin and oxytetracycline) and one Salmonella strain a single time prior to harvest. Antibiotic uptake in lettuce was compound-specific and generally low. Only sulfamethoxazole was detected in lettuce with increasing uptake corresponding to increasing sand content in soil. Increased drought stress resulted in increased uptake of lincomycin and decreased uptake of oxytetracycline and sulfamethoxazole. The internalization of Salmonella was highly dependent on the concentration of the pathogen in irrigation water. Irrigation water containing 5 Log CFU/mL Salmonella resulted in limited incidence of internalization. When irrigation water contained 8 Log CFU/mL Salmonella, the internalization frequency was significantly higher in lettuce grown in sand than in loam (p = 0.009), and was significantly higher in lettuce exposed to severe drought than in unstressed lettuce (p = 0.049). This work demonstrated how environmental factors affected the risk of contaminant uptake by food crops following wastewater irrigation.

This study investigated the occurrence of bisphenol A (BPA), atrazine and selected pharmaceutically active compounds (PhACs) in mangrove habitats in Singapore in 2012–2013, using multiple tools (sediment sampling, POCIS and filter feeder molluscs). Using POCIS, the same suite of contaminants (atrazine, BPA and eleven PhACs) was detected in mangrove waters in 28-days deployments in both 2012 and 2013. POCIS concentrations ranged from pg/L to μg/L. Caffeine, BPA, carbamazepine, E1, triclosan, sulfamerazine, sulfamethazine, and lincomycin were also detected in mangrove sediments from the low pg/g dw (e.g. carbamazepine) to ng/g dw (e.g. BPA). The detection of caffeine, carbamazepine, BPA, sulfamethoxazole or lincomycin in bivalve tissues also showed that these chemicals are bioavailable in the mangrove habitat. Since there are some indications that some pharmaceutically active substances may be biologically active in the low ppb range in marine species, further assessment should be completed based on ecotoxicological data specific to mangrove species.

The occurrence of pharmaceuticals in freshwater ecosystems provokes increasing concern due to their potential risk to non-target organisms and to human health. Pharmaceuticals are used in both human and veterinary medicine and are essentially released into the environment via wastewater treatment plants (WWTPs) and from livestock. In this study, 31 pharmaceuticals were analyzed in effluent and surface water upstream and downstream of two WWTPs in the Loue–Doubs rural karstic catchment in Eastern France. Diclofenac (965 and 2476 ng L⁻¹), sulfamethoxazole (655 and 1380 ng L⁻¹) and carbamazepine (566 and 1007 ng L⁻¹) displayed the highest levels in the effluents of both WWTPs. Diclofenac levels were also high in surface water samples 300 and 166 ng L⁻¹ in the River Doubs and the River Loue, respectively, followed by paracetamol (273 and 158 ng L⁻¹) and sulfamethoxazole (126 and 73 ng L⁻¹). In both rivers, the most critical compounds were found to be the antibiotic sulfamethoxazole (risk quotient (RQ) from 23.7 to 51.1) and ofloxacine (RQ from 1.1 to 18.9), which reached levels inducing toxic effects in aquatic organisms. This study showed that WWTP effluents are the major sources of the pharmaceuticals, but raw discharges from human residences, pastures and livestock manure represent significant sources of contamination of surface water and groundwater. The aim of this study was to assist scientists and authorities in understanding occurrence and sources of pharmaceuticals in order to improve water quality management in chalk streams.