Validation of a conductometric bienzyme biosensor for the detection of proteins as marker of organic matter in river samples

This article describes a conductometric bi-layer based bienzyme biosensor for the detection of proteins as a marker of organic matter in rivers. Proteins were chosen to be used as indicators of urban pollution. The working mechanism of the bienzyme biosensor is based on the enzymatic hydrolysis of proteins into several fractions (peptides and amino acids), which results in a local conductivity change depending of the concentration of proteins. In this work, we began with the optimization of biosensor response using bovine serum albumin (BSA) as standard protein. For this objective seven enzymatic biosensors were prepared: four enzymatic sensors with only one layer of enzyme (proteinase K, trypsin, pronase or protease X) and three other enzymatic sensors with two layers (first layer: membrane containing proteinase K; second layer: one of the three other enzymes: trypsin, pronase or protease X). The biosensors were obtained through the deposition of enzymatic layers and the cross-linking process between enzymes and BSA in saturated glutaraldehyde vapour. The response of the various biosensors, described previously, were compared with the values of total organic carbon (TOC), and those of organic nitrogen (Norg), as determined by the laboratory accredits (CEMAGREF of Lyon) using the traditional method of analysis (NF EN 1484, infrared spectroscopy) and (NF EN 25663, mineralization/colorimetry assay) respectively for each water sample obtained from di erent sites in Lyon (France). The linear correlations obtained with the response of the seven biosensors showed the most important indices of correlations for the biosensor with two enzymatic layers: proteinase K + pronase (pkp). The optimum conditions for the preparation of the pkp biosensor increased the sensitivity and gave a limit of quantification of 0.583 g/L for TOC and 0.218 g/L for Norg in water samples. This sensor shows good reproducibility (2.28%), a capacity to be used at temperatures range 10– 30°C (depending on the season) and moreover a long lifetime (5 weeks).     

Microsatellites and artificial neural networks: tools for the discrimination between natural and hatchery brown trout (Salmo trutta, L.) in Atlantic populations

Artificial Neural Networks (ANN) were applied to microsatellite data (highly variable genetic markers) to separate genetically differentiated forms of brown trout (Salmo trutta) in south-western France. A classic feed-forward network with one hidden layer was used. Training was performed using a back-propagation algorithm and reference samples representing the different genetic types. The hold-out and the leave-one-out procedures were used to test the validity of the network. They were chosen according to the populations and the questions analysed. The informative content of the different variables used for the distinction (the alleles of the different loci) was also evaluated using the Garson–Goh algorithm. The results of learning gave high percentages of well-classified individuals (up to 95% for the test with the hold-out analysis). This confirms that ANNs are suitable for such genetic analyses of populations. From a biological point of view, the study enabled evaluation of the genetic composition and differentiation of different river populations and of the impact of stocking.     

Plant Bioavailability of “natural” and “model” Humic acid‐bound [14c] Atrazine residues

The release of bound [14C] atrazine residues and their uptake by maize plants was investigated.

“Natural”; humic acids, extracted from a brown soil, and “model”; humic acids, prepared from catechol, both containing bound [14C] atrazine residues were incubated with plants in soil. After 21 days, the maize plants contained 0.7% (plants grown in soil mixed with “natural”; humic acids) to 1.7% (plants grown in soil mixed with “model”; humic acids) of the radioactivity originally introduced.

The roots contained 55 to 70% of the [14C] residues whereas the remainder was present in the shoots. A significant amount of the total [14C] residues (29 to 53%) became again bound in plant tissues, whereas the, majority of extractable [14C] residues was present in the form of conjugates.

The behaviour of “model”; humic acid‐bound residues was comparable to that of “natural”; humic acid‐bound residues or soil‐bound residues.     

A model for tropospheric multiphase chemistry: application to one cloudy event during the CIME experiment

A multiphase box model for a remote environment of the troposphere has been developed with an explicit chemistry for both gas and aqueous phase. The model applied to a set of measurements performed by Voisin et al. (2000) during the European CIME experiment for a cloud event on 13th December 1997 at the top of the Puy de Dôme (France). The results of the simulation are compared to the measurements in order to follow the evolution of the ambient chemical composition as a function of the pH and of the varying water content. After verifying that the model retrieves the main features observed in the behavior of species in the cloud droplets, a detailed analysis of the simulated chemical regime is performed. It essentially discusses the sources and sinks of radical in aqueous phase, the relative importance of the oxidation pathways of volatile organic compounds by the main radicals and the conversion of S(IV) into S(VI) which seems to be influenced by the presence of peroxonitric acid, HNO₄, in aqueous phase in the environmental conditions that are considered with low H₂O₂. These numerical results are then compared with the theoretical study from Herrmann et al. (2000), who proposed a slightly different mechanism, including C2 chemistry and transition metal chemistry whereas they neglect some reaction pathways, such as the one involving OHCH₂O₂ radical. This double confrontation between model results and both real experimental data and numerical results from Herrmann et al. (1999c) underlines limitations of such modeling approach that does not include any dynamical or microphysical coupling but also demonstrates its capability to identify the main oxidants or reactants in aqueous phase in real environmental conditions more realistic than a purely theoretical approach. The originality of this study resides in the explicit and exhaustive ways the chemical reactions are treated in aqueous phase and in a first attempt to compare such a detailed chemical scheme to real environmental conditions.     

Unexpected effects of sublethal doses of insecticide on the peripheral olfactory response and sexual behavior in a pest insect

Pesticides have long been used as the main solution to limit agricultural pests, but their widespread use resulted in chronic or diffuse environmental pollutions, development of insect resistances, and biodiversity reduction. The effects of low residual doses of these chemical products on organisms that affect both targeted species (crop pests) but also beneficial insects became a major concern, particularly because low doses of pesticides can induce unexpected positive—also called hormetic—effects on insects, leading to surges in pest population growth at greater rate than what would have been observed without pesticide application. The present study aimed to examine the effects of sublethal doses of deltamethrin, one of the most used synthetic pyrethroids, known to present a residual activity and persistence in the environment, on the peripheral olfactory system and sexual behavior of a major pest insect, the cotton leafworm Spodoptera littoralis. We highlighted here a hormetic effect of sublethal dose of deltamethrin on the male responses to sex pheromone, without any modification of their response to host-plant odorants. We also identified several antennal actors potentially involved in this hormetic effect and in the antennal detoxification or antennal stress response of/to deltamethrin exposure.     

Determination of soil content in chlordecone (organochlorine pesticide) using near infrared reflectance spectroscopy (NIRS)

Chlordecone is a toxic organochlorine insecticide that was used in banana plantations until 1993 in the French West Indies. This study aimed at assessing the potential of near infrared reflectance spectroscopy (NIRS) for determining chlordecone content in Andosols, Nitisols and Ferralsols from Martinique. Using partial least square regression, chlordecone content conventionally determined through gas chromatography–mass spectrometry could be correctly predicted by NIRS (Q² = 0.75, R² = 0.82 for the total set), especially for samples with chlordecone content <12 mg kg⁻¹ or when the sample set was rather homogeneous (Q² = 0.91, R² = 0.82 for the Andosols). Conventional measures and NIRS predictions were poorly correlated for chlordecone content >12 mg kg⁻¹, nevertheless ca. 80% samples were correctly predicted when the set was divided into three or four classes of chlordecone content. Thus NIRS could be considered a time- and cost-effective method for characterising soil contamination by chlordecone.     

Comprehensive primary particulate organic characterization of vehicular exhaust emissions in France

A study to characterize primary particulate matter (PM_2.5 and PM₁₀) from the French vehicular fleet was conducted during winter 2008, in a tunnel in Marseille, France. The carbonaceous fraction represents 70% of the aerosol mass and elemental carbon fraction (EC) represent 60% of the carbonaceous fraction. The organic carbon OC was characterized in term of its water soluble fraction, functionalization rate and HULIS content. Seventy trace organic compounds including alkanes, polycyclic aromatic hydrocarbons (PAH), petroleum biomarkers and carboxylic acids were also quantified, in order to determine an organic emission profile for chemical mass balance modeling studies. Such source profiles were still missing in Europe and particularly in France. The profile obtained in this study is consistent with profiles determined in tunnel or dynamometer studies performed in other countries during the last ten years. These results suggest that organic compounds profiles from vehicular exhaust emissions are not significantly influenced by the geographic area and are thus suitable for use in aerosol source apportionment modeling applied across extensive regions. The chemical profile determined here is very similar to those obtained for diesel emissions with high concentrations of EC relative to OC (EC/OC = 1.8) and low concentrations of the higher molecular weight PAH. These results are consistent with the high proportion of diesel vehicles in the French fleet (49%).     

Ozone risk assessment for plants: central role of metabolism-dependent changes in reducing power

The combination of stomatal-dependent ozone flux and total ascorbate level is currently presented as a correct indicator for determining the degree of sensitivity of plants to ozone. However, the large changes in carbon metabolism could play a central role in the strategy of the foliar cells in response to chronic ozone exposure, participating in the supply of reducing power and carbon skeletons for repair and detoxification, and modifying the stomatal mode of functioning. To reinforce the accuracy of the definition of the threshold for ozone risk assessment, it is proposed to also consider the redox pool (NAD(P)H), the ratio between carboxylases and the water use efficiency as indicators of the differential ozone tolerance of plants.     

Comparative toxicity of imidacloprid, of its commercial liquid formulation and of diazinon to a non-target arthropod, the microcrustacean Daphnia magna

Imidacloprid (IMI) is at the moment the insecticide with the world's fastest growing sales and is considered possible replacement for the widely used organophosphorus pesticide, diazinon, which is subject to phased revocation in many countries. In this study, biochemical, reproductive and survival parameters of the water flea (Daphnia magna) after chronic exposure to IMI, its commercial liquid formulation Confidor SL 200 and diazinon are presented and compared. According to the lowest observed effect concentrations, diazinon is more toxic to the reproduction of D. magna than IMI and Confidor SL 200, which exert similar toxicity. The same was observed for the survival, except that Confidor SL 200 is more toxic than IMI. In polluted aquatic environments, the actual levels of diazinon are potentially chronically hazardous to the reproduction of D. magna (risk quotient >1). According to very few measured environmental levels of IMI, the latter is not expected to be chronically hazardous, unless it is accidentally spilled in a small pond. In such case, the predicted concentrations of IMI would present a potential chronic risk to D. magna, and a potential acute risk to other aquatic invertebrates. In the future, higher environmental levels of IMI are expected due to its increasing use and physico-chemical properties. The literature survey summarized in this work suggests that further ecotoxicological studies with a broader spectrum of aquatic organisms are needed before IMI is classified as safer than currently applied pesticides.     

Organic pollutants in compost and digestate. Part 2. Polychlorinated dibenzo-p-dioxins, and -furans, dioxin-like polychlorinated biphenyls, brominated flame retardants, perfluorinated alkyl substances, pesticides, and other compounds

Compost and digestate are important recycling fertilizers and have beneficial effects on soil parameters. However, they can contain significant amounts of organic pollutants. Here, the first comprehensive data set on dibenzo-p-dioxins and -furans (PCDD/F), dioxin-like polychlorinated biphenyls (DL-PCB), brominated flame retardants, perfluorinated alkyl substances (PFAS), pesticides, phthalates, nonylphenol and chlorinated paraffins (CP) in source-separated compost and digestate from Switzerland is presented (n = 3-18). The median summation 17PCDD/F and summation 12DL-PCB concentrations were at 3.2 ng I-TEQ kg(-1)dry weight (dw) and 3.0 ng WHO-TEQ kg(-1)dw, respectively. Brominated diphenyl ether 209 (BDE 209) accounted for 72% of the total polyBDE content (10 microg kg(-1)dw). Hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBPA) levels were at 100 and 0.51 microg kg(-1)dw, respectively. PFAS were identified for the first time in compost and digestate (median concentration 6.3 microg kg(-1)dw, summation 21compounds). Out of 269 pesticides analysed, 30 fungicides, 14 herbicides, eight insecticides and one acaricide were detected. Di-(2-ethylhexyl)phthalate (DEHP) median concentration accounted for 280 microg kg(-1)dw and nonylphenol was below the detection limit of 1 mg kg(-1)dw. The sum of short and medium chain CP was between 90 and 390 microg kg(-1)dw. The concentrations observed were at or above the levels found in background soils, which are the main recipient of compost and digestate. Where actually applied, compost can contribute considerably to the total input of organic pollutants to the soil. However, on a total Swiss agricultural area base, inputs seem to be limited.