Veterinary pharmaceutical contamination in mixed land use watersheds: from agricultural headwater to water monitoring watershed.

Veterinary pharmaceuticals, widely used in intensive livestock production, may contaminate surface waters. Identifying their sources and pathways in watersheds is difficult because i) most veterinary pharmaceuticals are used in human medicine as well and ii) septic or sewer wastewater treatment plants (WWTP) can release pharmaceuticals into surface water, even in agricultural headwater watersheds. This study aimed to analyze the spatiotemporal variability of animal-specific, mixed-use, and human-specific pharmaceuticals, from agricultural headwaters with intensive livestock production and a WWTP to a watershed used for Water Framework Directive monitoring. Grab sampling was performed during one hydrological year upstream and downstream from a WWTP and at three dates in seven nested watersheds with areas of 1.9-84.1km2. Twenty pharmaceuticals were analyzed. Animal-specific pharmaceuticals were detected at all sampling dates upstream and downstream from the WWTP and at concentrations higher than those of human-specific pharmaceuticals. The predominance of animal-specific and mixed-use pharmaceuticals vs. human-specific pharmaceuticals observed at these sampling points was confirmed at the other sampling points. Animal-specific pharmaceuticals were detected mainly during runoff events and periods of manure spreading. A large percentage of mixed-use pharmaceuticals could come from animal sources, but it was difficult to determine. Mixed-use and human-specific pharmaceuticals predominated in the largest watersheds when runoff decreased. In areas of intensive livestock production, mitigation actions should focus on agricultural headwater watersheds to decrease the number of pathways and the transfer volume of veterinary pharmaceuticals, which can be the main contaminants.

Storage of natural water samples and preservation techniques for pharmaceutical quantification.

In order to perform a human and ecological risk assessment of pharmaceutical products (PPs) in natural waters, it is necessary to accurately quantify a broad variety of PPs at low concentrations. Although numerous currently implemented analytical methodologies, less is known about the preservation of PPs in natural water samples within the period before analysis (holding time, storage conditions). This paper is the first literature review about the stability of PPs in natural waters (surface and groundwaters) during sample storage. The current work focuses on a comparison of the performances of the available preservation techniques (filtration, container materials, storage temperature, preservative agents, etc.) for PPs in samples. All 58 reviewed PPs may be successfully stabilized during 7 days in surface waters by at least one appropriate methodology regarding temperature, acidic and non-acidic preservatives. When temperature is not a sufficient preservation parameter for some PPs (hormones and fluoxetine) its combination with the addition of chemical agents into the samples may prolong the integrity of the PPs during storage in surface water. There is a strong need to use standard protocols to assess and compare the stability of PPs in environmental water matrices during storage as well as during analytical preparation or analysis (European criteria 2002/657/EC). Since the stability of PPs during sample storage is a critical parameter that could call into question the quality of the data provided for the concentrations, the design of stability studies should rigorously take into account all critical parameters that could impact the concentrations of the PPs with time.

Development of microbial and chemical MST tools to identify the origin of the faecal pollution in bathing and shellfish harvesting waters in France.

The microbiological quality of coastal or river waters can be affected by faecal pollution from human or animal sources. An efficient MST (Microbial Source Tracking) toolbox consisting of several host-specific markers would therefore be valuable for identifying the origin of the faecal pollution in the environment and thus for effective resource management and remediation. In this multidisciplinary study, after having tested some MST markers on faecal samples, we compared a selection of 17 parameters corresponding to chemical (steroid ratios, caffeine, and synthetic compounds), bacterial (host-specific Bacteroidales, Lactobacillus amylovorus and Bifidobacterium adolescentis) and viral (genotypes I-IV of F-specific bacteriophages, FRNAPH) markers on environmental water samples (n = 33; wastewater, runoff and river waters) with variable Escherichia coli concentrations. Eleven microbial and chemical parameters were finally chosen for our MST toolbox, based on their specificity for particular pollution sources represented by our samples and their detection in river waters impacted by human or animal pollution; these were: the human-specific chemical compounds caffeine, TCEP (tri(2-chloroethyl)phosphate) and benzophenone; the ratios of sitostanol/coprostanol and coprostanol/(coprostanol+24-ethylcopstanol); real-time PCR (Polymerase Chain Reaction) human-specific (HF183 and B. adolescentis), pig-specific (Pig-2-Bac and L. amylovorus) and ruminant-specific (Rum-2-Bac) markers; and human FRNAPH genogroup II.

Release of trace elements in wetlands: role of seasonal variability.

Dissolved concentrations were determined for Fe, Mn, Al, Cu, Zn, La, U, Th, Cd and As in a wetland and its recipient stream to reveal the effect of seasonal changes in environmental conditions on the cycling and transfer of trace elements at the transition between terrestrial and aquatic ecosystems. These preliminary results from the wetland show marked seasonal changes in dissolved concentration for all elements except Zn and Cu. Concentrations are found to be low until about mid-February and then increase abruptly. The onset of trace element release appears to coincide with a marked decline in redox potential and increase of organic carbon content. Because this decline is itself correlated with a pronounced increase in temperature and dissolved Fe. Mn and organic carbon content, we suggest that the microorganisms which use soil iron and manganese oxy-hydroxides as electron acceptors catalyzed the change in redox conditions and induced an increase of DOC. Temporal changes were also observed in the recipient stream which showed marked positive concentration peaks during stormflow events (except Zn). The seasonal processes occurring in the wetland appear to play a major role in determining the amount of trace elements which are transferred from the wetland to the river.