Utilization of long duration high-volume sampling coupled to SPME-GC-MS/MS for the assessment of airborne pesticides variability in an urban area (Strasbourg,France) during agricultural application

Atmospheric samples have been collected between 14 March and 12 September 2012 on a 2-week basis (15 days of sampling and exchange of traps each 7 days) in Strasbourg (east of France) for the analysis of 43 pesticides. Samples (particle and gas phases) were separately extracted using Accelerated Solvent Extraction (ASE) and pre-concentrated by Solid Phase Micro-Extraction (SPME) before analysis by gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). Four SPME consecutive injections at distinct temperatures were made in order to increase the sensitivity of detection for the all monitored pesticides. Currently used detected pesticides can be grouped in four classes; those used in maize crops (acetochlor, benoxacor, dicamba, s-metolachlor, pendimethalin, and bromoxynil), in cereal crops (benoxacor, chlorothalonil, fenpropimorph, and propiconazole), in vineyards (tebuconazole), and as herbicides for orchards, meadows of green spaces (2,4-MCPA, trichlopyr). This is in accordance with the diversity of crops found in the Alsace region and trends observed are in accordance with the period of application of these pesticides. Variations observed permit also to demonstrate that the long time sampling duration used in this study is efficient to visualize temporal variations of airborne pesticides concentrations. Then, long time high-volume sampling could be a simple method permitting atmospheric survey of atmospheric contamination without any long analysis time and consequently low cost.     

Carbon mineralization,microbial activity and metal dynamics in tailing ponds amended with pig slurry and marble waste

A field experiment was set up in Cartagena-La Unión Mining District, SE Spain, aimed at evaluating the short-term effects of pig slurry (PS) amendment alone and together with marble waste (MW) on organic matter mineralization, microbial activity and stabilization of heavy metals in two tailing ponds. These structures pose environmental risk owing to high metals contents, low organic matter and nutrients, and null vegetation. Carbon mineralization, exchangeable metals and microbiological properties were monitored during 67 d. The application of amendments led to a rapid decrease of exchangeable metals concentrations, except for Cu, with decreases up to 98%, 75% and 97% for Cd, Pb and Zn, respectively. The combined addition of MW + PS was the treatment with greater reduction in metals concentrations. The addition of PS caused a significant increase in respiration rates, although in MW + PS plots respiration was lower than in PS plots. The mineralized C from the pig slurry was low, approximately 25–30% and 4–12% for PS and MW + PS treatments, respectively. Soluble carbon (Csol), microbial biomass carbon (MBC) and β-galactosidase and β-glucosidase activities increased after the application of the organic amendment. However, after 3 d these parameters started a decreasing trend reaching similar values than control from approximately day 25 for Csol and MBC. The PS treatment promoted highest values in enzyme activities, which remained high upon time. Arylesterase activity increased in the MW + PS treatment. Thus, the remediation techniques used improved soil microbiological status and reduced metal availability. The combined application of PS + MW reduced the degradability of the organic compounds.     

Variation patterns in individual fish responses to chemical stress among estuaries, seasons and genders: the case of the European flounder (Platichthys flesus) in the Bay of Biscay

The objective was to describe and model variation patterns in individual fish responses to contaminants among estuaries, season and gender. Two hundred twenty-seven adult European flounders were collected in two seasons (winter and summer) in four estuaries along the Bay of Biscay (South West France), focusing on a pristine system (the Ster), vs. three estuaries displaying contrasted levels of contaminants (the Vilaine, Loire and Gironde). Twenty-three variables were measured by fish, considering the load of contaminants (liver metals, liver and muscle persistent organic pollutants, muscle polycyclic aromatic hydrocarbons); the gene expression (Cyt C oxydase, ATPase, BHMT, Cyt P450 1A1, ferritin); the blood genotoxicity (Comet test); and liver histology (foci of cellular alteration–tumour, steatosis, inflammation, abnormal glycogen storage). Canonical redundancy analysis (RDA) was used to model these variables using gender, season and estuary of origin as explanatory variables. The results underlined the homogeneity of fish responses within the pristine site (Ster) and more important seasonal variability within the three contaminated systems. The complete model RDA was significant and explained 35 % of total variance. Estuary and season respectively explained 30 and 5 % of the total independent variation components, whilst gender was not a significant factor. The first axis of the RDA explains nearly 27 % of the total variance and mostly represents a gradient of contamination. The links between the load of contaminants, the expression of several genes and the biomarkers were analysed considering different levels of chemical stress and a possible multi-stress, particularly in the Vilaine estuary.     

Kinetic aspects and identification of by-products during the ozonation of bitertanol in agricultural wastewaters

The degradation of bitertanol by ozone treatment is investigated. Solutions of bitertanol (8.4 μg mL^?1) were prepared either by dissolution of the standard or by dilution of Gaucho Blé seed loading solution and then ozonated under different conditions. Evolution of the concentrations of bitertanol and its ozonation by-products in both solutions was monitored by HPLC–UV as a function of the treatment time for a concentration of 100 g m^?3 of ozone in the inlet gas. Bitertanol degradation was found to follow a pseudo-first order reaction in both cases. However, the rate of the reaction in diluted seed loading solution was much lower (0.19 vs. 0.27 min^?1 in standard solution) and was close to the reaction rate observed in the presence of a radical scavenger, tert-butanol (0.11 min^?1). Thus, it may be suggested that additives present in the seed loading solution may play the role of radical scavengers. Study of ozone concentration in the inlet gas (from 25 to 100 g m^?3) showed that ozone degradation is also a first-order reaction with respect to ozone. Four ozonation by-products were highlighted, collected and identified by HPLC coupled with an ion trap mass spectrometer using positive electrospray ionization mode. A degradation pathway of bitertanol was finally proposed.     

Development of a livestock odor dispersion model: part II. Evaluation and validation

A livestock odor dispersion model (LODM) was developed to predict odor concentration and odor frequency using routine hourly meteorological data input. The odor concentrations predicted by the LODM were compared with the results obtained from other commercial models (Industrial Source Complex Short-Term model, version 3, CALPUFF) to evaluate its appropriateness. Two sets of field odor plume measurement data were used to validate the model. The model-predicted mean odor concentrations and odor frequencies were compared with those measured. Results show that this model has good performance for predicting odor concentrations and odor frequencies.     

Evaluation of saline tracer performance during electrical conductivity groundwater monitoring

Saline solutions are the most commonly used hydrological tracers, because they can be easily and economically monitored by in situ instrumentation such as electrical conductivity (EC) loggers in wells or by geoelectrical measurements. Unfortunately, these low-cost techniques only provide information on the total concentration of ions in solution, i.e., they cannot resolve the ionic composition of the aqueous solution. This limitation can introduce a bias in the estimation of aquifer parameters where sorption phenomena between saline tracers and sediments become relevant. In general, only selected anions such as Cl(-) and Br(-) are recognised to be transported unretarded and they are referred to as conservative tracers or mobile anions. However, cations within the saline tracer may interact with the soil matrix through a range of processes such as ion exchange, surface complexation and via physical mass-transfer phenomena. Heterogeneous reactions with minerals or mineral surfaces may not be negligible where aquifers are composed of fine alluvial sediments. The focus of the present study was to examine and to quantify the bias between the aquifer parameters estimated during model-based interpretation of experimental data of EC measurements of saline tracer relative to the aquifer parameters found by specific measurements (i.e. via ionic chromatography, IC) of truly conservative species. To accomplish this, column displacement experiments with alluvial aquifer materials collected from the Po lowlands (Italy) were performed under water saturated conditions. The behaviour of six selected, commonly used saline tracers (i.e., LiCl, KCl, and NaCl; LiBr, KBr, and NaBr) was studied and the data analysed by inverse modelling. The results demonstrate that the use of EC as a tracer can lead to an erroneous parameterisation of the investigated porous media, if the reactions between solute and matrix are neglected. In general, errors were significant except for KCl and KBr, which is due to the weak interaction between dissolved K(+) and the sediment material. The study shows that laboratory scale pre-investigations can help with tracer selection and to optimise the concentration range targeted for in situ multilevel monitoring by unspecific geoelectrical instrumentation.     

Influence of global change on phytoplankton and nutrient cycling in the Elbe River

The effects of changing climatic and socioeconomic conditions on the water quality of the Elbe River were investigated using the deterministic model QSim. Since the impact of global change on river water quality marks the endpoint of various processes in the catchment and in the atmosphere, this study was performed within a network of interacting models that determined input parameters for water quality simulations. The development of phytoplankton and nutrient concentrations under conditions of global change was modeled along a 700 km stretch of the river. The simulations revealed a strong, scale-dependent effect of climate change on phytoplankton biomass, leading to a longitudinal shift of the dominating processes (primary productivity vs. respiration) along the river continuum. Under reduced flow, combined with increasing temperature and global radiation, phytoplankton biomass increased and phytoplankton maxima shifted in upstream direction, followed by higher system respiration rates in the adjacent downstream sections. In contrast, higher flow shifted the phytoplankton maximum toward the downstream sections. Even a drastic reduction of phosphorus inputs from anthropogenic sources had only limited influence on algal biomass, due to the ability of algal cells to store phosphorus. A strong reduction in P-inputs especially in the headwaters would be necessary to counterbalance the possible climate-induced effects on algal biomass.     

Seasonal atmospheric deposition variations of polychlorinated biphenyls (PCBs) and comparison of some deposition sampling techniques

Introduction  

Ambient air and bulk deposition samples were collected between June 2008 and June 2009. Eighty-three polychlorinated biphenyl (PCB) congeners were targeted in the samples.