Occurrence of pharmaceuticals in WWTP effluents and their impact in a karstic rural catchment of Eastern France.

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.

PAH occurrence in chalk river systems from the Jura region (France). Pertinence of suspended particulate matter and sediment as matrices for river quality monitoring.

This study investigates the variations of polycyclic aromatic hydrocarbon (PAH) levels in surface water, suspended particulate matter (SPM) and sediment upstream and downstream of the discharges of two wastewater treatment plant (WWTP) effluents. Relationships between the levels of PAHs in these different matrices were also investigated. The sum of 16 US EPA PAHs ranged from 73.5 to 728.0 ng L(-1) in surface water and from 85.4 to 313.1 ng L(-1) in effluent. In SPM and sediment, ∑16PAHs ranged from 749.6 to 2,463 µg kg(-1) and from 690.7 µg kg(-1) to 3,625.6 µg kg(-1), respectively. Investigations performed upstream and downstream of both studied WWTPs showed that WWTP discharges may contribute to the overall PAH contaminations in the Loue and the Doubs rivers. Comparison between gammarid populations upstream and downstream of WWTP discharge showed that biota was impacted by the WWTP effluents. When based only on surface water samples, the assessment of freshwater quality did not provide evidence for a marked PAH contamination in either of the rivers studied. However, using SPM and sediment samples, we found PAH contents exceeding sediment quality guidelines. We conclude that sediment and SPM are relevant matrices to assess overall PAH contamination in aquatic ecosystems. Furthermore, we found a positive linear correlation between PAH contents of SPM and sediment, showing that SPM represents an integrating matrix which is able to provide meaningful data about the overall contamination over a given time span.

Unexpected toxic interactions in the freshwater amphipod Gammarus pulex (L.) exposed to binary copper and nickel mixtures.

To document the toxicity of copper and nickel in binary mixtures, freshwater amphipods Gammarus pulex were exposed to the metals given independently or as mixtures. Toxicity to Cu alone was relatively high: 96-h LC10 and LC50 were found at 91 and 196 µg L(-1), respectively. Toxicity to Ni alone was very low, with 96-h LC10 and LC50 of 44,900 and 79,200 µg L(-1), respectively. Mixture toxicities were calculated from single toxicity data using conventional models. Modeled toxicity was then compared with the measured toxicity of the binary mixture. Two kinds of mixtures were tested. Type I mixtures were designed as combinations of Cu and Ni given at the same effect concentrations, when taken independently, to identify possible interactions between copper and nickel. In type II mixtures, Cu concentrations varied from 0 to 600 µg L(-1) while the nickel concentration was kept constant at 500 µg L(-1) to mimic conditions of industrial wastewater discharges. Ni and Cu showed synergic effects in type I mixtures while type II mixtures revealed antagonistic effects. Low doses of Ni reduced Cu toxicity towards G. pulex. These results show that even for simple binary mixtures of contaminants with known chemistry and toxicity, unexpected interactions between the contaminants may occur. This reduces the reliability of conventional additivity models.

Evaluation of the phytotoxicity of polycontaminated industrial effluents using the lettuce plant (Lactuca sativa) as a bioindicator.

Industrial wastewater containing heavy metals is generally decontaminated by physicochemical treatment consisting in insolublizing the contaminants and separating the two phases, water and sludge, by a physical process (filtration, settling or flotation). However, chemical precipitation does not usually remove the whole pollution load and the effluent discharged into the environment can be toxic even if it comes up to regulatory standards. To assess the impact of industrial effluent from 4 different surface treatment companies, we performed standardized bioassays using seeds of the lettuce Lactuca sativa. We measured the rate of germination, and the length and mass of the lettuce plantlet. The results were used to compare the overall toxicity of the different effluents: effluents containing copper and nickel had a much higher impact than those containing zinc or aluminum. In addition, germination tests conducted using synthetic solutions confirmed that mixtures of metals have higher toxicity than the sum of their separate constituents. These biological tests are cheap, easy to implement, reproducible and highlight the effects caused by effluent treated with the methods commonly applied in industry today. They could be routinely used to check the impact of industrial discharges, even when they meet regulatory requirements for the individual metals.

High sensitivity of Gammarus sp. juveniles to deltamethrin: outcomes for risk assessment.

Amphipods from the genus Gammarus are among the most frequently used organisms in ecotoxicological testing and in situ bioindication. Because of their importance in risk assessment, it is necessary to understand the potential roles of life stage, population source and inter-specific differences on the sensitivity of these organisms to contaminants. In the present study, the acute toxicity of deltamethrin, a commonly used pyrethroid insecticide, has been tested for Gammarus fossarum and Gammarus pulex (Crustacea, Amphipoda) to document the inter- and intra-specific variability at different developmental stages. Adult G. fossarum were about two-fold more sensitive to deltamethrin than adult G. pulex, 96-h LC50 being 33.2 and 68.0 ng L(-1), respectively. However, in the same species, significant differences of sensitivity were observed between individuals from different locations. Furthermore, G. fossarum from certain localities were less sensitive to deltamethrin than certain G. pulex. In addition, juveniles of both species were about 14- to 22-fold more sensitive to deltamethrin than adults: 48-h LC50 in G. fossarum and G. pulex juveniles were 4.0 and 5.7 ng L(-1). Therefore, lethal effects of deltamethrin on Gammarus sp. populations likely depend more on juvenile response rather than on adult response. Since juveniles were also the most abundant population component, the present results show that risk assessment should consider at this developmental stage.

Mixture toxicity assessment of wood preservative pesticides in the freshwater amphipod Gammarus pulex (L.).

All over the world, insecticides and fungicides are used to protect wood against pathogens. To document the environmental toxicity of wood preservative mixtures, freshwater amphipods Gammarus pulex (L.) were submitted to organic pesticides given independently or in mixtures. When given independently at environmentally realistic concentrations, propiconazole and tebuconazole (triazoles fungicides) were not toxic for G. pulex, 3-iodo-2-propinyl butyl carbamate (IPBC, fungicide) was moderately toxic, and cypermethrin (pyrethroid insecticide) was extremely toxic. 96-h LC50 were, respectively, 4703, 1643, 604, and 0.09 microg L(-1). When amphipods were submitted to a mixture mimicking the composition of a commercial solution (18.2% of cypermethrin, 45.8% propiconazole, 17.2% tebuconazole, 18.8% IPBC), the overall toxicity was equal to that of the most toxic component, namely cypermethrin. But, when organisms were submitted to the real commercial mixture containing pesticides, solvents and additives, the toxic effects were markedly higher. Moreover, a third mixture with only 0.002% cypermethrin showed lethality 2.5-18-fold higher than those predicted by the commonly used models. The present results show that toxicity of wood preservative mixtures cannot be assessed starting only from the toxicities of each single component. Furthermore, the present data strongly suggest that the environmental impacts of wood preservative mixtures might be frequently underestimated.