A full life-cycle bioassay with Cantareus aspersus shows reproductive effects of a glyphosate-based herbicide suggesting potential endocrine disruption.

A full life-cycle (240 days) bioassay using the terrestrial snail, Cantareus aspersus, allowing exposure during embryogenesis and/or the growth and reproduction phases, was used to assess the effects of Bypass®, a glyphosate-based herbicide (GlyBH), on a range of endpoints, including parameters under endocrine control. As a positive control, a mixture (R-A) made of diquat (Reglone®) and nonylphenols (NP, Agral®), known for its endocrine disrupting effects in other organisms, was tested. At environmental concentrations, both pesticides (R-A mixture and GlyBH) enhanced growth but reduced reproduction. The R-A mixture acted mainly on the fecundity through a delay in egg-laying of approximately 20 days and a strongly reduced number of clutches. This latter dysfunction may be caused by a permanent eversion of the penis, suggesting a disrupting effect at the neuro-endocrine level, which prevented normal mating. GlyBH acted on fertility, possibly due to a decrease in the fertilization of eggs laid by adults exposed during their embryonic development. These results, associated with the absence of observed effects on gonad histology of GlyBH exposed snails, suggested that the underlying mechanisms are neuro-endocrine.

Cross-linked cyclodextrin-based material for treatment of metals and organic substances present in industrial discharge waters.

In this study, a polymer, prepared by crosslinking cyclodextrin (CD) by means of a polycarboxylic acid, was used for the removal of pollutants from spiked solutions and discharge waters from the surface treatment industry. In spiked solutions containing five metals, sixteen polycyclic aromatic hydrocarbons (PAH) and three alkylphenols (AP), the material exhibited high adsorption capacities: >99% of Co2+, Ni2+ and Zn2+ were removed, between 65 and 82% of the PAHs, as well as 69 to 90% of the APs. Due to the structure of the polymer and its specific characteristics, such as the presence of carboxylic groups and CD cavities, the adsorption mechanism involves four main interactions: ion exchange, electrostatic interactions and precipitation for metal removal, and inclusion complexes for organics removal. In industrial discharge waters, competition effects appeared, especially because of the presence of calcium at high concentrations, which competed with other pollutants for the adsorption sites of the adsorbent.

How contamination sources and soil properties can influence the Cd and Pb bioavailability to snails.

To better understand the fate of metals in the environment, numerous parameters must be studied, such as the soil properties and the different sources of contamination for the organisms. Among bioindicators of soil quality, the garden snail (Cantareus aspersus) integrates multiple sources (e.g. soil, plant) and routes (e.g. digestive, cutaneous) of contamination. However, the contribution of each source on metal bioavailability and how soil properties influence these contributions have never been studied when considering the dynamic process of bioavailability. Using accumulation kinetics, this study showed that the main assimilation source of Cd was lettuce (68%), whereas the main source of Pb was the soil (90%). The plant contribution increased in response to a 2-unit soil pH decrease. Unexpectedly, an increase in the soil contribution to metal assimilation accompanied an increase in the organic matter (OM) content of the soil. For both metals, no significant excretion and influence of source on excretion have been modelled either during exposure or depuration. This study highlights how the contribution of different sources to metal bioavailability changes based on changes in soil parameters, such as pH and OM, and the complexity of the processes that modulate metal bioavailability.

Responses of wild small mammals to arsenic pollution at a partially remediated mining site in Southern France.

Partial remediation actions at a former gold mine in Southern France led to a mosaic of contaminated and rehabilitated zones. In this study, the distribution of arsenic and its potential adverse effects on small mammals were investigated. The effectiveness of remediation for reducing the transfer of this element into wildlife was also discussed. Arsenic levels were measured in the soil and in the stomach contents, livers, kidneys, and lungs of four small mammal species (the wood mouse (Apodemus sylvaticus), the Algerian mouse (Mus spretus), the common vole (Microtus arvalis), and the greater white-toothed shrew (Crocidura russula)). The animals were caught at the former extraction site, in zones with three different levels of remediation treatments, and at a control site. Arsenic concentrations in the soil were highly spatially heterogeneous (ranging from 29 to 18,900 µg g(-1)). Despite the decrease in arsenic concentrations in the remediated soils, both wood mice and Algerian mice experienced higher oral exposure to arsenic in remediated zones than in the control area. The accumulated arsenic in their organs showed higher intra-zonal variability than the arsenic distribution in the soil, suggesting that, in addition to remediation processes, other variables can help explain arsenic transfer to wildlife, such as the habitat and diet preferences of the animals or their mobility. A weak but significant correlation between arsenic concentration and body condition was observed, and weak relationships between the liver/kidney/lung mass and arsenic levels were also detected, suggesting possible histological alterations.

Snails as indicators of pesticide drift, deposit, transfer and effects in the vineyard.

This paper presents a field-study of real pesticide application conditions in a vineyard. The objective was to measure the exposure, the transfer and the effects of pesticides on a non-target soil invertebrate, the land snail Helix aspersa. There was no drift of the herbicides (glyphosate and glufosinate) whereas the fungicides (cymoxanil, folpet, tebuconazole and pyraclostrobin) were detected up to 20 m from the treated area. For folpet and particularly tebuconazole, spray deposits on soil (corresponding to losses for the intended target i.e. the vine leaves) were high (41.1% and 88.8% loss of applied dose, respectively). For herbicides, the target was the soil and losses (percentage of compounds which did not reach the soil) were of 22% for glufosinate and 52% for glyphosate. In the study plot, glyphosate was transferred to and accumulated in snail tissues (4 mg kg(-1) dry weight, dw), as was its metabolite AMPA (8 mg kg(-1) dw) which could be in relation with the reduced growth observed in snails. No effects on snail survival or growth were found after exposure to the other organic compounds or to copper and sulphur-fungicides, although transfer of tebuconazole, pyraclostrobin and copper occurred. This study brings original field data on the fate of pesticides in a vineyard agro-ecosystem under real conditions of application and shows that transfer and effects of pesticides to a non-target organism occurred.

Optimization of extraction procedure and chromatographic separation of glyphosate, glufosinate and aminomethylphosphonic acid in soil.

Analysing herbicides in soil is a complex issue that needs validation and optimization of existing methods. An extraction and analysis method was developed to assess concentrations of glyphosate, glufosinate and aminomethylphophonic acid (AMPA) in field soil samples. After testing extractions by accelerated solvent extraction and ultrasonic extraction, agitation was selected with the best recoveries. Water was preferred as solvent extraction because it resulted in a cleaner chromatogram with fewer impurities than was the case with alkaline solvents. Analysis was performed by FMOC pre-column derivatization followed by high-performance liquid chromatography (HPLC) on a 300 mm C(18) column which permitted enhanced separation and sensitivity than a 250 mm C(18) column and increased resistance than the NH(2) column for soil samples. This extraction and analysis method allowing a minimum of steps before the injection in the HPLC with fluorescence detection is efficient and sensitive for a clay-loamy soil with detection limits of 103 µg kg(-1) for glyphosate, 15 µg kg(-1) for glufosinate and 16 µg kg(-1) for AMPA in soil samples.

Towards the development of an embryotoxicity bioassay with terrestrial snails: screening approach for cadmium and pesticides.

Currently no bioassays are available to assess the embryotoxicity of chemicals with terrestrial soil invertebrates. We therefore presented a new method for embryotoxicity testing with snail eggs: a relevant biological material that incubates in soil and that can be exposed to contaminants from leachates and soil solution. The effects of aqueous solutions of two herbicide formulations, Reglone(®) (active ingredient (a.i.), diquat) and Roundup(®) or its a.i., glyphosate, of a surfactant (Agral(®) 90, a.i., nonylphenol polyethoxylates) and of cadmium (Cd) were studied. Endpoints were the hatching success and observations of embryo abnormalities after exposure. Roundup(®) was found to be more toxic than its a.i. alone (EC50(a.i.)=18 mg/l and about 1300 mg/l, respectively). Reglone(®) (EC50(a.i.)=0.72 mg/l) and Agral(®) (EC50(a.i.) ≈ 50 mg/l) were also tested together, revealing that Reglone(®) accounted for more than 99% of the mixture's toxicity. An antagonistic interaction between the two substances was found. For Cd (EC50=3.9 mg/l), a significant transfer from exposure medium to eggs was emphasized, particularly affecting the albumen. Abnormalities of embryogenesis in non-hatched embryos depended on the substance and the concentration considered.