Long-term pollution by chlordecone of tropical volcanic soils in the French West Indies: New insights and improvement of previous predictions.

Chlordecone (CLD), was widely applied in banana fields in the French West Indies from 1972 to 1993. The WISORCH model was constructed to assess soil contamination by CLD and estimated that it lasts from 100 to 600 years, depending on leaching intensity and assuming no degradation. However, recent studies demonstrated that CLD is degraded in the environment, hence questioning the reliability of previous estimations. This paper shows how to improve the model and provides insights into the long-term dissipation of CLD. In-situ observations were made in nearly 2545 plots between 2001 and 2020, and 17 plots were sampled at two dates. Results of soil analyses showed an unexpected 4-fold decrease in CLD concentrations in the soil, in contrast to simulations made using the first version of WISORCH at the time. Neither erosion, nor CLD leaching explained these discrepancies. In a top-down modeling approach, these new observations of CLD concentrations led us to implement a new dissipation process in the WISORCH model that corresponds to a DT50 dissipation half-life of 5 years. The new version of the improved model allowed us to update the prediction of the persistence of soil pollution, with soil decontamination estimated for the 2070s. This development calls for re-evaluation of soil pollution status. Further validation of the new version of WISORCH is needed so it can contribute to crop management on contaminated soil.

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.

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.

Physical limitation of pesticides (chlordecone) decontamination in volcanic soils: fractal approach and numerical simulation.

In the French West Indies, the chlordecone (organochloride pesticide) pollution is now diffuse becoming new contamination source for crops and environment (water, trophic chain). Decontamination by bioremediation and chemical degradation are still under development but the physical limitations of these approaches are generally not taken into account. These physical limitations are related to the poor physical accessibility to the pesticides in soils because of the peculiar structural properties of the contaminated clays (pore volume, transport properties, permeability, and diffusion). Some volcanic soils (andosols), which represent the half of the contaminated soils in Martinique, contain nanoclay (allophane) with a unique structure and porous properties. Andosols are characterized by pore size distribution in the mesoporous range, a high specific surface area, a large pore volume, and a fractal structure. Our hypothesis is that the clay microstructure characteristics are crucial physico-chemical factors strongly limiting the remediation of the pesticide. Our results show that allophane microstructure (small pore size, hierarchical microstructure, and tortuosity) favors accumulation of chlordecone, in andosols. Moreover, the clay microporosity limits the accessibility of microorganisms and chemical species able to decontaminate because of poor transport properties (permeability and diffusion). We model the transport properties by two approaches: (1) we use a numerical model to simulate the structure of allophane aggregates. The algorithm is based on a cluster-cluster aggregation model. From the simulated data, we derived the pore volume, specific surface area, tortuosity, permeability, and diffusion. We show that transport properties strongly decrease because of the presence of allophane. (2) The fractal approach. We characterize the fractal features (size of the fractal aggregate, fractal dimension, tortuosity inside allophane aggregates) and we calculate that transport properties decrease of several order ranges inside the clay aggregates. These poor transport properties are important parameters to explain the poor accessibility to pollutants in volcanic soils and should be taken into account by future decontamination process. We conclude that for andosols, this inaccessibility could render inefficient some of the methods proposed in the literature.

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.