Responses of soil nitrification activities to copper after a moisture stress.

Some steps of the soil nitrogen (N) cycle are sensitive to environmental pressures like soil moisture or contamination, which are expected to evolve during the next decades. Individual stresses have been well studied, but their combination is not yet documented. In this work, we aimed at assessing the importance of the soil moisture on the impact of copper (Cu) contaminations on the N cycling soil function using the potential nitrification activities (PNA) as bioindicator. A two-step experiment was performed. First, a loamy soil was incubated 5 weeks in either 30, 60, or 90% of its water holding capacity (WHC) or alternating drought and rewetting periods. Thereafter, soil samples were exposed to a gradient of Cu concentrations through a bioassay involving nitrification. The dose-response curves of PNA in function of added Cu were modeled to calculate the effective Cu concentrations, namely ECx with x being the percentage of PNA inhibition. These values were then compared between experimental conditions to highlight differences in threshold values. The preincubation moisture treatments significantly affected the PNA responses to the secondary Cu stress with, for instance, hormetic responses in all cases except for the dry-rewetting treatment. Small PNA inhibitions were estimated for high Cu doses in the soils with low water contents (30% WHC) or submitted to dry-rewetting cycles, contrarily to the patterns observed for the soils with high water contents (90% WHC) or submitted to a single period of drought. Overall, significant differences were found in estimated ECx values between moisture treatments.

Evidence for the widespread occurrence of short- and medium-chain chlorinated paraffins in fish collected from the Rhône River basin (France).

Chlorinated paraffins (CPs) are high-volume chemicals used in numerous industrial applications. Their quantitative analysis is extremely challenging and this work presents the optimization of an analytical method based on gas chromatography hyphenated with electron capture negative ionization time-of-flight high-resolution mass spectrometry (GC-ECNI-TOF HRMS) for the simultaneous determination of short-chain and medium-chain CPs (SCCPs and MCCPs, respectively) in fish tissues (i.e. dorsal muscle). The resolution of the TOF-MS analyzer reduced or eliminated isobaric interferences and the CP response was optimized through Design of Experiment. A simple clean-up procedure based on adsorption chromatography further removed some potentially interfering organochlorines. Good selectivity, linearity and accuracy were achieved; method detection limits or limits of reporting were compatible with expected levels in wild fish (0.03-0.35 ng g-1 wet weight, ww, depending on the congener). This method was proven suitable for the analysis of CPs in tissues of common barbel Barbus, a fish species frequently used for water quality monitoring purposes in Europe. SCCPs and MCCPs were found to be widespread within the Rhône river basin (France). At all locations, MCCP concentrations (1.3-72.7 ng g-1 ww) were higher than those of SCCPs (0.3-10.6 ng g-1 ww) and levels were systematically lower than the proposed Predicted No Effect Concentrations (PNECs). Spatial variations of SCCP composition profiles largely surpassed those of MCCPs, suggesting the influence of local sources.