Ability of aerated compost tea to increase the mobility and phytoextraction of copper in vineyard soil.

Aerated compost tea (ACT) contains soluble humic substances (SHS) that are expected to alter the dynamics and ecotoxicity of Cu in soil. This study investigated the efficiency of ACT in enhancing the mobility and phytoextraction of Cu in vineyard soil. Crimson clover (Trifolium incarnatum L.) was grown on a vineyard soil at three concentrations of Cu (90, 261 and 432 mg kg-1), and supplied (or not) with ACT, then sampled after 56 days to determine the amount of Cu phytoextracted. Soil was extracted with 0.01 M KCl and potentiometric analyses were performed to measure the impact of ACT on the speciation of Cu in the extraction solution. ACT was found to increase the mobility of Cu in the soil by a factor of 3-14 depending on the soil Cu content and on the soil extraction date. The increase in Cu mobility was associated with an increase in absorbance at 254 nm and with a decrease in the free ionic fraction of Cu in the KCl extract, suggesting that Cu was mainly mobilized by the SHS present in the compost tea, and through a ligand-controlled dissolution process. ACT increased Cu phytoextraction at Cu90 and Cu261 by on average 80% thanks to its positive impact on plant growth, and on Cu accumulation in plant shoots, whereas it reduced Cu phytoextraction at Cu432 due to its deleterious effect on plant growth at this soil Cu content. ACT is thus an efficient way to increase the phytoavailability of Cu in soil, but probably should not be used in vineyard soils that are highly contaminated by Cu. To obtain Cu phytoextraction yields in line with the needs of the wine sector, the use of ACT needs to be associated with the cultivation of a Cu-accumulating plant.

Changes over time in organic matter dynamics and copper solubility in a vineyard soil after incorporation of cover crop residues: Insights from a batch experiment.

Cover crops (CCs) are increasingly used in viticulture because they benefit the soil and the environment in many ways. This study investigated the extent to which the incorporation of CC residues altered organic matter (OM) and Cu dynamics in a Cu-contaminated vineyard topsoil. A 92-day incubation period was used to monitor changes over time in carbon mineralization, carbon hydrolytic enzyme activity, concentration and optical properties of dissolved organic matter (DOM), and Cu solubility after the addition (or not) of two CC residues, oat or faba bean. The results revealed that adding CCs transitorily increased the concentration of DOM in soil solution, as well as the activity of C hydrolytic enzymes and C mineralization rates. DOM content was approximately two orders of magnitude higher in CC-amended soils than in the control soil on day 0, after which it gradually decreased to reach concentrations similar to those measured in the control soil on day 92. Analyses of DOM optical properties showed that its molecular weight and degree of humification increased over time with a decrease in its concentration. The close relationship between DOM and Cu concentrations in the soil solution suggests that degradation of CCs releases soluble forms of C capable of complexing and solubilizing Cu, and hence that incorporating CC residues can transitorily increase the solubility of Cu in vineyard topsoils. Despite their different C:N ratios, oat and faba bean had almost the same effect on Cu dynamics, implying that C inputs played a prominent role in explaining the interactions between OM and Cu within the timeframe of our experiment. In conclusion, this study enabled recommendations on how to mitigate the risk of Cu ecotoxicity associated with incorporating CCs in Cu-contaminated vineyard soils.

Do DOM optical parameters improve the prediction of copper availability in vineyard soils?

Accumulation of copper (Cu) in soils due to the application of fungicides may be toxic for organisms and hence affect winegrowing sustainability. Soil parameters such as pH and dissolved organic matter (DOM) are known to affect the availability of Cu. In this study, we investigated the contribution of chromophoric and fluorescent DOM properties to the prediction of Cu availability in 18 organic vineyard soils in the Bordeaux winegrowing area (France). The DOM parameters, assessed through absorbance and fluorescence analyses, and proxies for Cu availability (total soluble Cu and free ionic Cu2+) were measured in 0.01 M KCl extracts. Total soluble Cu (CuKCl) varied 23-fold while free ionic Cu2+ varied by a factor of 4600 among the soils. DOC concentrations were similar among the soils, but the samples differed in the quality of DOM as assessed by optical spectroscopy. Multilinear regression models with and without DOM quality parameters were investigated to predict Cu availability. The best model for CuKCl successfully explained 83% of variance and included pH, CuT, and two DOM fluorescence quality indices, the FI fluorescence index, which distinguishes between microbial and higher plant origins, and the HIX humification index. For the prediction of Cu2+, pH alone explained 88% of variance and adding DOM parameters did not improve modelling. The two Cu availability proxies were related to pH. This study confirms the prominent role of pH in Cu availability and underlines the importance of DOM quality to better predict Cu solubility.

Multielementary (Cd, Cu, Pb, Zn, Ni) Stable Isotopic Exchange Kinetic (SIEK) method to characterize polymetallic contaminations.

A new method is proposed to precisely and simultaneously quantify the exchangeable pool of metals in soils and to describe its reactivity at short- and long-term. It is based on multielementary Stable Isotopic Exchange Kinetics (multi-SIEK), first validated by a comparison between two monoelementary radioactive ((109)Cd*, (65)Zn*) IEK experiments, a mono- ((106)Cd) and multi- ((62)Ni, (65)Cu, (67)Zn, (106)Cd, (204)Pb) SIEK. These experiments were performed on a polluted soil located near the Zn smelter plant of Viviez (Lot watershed, France). The IEK results obtained for Cd and Zn were consistent across the experiments. (109)Cd*, (65)Zn* IEK, and multi-SIEK were then applied on 3 non- and moderate impacted soils that also provided consistent results for Cd and Zn. Within these experimental conditions, it can be concluded that no competition occurs between Cd, Zn, and the other metals during SIEK. Multi-SIEK results indicate that the isotopically exchangeable pool of Ni, Zn, and Cu are small (E(Ni), E(Zn), and E(Cu) values up to 17%) whatever the pollution degree of the soils considered in this study and whatever the duration of the interaction. On the contrary, Cd displays the highest E values (from 35% to 61% after 1 week), and E(Pb) displays a maximum value of 26% after 1 week. The multi-SIEK provides useful information on metal sources and reactivity relationship. Ni would be located in stable pedogenic phases according to its very low enrichment factor. The low E(Zn) and E(Cu) are consistent with location of Zn and Cu in stable phases coming from tailings erosion. Though Pb enrichments in soils may also be attributed to tailings particles, its larger exchangeable pool suggests that the Pb-bearing phases are more labile than those containing Zn and Cu. The high mobility of Cd in upstream soils indicates that it has been mostly emitted as reactive atmospheric particles during high temperature ore-treatment.

Stable Cu Isotope Ratios Show Changes in Cu Uptake and Transport Mechanisms in Vitis vinifera Due to High Cu Exposure.

Even though copper (Cu) is an essential plant nutrient, it can become toxic under certain conditions. Toxic effects do not only depend on soil Cu content, but also on environmental and physiological factors, that are not well understood. In this study, the mechanisms of Cu bioavailability and the homeostasis of Vitis vinifera L. cv. Tannat were investigated under controlled conditions, using stable Cu isotope analysis. We measured Cu concentrations and δ65Cu isotope ratios in soils, soil solutions, roots, and leaves of grapevine plants grown on six different vineyard soils, in a 16-week greenhouse experiment. The mobility of Cu in the soil solutions was controlled by the solubility of soil organic matter. No direct relationship between Cu contents in soils or soil solutions and Cu contents in roots could be established, indicating a partly homeostatic control of Cu uptake. Isotope fractionation between soil solutions and roots shifted from light to heavy with increasing Cu exposure, in line with a shift from active to passive uptake. Passive uptake appears to exceed active uptake for soil solution concentrations higher than 270 µg L-1. Isotope fractionation between roots and leaves was increasingly negative with increasing root Cu contents, even though the leaf Cu contents did not differ significantly. Our results suggest that Cu isotope analysis is a sensitive tool to monitor differences in Cu uptake and translocation pathways even before differences in tissue contents can be observed.

Kinetic degradation processes of butyl- and phenyltins in soils.

The degradation of organotin compounds (OTC) in agricultural and forest soils is studied in sandy soil samples. Individual experiments involving the three butyl- and the three phenyltins were carried out during 90 d in controlled conditions (darkness, 28 degrees C, aerobic conditions, 13% moisture) and with spiking concentration representative of environmental levels (20-50 micrg(Sn) kg(-1)). After the validation of first-order degradation kinetic model, mechanisms involved throughout the study were considered. Degradation pathways are proposed for butyl- and phenyltins and discussed according to literature data. The degradation of mono- (MBT, MPhT), di-organotins (DBT, DPhT) and TBT is clearly identified as a single successive loss of an organic group whereas TPhT is directly degraded to MPhT. The half-life times were dependent on their substitution degree, ranging from 24 (TPhT) to 220 (MBT) d. The less substituted the OTC is, the more persistent it is. In the range 4.3-5.7, pH does not seem to influence OTC degradation under the present operating conditions. Finally this study shows the significant persistence in soil samples in our experimental conditions for most of studied organotins and highlights the potential impact on soil quality.

Using a dune forest as a filtering ecosystem for water produced by a treatment plant - One decade of environmental assessment.

A dune forest in SW France composed of maritime pines was irrigated with treated wastewater for a decade in an experiment (including irrigated plots versus control plots) to evaluate the environmental impact of applying wastewater on the water table, soil properties, and plants. The amount of treated wastewater (1921 mm yr-1) applied was twice the annual precipitation. Nutrient inputs were also very high, particularly nitrogen (N: 539 kg-N ha-1 yr-1), phosphorus (P: 102 kg-P ha-1 yr-1), and calcium (Ca: 577 kg-Ca ha-1 yr-1). Irrigation caused a rise in the water table, and increased its sodium (Na), NO3-, potassium (K), and calcium concentrations. Soil properties were affected by irrigation at least down to a depth of 1.2 m. After eight years of irrigation, soil pH had increased by 1.4 units, and soil available P content (POlsen) increased nearly 8-fold. In the short-term (i.e. 1-3 years), irrigation with treated wastewater improved growth, standing biomass, and the nutritional status of the vegetation. But tree dieback started in the fourth year of irrigation and worsened until the end of the monitoring period when almost all the irrigated trees were dead or moribund. The understory composition was drastically modified by irrigation, with an increase in α-biodiversity and in the biomass of herbaceous species, and a reduction in woody species abundance. The factor that best explained tree dieback was manganese nutrition (Mn): (i) the Mn content of the tree foliage was negatively affected by irrigation and below the deficiency values reported for pine species, and (ii) soil available Mn (CaCl2 extraction) decreased by half in the topsoil layer. Manganese deficiency was probably the consequence of the increase in soil pH, which in turn reduced soil Mn availability. Tree dieback was not related to either to a macronutrient deficiency or to toxicity caused by a trace element.

RECOTOX, a French initiative in ecotoxicology-toxicology to monitor, understand and mitigate the ecotoxicological impacts of pollutants in socioagroecosystems.

RECOTOX is a cross-cutting initiative promoting an integrated research to respond to the challenges of monitoring, understanding, and mitigating environmental and health impacts of pesticides in agroecosystems. The added value of RECOTOX is to develop a common culture around spatial ecotoxicology including the whole chain of pressure-exposure-impact, while strengthening an integrated network of in natura specifically equipped sites. In particular, it promotes transversal approaches at relevant socioecological system scales, to capitalize knowledge, expertise, and ongoing research in ecotoxicology and, to a lesser extent, environmental toxicology. Thus, it will open existing research infrastructures in environmental sciences to research programs in ecotoxicology of pesticides.

Predictive statistical modelling of cadmium content in durum wheat grain based on soil parameters.

Regulatory limits on cadmium (Cd) content in food products are tending to become stricter, especially in cereals, which are a major contributor to dietary intake of Cd by humans. This is of particular importance for durum wheat, which accumulates more Cd than bread wheat. The contamination of durum wheat grain by Cd depends not only on the genotype but also to a large extent on soil Cd availability. Assessing the phytoavailability of Cd for durum wheat is thus crucial, and appropriate methods are required. For this purpose, we propose a statistical model to predict Cd accumulation in durum wheat grain based on soil geochemical properties related to Cd availability in French agricultural soils with low Cd contents and neutral to alkaline pH (soils commonly used to grow durum wheat). The best model is based on the concentration of total Cd in the soil solution, the pH of a soil CaCl2 extract, the cation exchange capacity (CEC), and the content of manganese oxides (Tamm's extraction) in the soil. The model variables suggest a major influence of cadmium buffering power of the soil and of Cd speciation in solution. The model successfully explains 88% of Cd variability in grains with, generally, below 0.02 mg Cd kg-1 prediction error in wheat grain. Monte Carlo cross-validation indicated that model accuracy will suffice for the European Community project to reduce the regulatory limit from 0.2 to 0.15 mg Cd kg-1 grain, but not for the intermediate step at 0.175 mg Cd kg-1. The model will help farmers assess the risk that the Cd content of their durum wheat grain will exceed regulatory limits, and help food safety authorities test different regulatory thresholds to find a trade-off between food safety and the negative impact a too strict regulation could have on farmers.

Metal concentrations in edible mushrooms following municipal sludge application on forest land.

In the context of biosolids utilisation in forestry, effects of sludge application on mushroom metal concentration were studied in six sites of maritime pine forests in the South-West of France. Municipal sludge were applied at a rate of 6 T dry matter per hectare. Edible mushrooms were collected two years after sludge application. As, Cd, Cu, Hg, Pb, Se and Zn concentrations were determined. Results showed a high variability for trace element concentrations in mushrooms collected from control areas. No significant correlation was found between soil parameters (pH and trace elements concentrations) and mushroom trace element concentrations. Even if the concentration of trace metals increased in the soils, sludge application did not affect As, Cu, Se and Zn concentrations in carpophores but slightly increased Cd, Pb and Hg concentrations on some sites. This effect is dependent on sludge type and sites.

TBT and TPhT persistence in a sludged soil.

The persistence of tributyltin (TBT) and triphenyltin (TPhT) in soils was studied, taking into consideration the quantity of sewage sludge, TBT and TPhT concentrations in soil as well as the soil pH. The organotin compounds (OTC) were introduced into the soil via a spiked urban sludge, simulating agricultural practise. OTC speciation was achieved after acidic extraction of soil samples followed by gas chromatography-pulsed flame photometric analysis (GC-PFPD). Leaching tests conducted on a spiked sludge showed that more than 98% of TBT are sorbed on the sludge. TBT persistence in soil appeared to depend on its initial concentration in sludge. Thus, it was more important when concentration is over 1000 microg(Sn) kg(-1) of sludge. More than 50% of the initial TBT added into the soil were still present after 2 months, whatever the experimental conditions. The main degradation product appeared to be dibutyltin. About 90% of TPhT were initially sorbed on sludge, whatever the spiking concentration in sludge was. However, TPhT seemed to be quantitatively exchangeable at the solid/liquid interface, according to the leaching tests. It was also significantly degraded in sludged soil as only about 20% of TPhT remain present after 2 months, the monophenyltin being the main degradation product. pH had a significant positive effect on TBT and particularly TPhT persistence, according to the initial amounts introduced into the soil. Thus, at pH over 7 and triorganotin concentration over 100 microg(Sn) kg(-1), less than 10% of TBT but about 60% of TPhT were degraded. When the sludge was moderately contaminated by triorganotins (typically 50 microg(Sn) kg(-1) in our conditions) the pH had no effect on TBT and TPhT persistence.

Report on the fifth meeting of INRA's national network of ecotoxicologists, ECOTOX.

The fifth meeting of INRA's national network of ecotoxicologists took place on 25 to 27 November 2014 in Biarritz, France. The main aim of the meeting was to bring together ecotoxicologists from INRA and associated partners, providing them ample opportunity to share and discuss their latest scientific results as well as the national policy of research in ecotoxicology and to precise perspectives for the network.

Tributyltin and triphenyltin uptake by lettuce.

This paper provides quantitative information on the transfer of TBT (tributyltin) and TPhT (triphenyltin) from sludged soil to cultivated lettuce. The effect of their initial concentrations in the soil (varying from 20 to 50 microg(Sn)kg(-1) for each triorganotin), sludge amount (between 1% and 9%), and cultivation duration (32-54 days) was evaluated by means of experimental designs. The impact of the cultivation temperature at 13 degrees C and 19 degrees C on organotin fate in the soil/plant system was also considered. The final concentration of a given organotin in the plant roots was found to depend directly on its initial concentration in the soil. A total of (85+/-15)% of initial TBT in the soil was still present at the end of the experiments, regardless of the cultivation duration. Consequently, TBT appeared to be taken up by lettuce continually. A total of (75+/-5)% of TPhT was found to be degraded in the soil at 54 days. So, this compound could have been taken up by the plant at the beginning of the cultivation. Sludge amount seemed to have a negative effect on TPhT concentration in a plant at 32 days. This could be due to the quantitative TPhT sorption onto the sludge, observed just after spiking. Organotin plant uptake appeared to be more important at 19 degrees C than at 13 degrees C. TBT and TPhT were mainly accumulated in the roots, and up to 2% and 10% of TPhT and TBT, respectively, were translocated to the shoots. Despite TPhT degradation, products in large amounts were present in the soil and were not significantly taken up by the plant. They possibly remained immobilized on solid phases of the sludged soil.

Analytical advances in butyl-, phenyl- and octyltin speciation analysis in soil by GC-PFPD.

The development and validation of a method for organotin analysis in soils, including butyl-, phenyl- and octyl-tins, are described in this study. The influence of pretreatment step based on sample lyophilization was first studied. Different solid-liquid extraction techniques including mechanical stirring (MSAE), accelerated solvent (ASE), microwave (MAE) and ultrasound (UAE), were compared. MSAE gave the best recoveries and repeatability and was thus chosen for OTC extraction from soils. Then, ethylation/extraction step before GC-PFPD analysis was investigated and the best derivatisation conditions were assessed in order to achieve a simple, non-expensive and reliable routine procedure. Finally, the robustness of the method was tested by the analysis of several soils with different organic matter content allowing the validation of developed protocol. The method appears to be reliable and accurate for the OTC determination in a broad range of soils.