Evidence of Chlordecone Resurrection by Glyphosate in French West Indies.

The widespread use of pesticides in agriculture during the last several decades has contaminated soils and different Critical Zone (CZ) compartments, defined as the area extended from the top of the vegetation canopy to the groundwater table, and it integrates interactions of the atmosphere, lithosphere, biosphere, and hydrosphere. However, the long-term fate, storage, and transfer dynamics of persistent pesticides in CZ in a changing world remain poorly understood. In the French West Indies, chlordecone (CLD), a toxic organochlorine insecticide, was extensively applied to banana fields to control banana weevil from 1972 to 1993 after which it was banned. Here, to understand CZ trajectories we apply a retrospective observation based on marine sediment core analyses to monitor long-term CLD transfer, fate, and consequences in Guadeloupe and Martinique islands. Both CLD profiles show synchronous chronologies. We hypothesized that the use of glyphosate, a postemergence herbicide, from the late 1990s onward induced CZ modification with an increase in soil erosion and led to the release of the stable CLD stored in the soils of polluted fields. CLD fluxes drastically increased when glyphosate use began, leading to widespread ecosystem contamination. As glyphosate is used globally, ecotoxicological risk management strategies should consider how its application affects persistent pesticide storage in soils, transfer dynamics, and widespread contamination.

Physico-chemical and agronomic results of soil remediation by In Situ Chemical Reduction applied to a chlordecone-contaminated nitisol at plot scale in a French Caribbean banana plantation.

The In Situ Chemical Reduction (ISCR) process was tested in a nitisol in a French Caribbean banana plantation using five different soil amendments. The addition of 2.8% or 4.0% of Zero Valent Iron (ZVI; dw/dw, 2 different trial plots) in the 0-40-cm soil layer lowered the initial chlordecone (CLD) concentration by up to 74% or 69% in 37 days or 94 days, with 75% of the decrease achieved after only 21 or 24 days of treatment depending on the trial plot. The addition of commercially available Daramend® was also tested by applying the 6% dose (dw/dw) recommended by the manufacturer and using either the regular alfalfa-based product or a bagasse-based product specifically formulated for the study. Both significantly lowered CLD concentrations, but to a lesser extent than with the ZVI-only amendment. A bagasse-ZVI mixture prepared on site produced results slightly better than the two Daramend®. The percentage decreases in CLD concentrations were correlated with the negative redox potentials achieved. In all the trial plots, dechlorinated transformation products appeared in the soil and soil water as the CLD concentrations decreased, with H atoms replacing up to 4 and 7 of the 10 Cl atoms, respectively. None of these degradation products appeared to accumulate in the soil or soil water during the treatment. Instead, the reverse occurred, with an overall downward trend in their concentrations over time. The effects of ISCR treatment on agronomic and human health-related parameters were measured in three different crops. The radishes produced with some treatments were visually of lower quality or smaller in size than those grown in the control plots. Lower yields were observed for the cucumbers and sweet potatoes grown after applying the bagasse-based amendments. Mortality among cucumber seedlings was observed after treatment with ZVI only. Simple operational solutions should suffice to remedy these negative agronomic effects. As regards human health-related effects, the CLD concentrations in radishes grown with three of the amendments were significantly lower than in the two control plots and well below the maximum residue level (MRL), which was substantially exceeded in the radishes grown on untreated soil. For cucumbers, the treatments with regular Daramend® and with a local bagasse-ZVI mixture produced fruits with CLD below the MRL and also below the concentrations in one of the two control plots. As for the sweet potatoes, adding a bagasse-ZVI mixture had a significant positive effect by decreasing contamination below the levels in the two control plots and below the MRL.

Spatio-temporal variability of water pollution by chlordecone at the watershed scale: what insights for the management of polluted territories?

Chlordecone, applied on soils until 1993 to control banana weevil, has polluted water resources in the French West Indies for more than 40 years. At the watershed scale, chlordecone applications were not homogenous, generating a spatial heterogeneity of the pollution. The roles of climate, hydrology, soil, agronomy, and geology on watershed functioning generate a temporal heterogeneity of the pollution. This study questions the interactions between practices and the environment that induce such variability. We analyzed hydrological and water pollution datasets from a 2-year monitoring program on the Galion watershed in Martinique (French West Indies). We conjointly analyzed (i) weekly chlordecone (CLD) concentration monitored on 3 river sampling sites, (ii) aquifer piezometric dynamics and pollutions, and (iii) agricultural practices on polluted soils. Our results showed that chlordecone pollution in surface waters are characterized by annual trends and infra-annual variations. Aquifers showed CLD concentration 10 times higher than surface water, with CLD concentration peaks during recharge events. We showed strong interactions between rainfall events and practices on CLD pollution requiring a systemic management approach, in particular during post-cyclonic periods. Small sub-watershed with high CLD pollution appeared to be a substantial contributor to CLD mass transfers to the marine environment via rivers and should therefore receive priority management. We suggest increasing stable organic matter return to soil as well as external input of organic matter to reduce CLD transfers to water. We identified hydrological conditions-notably drying periods-and tillage as the most influential factors on CLD leaching. In particular, tillage acts on 3 processes that increases CLD leaching: organic matter degradation, modification of water paths in soil, and allophane clay degradation.

Relationships between past and present pesticide applications and pollution at a watershed outlet: The case of a horticultural catchment in Martinique, French West Indies.

The understanding of factors affecting pesticide transfers to catchment outlet is still at a very early stage in tropical context, and especially on tropical volcanic context. We performed on-farm pesticide use surveys during 87 weeks and monitored pesticides in water weekly during 67 weeks at the outlet of a small catchment in Martinique. We identified three types of pollution. First, we showed long-term chronic pollution by chlordecone, diuron and metolachlor resulting from horticultural practices applied 5-20 years ago (quantification frequency higher than 80%). Second, we showed peak pollution. High amounts of propiconazole and fosthiazate applied at low frequencies caused river pollution peaks for weeks following a single application. Low amounts of diquat and diazinon applied at low frequencies also caused pollution peaks. The high amounts of glyphosate applied at high frequency resulted into pollution peaks by glyphosate and aminomethylphosphonic acid (AMPA) in 6 and 20% of the weeks. Any intensification of their uses will result in higher pollution levels. Third, relatively low amounts of glufosinate-ammonium, difenoconazol, spinosad and metaldehyde were applied at high frequencies. Unexpectedly, such pesticides remained barely detected (<1.5%) or undetected in water samples. We showed that AMPA, fosthiazate and propiconazole have serious leaching potential. They might result in future chronic pollution of shallow aquifers alimenting surface water. We prove that to avoid the past errors and decrease the risk of long-term pollution of water resources, it is urgent to reduce or stop the use of pesticides with leaching potential by changing agricultural practices.

Soil thresholds and a decision tool to manage food safety of crops grown in chlordecone polluted soil in the French West Indies.

Due to the persistent pollution of soils by an organochlorine, chlordecone (CLD also known as Kepone ©) in the French West Indies, some crops may be contaminated beyond the European regulatory threshold, the maximum residue limit (MRL). Farmers need to be able to foresee the risk of not complying with the regulatory threshold in each field and for each crop, if not, farmers whose fields are contaminated would have to stop cultivating certain crops in the fields concerned. To help farmers make the right choices, we studied the relationship between contamination of the soil and contamination of crops. We showed that contamination of a crop by CLD depended on the crop concerned, the soil CLD content and the type of soil. We grouped crop products in three categories: (i) non-uptakers and low-uptakers, (ii) medium-uptakers, and (iii) high-uptakers, according to their level of contamination and the resulting risk of exceeding MRL. Using a simulation model, we computed the soil threshold required to ensure the risk of not complying with MRL was sufficiently low for each crop product and soil type. Threshold values ranged from 0.02 µgkg-1 for dasheen grown in nitisol to 1.7 µgkg-1 for yam grown in andosol in the high-uptake category, and from 1 µgkg-1 for lettuce grown in nitisol to 45 µgkg-1 for the leaves of spring onions grown in andosol in the medium-uptake category. Contamination of non-uptakers and low-uptakers did not depend on soil contamination. With these results, we built an easy-to-use decision support tool based on two soil thresholds (0.1 and 1 µgkg-1) to enable growers to adapt their cropping system and hence to be able to continue farming.

Compost addition reduces porosity and chlordecone transfer in soil microstructure.

Chlordecone, an organochlorine insecticide, pollutes soils and contaminates crops and water resources and is biomagnified by food chains. As chlordecone is partly trapped in the soil, one possible alternative to decontamination may be to increase its containment in the soil, thereby reducing its diffusion into the environment. Containing the pesticide in the soil could be achieved by adding compost because the pollutant has an affinity for organic matter. We hypothesized that adding compost would also change soil porosity, as well as transport and containment of the pesticide. We measured the pore features and studied the nanoscale structure to assess the effect of adding compost on soil microstructure. We simulated changes in the transport properties (hydraulic conductivity and diffusion) associated with changes in porosity. During compost incubation, the clay microstructure collapsed due to capillary stresses. Simulated data showed that the hydraulic conductivity and diffusion coefficient were reduced by 95 and 70% in the clay microstructure, respectively. Reduced transport properties affected pesticide mobility and thus helped reduce its transfer from the soil to water and to the crop. We propose that the containment effect is due not only to the high affinity of chlordecone for soil organic matter but also to a trapping mechanism in the soil porosity.

Comparative fate of an organochlorine, chlordecone, and a related compound, chlordecone-5b-hydro, in soils and plants.

We address the problem of the comparative environmental fate of a pesticide, chlordecone (CLD), and a related compound, chlordecone-5b-hydro (CLD-5b-hydro). We used a large database including data from two types of contaminated volcanic soils, andosol and nitisol, and thirteen crops grown in the French West Indies in historically polluted soils. We performed in-depth statistical analysis of the effect of different parameters (soil type, crop, organ, etc.) on the ratio of CLD-5b-hydro to CLD in both soils and plants. The environmental fate of the two compounds differed depending on the type of soil. Proportionally, more CLD-5b-hydro than CLD was measured in nitisols than in andosols. Compared to CLD, we also found a preferential transfer of CLD-5b-hydro from the soil to the plant. Finally, mobilization of the two compounds differed according to the species of crop but also within the plant, with increasing ratios from the roots to the top of the plant. The properties of the compound played a key role in the underlying processes. Because CLD-5b-hydro is more soluble in water and has a lower K(ow) than CLD, CLD-5b-hydro (1) was more easily absorbed from soils by plants, (2) was less adsorbed onto plant tissues and (3) was transported in greater quantities through the transpiration stream. Due to the amounts of CLD-5b-hydro we measured in some plant parts such as cucurbit fruits, an assessment of the toxicity of this CLD monodechlorinated product is recommended.

Contamination of free-range ducks by chlordecone in Martinique (French West Indies): a field study.

The former use of chlordecone (CLD) in the French West Indies has resulted in long-term pollution of soils and subsequently of food chains. In contaminated areas, free-range ducks used to control weeds in orchards may be exposed to CLD through polluted soil ingestion. The question arises whether they may be consumed. Muscovy ducks were raised on a guava orchard planted on a soil moderately contaminated (410 µg CLD/kg dry matter). Ducks were raised indoor up to 6 weeks of age and allowed to range freely outdoors thereafter. Twenty-nine females were sequentially slaughtered by groups of 2 to 5 ducks, after 4, 16, 19, 22 or 26 weeks spent in the orchard or after 16-17 weeks in the orchard followed by 3, 6 or 9 weeks in a closed shelter for depuration. CLD concentration increased from 258 to 1051, 96 to 278, 60 to 169 and 48 to 145 µg/kg fresh matter (FM) as the exposure through grazing increased from 4 to 22 weeks, in liver, abdominal fat and leg with and without skin, respectively. Eggs collected in the orchard contained up to 1001 µg CLD/kg FM. All these values exceeded the Maximum Residue Limit (MRL) of 20 µg/kg FM. CLD concentration in all tissues was divided by around 10 within the 9-week confinement period. Despite this quite rapid decontamination, it is estimated that 12-13 weeks would be required to achieve the MRL in liver and in eggs, and 5-6 weeks in leg muscle. Such durations would be too long in practice. Thus, the consumption of products from free-range ducks should be avoided, even in areas mildly contaminated with CLD.

Effect of home food processing on chlordecone (organochlorine) content in vegetables.

Decades after their use and their ban, organochlorine pesticides still pollute soil, water and food and lead to human and ecosystem exposure. In the case of chlordecone, human exposure is mainly due to the consumption of polluted food. We studied the effect of preparation and cooking in five vegetable products, three root vegetables (yam, dasheen and sweet potato) and two cucurbits (cucumber and pumpkin), among the main contributors to exposure to chlordecone in food in the French West Indies. Boiling the vegetables in water had no effect on chlordecone content of the vegetables and consequently on consumer exposure. The peel was three to 40-fold more contaminated than the pulp except cucumber, where the difference was less contrasted. The edible part is thus significantly less contaminated and peeling is recommended after rinsing to reduce consumer exposure, particularly for food grown in home gardens with contaminated soils. The type of soil had no consistent effect on CLD distribution but plot did. Peel and pulp composition (lipids and fibers) appear to partially account for CLD distribution in the product.

Decision support tool for soil sampling of heterogeneous pesticide (chlordecone) pollution.

When field pollution is heterogeneous due to localized pesticide application, as is the case of chlordecone (CLD), the mean level of pollution is difficult to assess. Our objective was to design a decision support tool to optimize soil sampling. We analyzed the CLD heterogeneity of soil content at 0-30- and 30-60-cm depth. This was done within and between nine plots (0.4 to 1.8 ha) on andosol and ferralsol. We determined that 20 pooled subsamples per plot were a satisfactory compromise with respect to both cost and accuracy. Globally, CLD content was greater for andosols and the upper soil horizon (0-30 cm). Soil organic carbon cannot account for CLD intra-field variability. Cropping systems and tillage practices influence the CLD content and distribution; that is CLD pollution was higher under intensive banana cropping systems and, while upper soil horizon was more polluted than the lower one with shallow tillage (<40 cm), deeper tillage led to a homogenization and a dilution of the pollution in the soil profile. The decision tool we proposed compiles and organizes these results to better assess CLD soil pollution in terms of sampling depth, distance, and unit at field scale. It accounts for sampling objectives, farming practices (cropping system, tillage), type of soil, and topographical characteristics (slope) to design a relevant sampling plan. This decision support tool is also adaptable to other types of heterogeneous agricultural pollution at field level.

Relative bioavailability of tropical volcanic soil-bound chlordecone in laying hens (Gallus domesticus).

The former use of chlordecone (CLD) in the French West Indies has resulted in long-term pollution of soils and of food chains. CLD may be transferred into eggs of hens reared outdoors, through polluted soil ingestion. Tropical volcanic soils display variable capacities of pollutant retention: CLD is less available and more persistent in andosol than in nitisol. The impact of soil type on CLD bioavailability to hens was tested through a relative bioavailability study. The deposition of CLD in egg yolk and in abdominal fat was measured in 42 individually housed laying hens fed with diets containing graded levels of CLD from polluted andosol, nitisol, or spiked oil during 23 days. Within each ingested matrix, the concentration of CLD in yolk and in abdominal fat linearly increased with the amount of ingested CLD (P < 0.001). However, the response to andosol diets and to nitisol diets was not different from the response to oil diets (P > 0.1), indicating that CLD was equally bioavailable to laying hens, irrespective of the matrix. This suggests that the hen's gastrointestinal tract efficiently extracts CLD from the two tropical volcanic soils, regardless of their retention capacity. Thus, hens reared on polluted soils with CLD may lay contaminated eggs.

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 (Q(2) = 0.75, R(2) = 0.82 for the total set), especially for samples with chlordecone content <12 mg kg(-1) or when the sample set was rather homogeneous (Q(2) = 0.91, R(2) = 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.