Pesticide fate modelling in conservation tillage: Simulating the effect of mulch and cover crop on S-metolachlor leaching.

Conservation tillage practices mainly based on cover crops and no-tillage with accumulation of crop residues at the soil surface (mulch) modify the environmental fate of pesticides. However, only few pesticide fate models are able to consider mulch of crop residues as well as the effect of intermediate cover crops. Thus, the objective was to develop an approach to model the effects of crop residues left at the soil surface and cover crops on the fate of pesticides. This approach consisted in (1) considering the crop residues as a soil layer with specific physical, hydrodynamic and pesticide-reactivity properties close to that of a high organic content soil layer, and (2) introducing a correction factor of the potential evapotranspiration, estimated through a calibration step, to take into account the reduction of soil evaporation by the presence of a mulch. This approach was developed using MACRO as support pesticide model. To assess the model performances, we used the data from a field experiment designed in an irrigated maize monoculture under conservation tillage. Soil water content, water percolates, soil temperature and S-metolachlor herbicide concentrations in the leachate at 1m depth were measured during two years. The approach chosen to simulate the mulch effects allowed MACRO to make acceptable predictions of the observed water percolation, soil temperature and to a less extent herbicide leaching. However, it showed a poor performance to simulate the soil water content. Results are discussed in terms of further modelling options to better assess the environmental risks of pesticides under conservation tillage. This approach remains to be tested against various soils, crops, pesticides and types of mulch.

Biofilm vs. Planktonic Lifestyle: Consequences for Pesticide 2,4-D Metabolism by Cupriavidus necator JMP134.

The development of bacterial biofilms in natural environments may alter important functions, such as pollutant bioremediation by modifying both the degraders' physiology and/or interactions within the matrix. The present study focuses on the influence of biofilm formation on the metabolism of a pesticide, 2,4-dichlorophenoxyacetic acid (2,4-D), by Cupriavidus necator JMP134. Pure cultures were established in a liquid medium with 2,4-D as a sole carbon source with or without sand grains for 10 days. Bacterial numbers and 2,4-D concentrations in solution were followed by spectrophotometry, the respiration rate by gas chromatography and the surface colonization by electron microscopy. In addition, isotopic techniques coupled with Fatty Acid Methyl Ester (FAME) profiling were used to determine possible metabolic changes. After only 3 days, approximately 80% of the cells were attached to the sand grains and microscopy images showed that the porous medium was totally clogged by the development of a biofilm. After 10 days, there was 25% less 2,4-D in the solution in samples with sand than in control samples. This difference was due to (1) a higher (+8%) mineralization of 2,4-D by sessile bacteria and (2) a retention (15%) of 2,4-D in the biofilm matrix. Besides, the amount of carbohydrates, presumably constituting the biofilm polysaccharides, increased by 63%. Compound-specific isotope analysis revealed that the FAME isotopic signature was less affected by the biofilm lifestyle than was the FAME composition. These results suggest that sessile bacteria differ more in their anabolism than in their catabolism compared to their planktonic counterparts. This study stresses the importance of considering interactions between microorganisms and their habitat when studying pollutant dynamics in porous media.

Assessing human health risks from pesticide use in conventional and innovative cropping systems with the BROWSE model.

BACKGROUND: Reducing the risks and impacts of pesticide use on human health and on the environment is one of the objectives of the European Commission Directive 2009/128/EC in the quest for a sustainable use of pesticides. This Directive, developed through European national plans such as Ecophyto plan in France, promotes the introduction of innovative cropping systems relying, for example, on integrated pest management. Risk assessment for human health of the overall pesticide use in these innovative systems is required before the introduction of those systems to avoid that an innovation becomes a new problem. OBJECTIVES: The objectives of this work were to assess and to compare (1) the human exposure to pesticides used in conventional and innovative cropping systems designed to reduce pesticide needs, and (2) the corresponding risks for human health. METHODS: Humans (operator and residents) exposure to pesticides and risks for human health were assessed for each pesticide with the BROWSE model. Then, a method was proposed to represent the overall risk due to all pesticides used in one system. This study considers 3 conventional and 9 associated innovative cropping systems, and 116 plant protection products containing 89 different active substances (i.e. pesticides). RESULTS: The modelling results obtained with BROWSE showed that innovative cropping systems such as low input or no herbicide systems would reduce the risk for human health in comparison to the corresponding conventional cropping systems. On the contrary, BROWSE showed that conservation tillage system would lead to unacceptable risks in the conditions of our study, because of a high number of pesticide applications, and especially of some herbicides. For residents, the dermal absorption was the main exposure route while ingestion was found to be negligible. For operators, inhalation was also a predominant route of exposure. In general, human exposure to pesticides and human health risks were found to be correlated to the treatment frequency index TFI (number of registered doses of pesticides used per hectare for one copping season), confirming the relationship between the reduction of pesticide use and the reduction of risks. CONCLUSIONS: Assessment with the BROWSE model helped to identify cropping systems with decreased risks from pesticides for human health and to propose some improvements to the cropping systems by identifying the pesticides that led to unacceptable risks.

Formation of 2,4-D bound residues in soils: New insights into microbial metabolism.

The microbial contribution to the formation of bound residues in soils is studied by characterizing the metabolic activity of three microorganisms (Trametes versicolor, Fusarium solani and Ralstonia eutropha) on 14C-2,4-dichlorophenoxyacetic acid (2,4-D) during incubation in synthetic liquid media and soil. A fractionation protocol was applied to quantify the 14C-2,4-D that was incorporated into the biomass among biomolecular-like fractions. Successive fractionation of microbial biomass was implemented to break up and quantify the methanol/dichloromethane fraction (corresponding to the 14C-lipid-like fraction), the trichloroacetic acid fraction (or hydrolysed 14C-polysaccharide-like fraction) and the acid hydrolysable fraction (or the hydrolysed 14C-protein-like fraction). Relevant differences in the 2,4-D degradation and biomass radioactivity distribution among the three microorganisms were found. The 14C-protein-like fraction was the most consistent biomass fraction for reflecting the pesticide use capacity of the microorganisms under liquid and soil conditions. 2,4-D and its metabolite 4-chlorophenol were detected in methanol/dichloromethane and trichloroacetic acid fractions of the biomass of microorganisms exhibiting a low capacity to mineralize 2,4-D, thus proving that the microbial participation in the formation of bound residues while conserving the initial pesticide structure under natural soil conditions may be intimately associated with the lipid- and polysaccharide-like constituents. The fractionation protocol differentiates between 14C that is incorporated into biomass as a biomolecular constituent and the pesticide or its metabolites that accumulate in the biomass and thus correspond to the stricto sensu definition of bound residues.

Sequential use of the STICS crop model and of the MACRO pesticide fate model to simulate pesticides leaching in cropping systems.

The current challenge in sustainable agriculture is to introduce new cropping systems to reduce pesticides use in order to reduce ground and surface water contamination. However, it is difficult to carry out in situ experiments to assess the environmental impacts of pesticide use for all possible combinations of climate, crop, and soils; therefore, in silico tools are necessary. The objective of this work was to assess pesticides leaching in cropping systems coupling the performances of a crop model (STICS) and of a pesticide fate model (MACRO). STICS-MACRO has the advantage of being able to simulate pesticides fate in complex cropping systems and to consider some agricultural practices such as fertilization, mulch, or crop residues management, which cannot be accounted for with MACRO. The performance of STICS-MACRO was tested, without calibration, from measurements done in two French experimental sites with contrasted soil and climate properties. The prediction of water percolation and pesticides concentrations with STICS-MACRO was satisfactory, but it varied with the pedoclimatic context. The performance of STICS-MACRO was shown to be similar or better than that of MACRO. The improvement of the simulation of crop growth allowed better estimate of crop transpiration therefore of water balance. It also allowed better estimate of pesticide interception by the crop which was found to be crucial for the prediction of pesticides concentrations in water. STICS-MACRO is a new promising tool to improve the assessment of the environmental risks of pesticides used in cropping systems.

Sensitivity analysis of the STICS-MACRO model to identify cropping practices reducing pesticides losses.

STICS-MACRO is a process-based model simulating the fate of pesticides in the soil-plant system as a function of agricultural practices and pedoclimatic conditions. The objective of this work was to evaluate the influence of crop management practices on water and pesticide flows in contrasted environmental conditions. We used the Morris screening sensitivity analysis method to identify the most influential cropping practices. Crop residues management and tillage practices were shown to have strong effects on water percolation and pesticide leaching. In particular, the amount of organic residues added to soil was found to be the most influential input. The presence of a mulch could increase soil water content so water percolation and pesticide leaching. Conventional tillage was also found to decrease pesticide leaching, compared to no-till, which is consistent with many field observations. The effects of the soil, crop and climate conditions tested in this work were less important than those of cropping practices. STICS-MACRO allows an ex ante evaluation of cropping systems and agricultural practices, and of the related pesticides environmental impacts.

Glyphosate fate in soils when arriving in plant residues.

A significant fraction of pesticides sprayed on crops may be returned to soils via plant residues, but its fate has been little documented. The objective of this work was to study the fate of glyphosate associated to plants residues. Oilseed rape was used as model plant using two lines: a glyphosate-tolerant (GT) line and a non-GT one, considered as a crucifer weed. The effects of different fragmentation degrees and placements in soil of plant residues were tested. A control was set up by spraying glyphosate directly on the soil. The mineralization of glyphosate in soil was slower when incorporated into plant residues, and the amounts of extractable and non-extractable glyphosate residues increased. Glyphosate availability for mineralization increased when the size of plant residues decreased, and as the distribution of plant residues in soil was more homogeneous. After 80 days of soil incubation, extractable (14)C-residues mostly involved one metabolite of glyphosate (AMPA) but up to 2.6% of initial (14)C was still extracted from undecayed leaves as glyphosate. Thus, the trapping of herbicides in plant materials provided a protection against degradation, and crops residues returns may increase the persistence of glyphosate in soils. This pattern appeared more pronounced for GT crops, which accumulated more non-degraded glyphosate in their tissues.

Implementation of the effects of physicochemical properties on the foliar penetration of pesticides and its potential for estimating pesticide volatilization from plants.

Volatilization from plant foliage is known to have a great contribution to pesticide emission to the atmosphere. However, its estimation is still difficult because of our poor understanding of processes occurring at the leaf surface. A compartmental approach for dissipation processes of pesticides applied on the leaf surface was developed on the base of experimental study performed under controlled conditions using laboratory volatilization chamber. This approach was combined with physicochemical properties of pesticides and was implemented in SURFATM-Pesticides model in order to predict pesticide volatilization from plants in a more mechanistic way. The new version of SURFATM-Pesticide model takes into account the effect of formulation on volatilization and leaf penetration. The model was evaluated in terms of 3 pesticides applied on plants at the field scale (chlorothalonil, fenpropidin and parathion) which display a wide range of volatilization rates. The comparison of modeled volatilization fluxes with measured ones shows an overall good agreement for the three tested compounds. Furthermore the model confirms the considerable effect of the formulation on the rate of the decline in volatilization fluxes especially for systemic products. However, due to the lack of published information on the substances in the formulations, factors accounting for the effect of formulation are described empirically. A sensitivity analysis shows that in addition to vapor pressure, the octanol-water partition coefficient represents important physicochemical properties of pesticides affecting pesticide volatilization from plants. Finally the new version of SURFATM-Pesticides is a prospecting tool for key processes involved in the description of pesticide volatilization from plants.

Measuring Leaf Penetration and Volatilization of Chlorothalonil and Epoxiconazole Applied on Wheat Leaves in a Laboratory-Scale Experiment.

Estimation of pesticide volatilization from plants is difficult because of our poor understanding of foliar penetration by pesticides, which governs the amount of pesticide available for volatilization from the leaf surface. The description of foliar penetration is still incomplete because experimental measurements of this complex process are difficult. In this study, the dynamics of leaf penetration of C-chlorothalonil and C-epoxiconazole applied to wheat leaves were measured in a volatilization chamber, which allowed us to simultaneously measure pesticide volatilization. Fungicide penetration into leaves was characterized using a well-defined sequential extraction procedure distinguishing pesticide fractions residing at different foliar compartments; this enabled us to accurately measure the penetration rate constant into the leaves. The effect of pesticide formulation was also examined by comparing formulated and pure epoxiconazole. We observed a strong effect of formulation on leaf penetration in the case of a systemic product. Furthermore, the penetration rate constant of formulated epoxiconazole was almost three times that of pure epoxiconazole (0.47 ± 0.20 and 0.17 ± 0.07, respectively). Our experimental results showed high recovery rates of the radioactivity applied within the range of 90.5 to 105.2%. Moreover, our results confirm that pesticide physicochemical properties are key factors in understanding leaf penetration of pesticide and its volatilization. This study provides important and useful parameters for mechanistic models describing volatilization of fungicides applied to plants, which are scarce in the literature.

Prediction of the Fate of Organic Compounds in the Environment From Their Molecular Properties: A Review.

A comprehensive review of quantitative structure-activity relationships (QSAR) allowing the prediction of the fate of organic compounds in the environment from their molecular properties was done. The considered processes were water dissolution, dissociation, volatilization, retention on soils and sediments (mainly adsorption and desorption), degradation (biotic and abiotic), and absorption by plants. A total of 790 equations involving 686 structural molecular descriptors are reported to estimate 90 environmental parameters related to these processes. A significant number of equations was found for dissociation process (pKa), water dissolution or hydrophobic behavior (especially through the KOW parameter), adsorption to soils and biodegradation. A lack of QSAR was observed to estimate desorption or potential of transfer to water. Among the 686 molecular descriptors, five were found to be dominant in the 790 collected equations and the most generic ones: four quantum-chemical descriptors, the energy of the highest occupied molecular orbital (EHOMO) and the energy of the lowest unoccupied molecular orbital (ELUMO), polarizability (α) and dipole moment (µ), and one constitutional descriptor, the molecular weight. Keeping in mind that the combination of descriptors belonging to different categories (constitutional, topological, quantum-chemical) led to improve QSAR performances, these descriptors should be considered for the development of new QSAR, for further predictions of environmental parameters. This review also allows finding of the relevant QSAR equations to predict the fate of a wide diversity of compounds in the environment.

Modeling pesticide volatilization: testing the additional effect of gaseous adsorption on soil solid surfaces.

Pesticide volatilization from bare soil exhibits usually a diurnal cycle with a potentially large decrease when the soil surface dries. We assume here that this decrease may be due to the increase in adsorption of gaseous pesticides to soil under dry conditions. Thus, a precise description of the change with time of water content of the soil surface and of additional process such as gaseous adsorption is required. We used the Volt'Air model: we first extended the van Genuchten curve to drier conditions and then inserted a partitioning coefficient of the pesticide between the air-filled pore space and the soil constituents. This coefficient was calculated by a quantum-chemistry-based method with a dependence on the Specific Surface Area of the soil (SSA) and Relative Humidity (RH) of the air-filled pore space. These developments were assessed by comparing with two data sets on volatilization of trifluralin applied to bare soil. The updated Volt'Air model allowed a better description of the volatilization dynamics on a diurnal cycle (increasing efficiency factor from 0.85 to 0.96 and -2.73 to 0.17 and decreasing RMSE from 146 to 78 and 353 to 168 for both scenarios) as well as the effect of a rewetting situation. Recommendations are made for further refining the description of this process together with the soil water conditions.

Carbon-14-glyphosate behavior in relationship to pedoclimatic conditions and crop sequence.

The recognition of glyphosate [(-phosphonomethyl) glycine] behavioral patterns can be readily examined using a pedoclimatic gradient. In the present study, glyphosate adsorption-desorption and degradation were examined under different scenarios in relationship to soil properties and soil use applications. Three sites with varied pedoclimatic conditions and two crop sequences were selected. Adsorption-desorption and glyphosate distribution in mineralized, extractable, and nonextractable fractions were assessed under laboratory conditions. Glyphosate sorption was characterized by isotherms and glyphosate degradation using the distribution of C-glyphosate radioactivity among mineralized fractions, two extractable fractions (in water, ER1; in NHOH, ER2), and nonextractable fractions. Results showed sorption indices (distribution coefficient and Freundlich sorption coefficient : 13.4 ± 0.3-64.1 ± 0.9 L kg and 16.2-60.6, respectively), and hysteresis increased among soil sites associated with decreasing soil particle size <2 µm, soil organic matter, and other soil properties associated with soil granulometry. A multiple stepwise regression analysis was applied to estimate the relationship between values and soil properties. Cation exchange capacity, water field capacity, and Bray-1 P were the soil properties retained in the equation. Soils under continuous soybean [ (L.) Merr.] (monoculture) treatment exhibited reduced glyphosate adsorption and decreased hysteresis desorption relative to soils under rotation. To our knowledge, these results are the first to demonstrate that soils with identical properties exhibited different glyphosate retention capacities based on crop sequence. We propose possible explanations for this observation. Our results suggested that characterization of the variability in soil property gradients can serve to determine glyphosate behavioral patterns, which can establish a criterion for use in reducing potential environmental risks.

Gaseous deposition contributes to the contamination of surface waters by pesticides close to treated fields. A process-based model study.

The contribution of atmospheric pathways to surface waters contamination by pesticides has been demonstrated. At the local scale, modeling approaches as well as measurements show situations where the contribution of gaseous dry deposition is of the same order or even higher than the drift contribution. The approach presented here consists in estimating the gaseous emissions of pesticides applied in the field, their atmospheric dispersion, and finally their gaseous deposition into aquatic ecosystems at the local scale by running process-based models, that is, the one-dimensional model for pesticide volatilization following application on bare soil (Volt'Air) and the local-scale dispersion and deposition model (FIDES-2D), adapted for pesticides. A significant number of scenarios describes contrasted situations in terms of pedoclimatic conditions (covering 9 years of meteorological data), periods of pesticide application per year, physicochemical properties of the pesticides, and spatial configurations. The identification of the main factors governing gaseous deposition led to the definition of an effective emission factor which explains a large part of the deposition variability. Based on the model outputs, deposition curves are proposed, as a base for a new tool to assess the contribution of gaseous deposition to nontarget ecosystem contamination.

Fate of (14)C-organic pollutant residues in composted sludge after application to soil.

Organic micropollutants may be present in biosolids, leading to soil contamination when they are recycled in agriculture. A sludge spiked with (14)C-labelled glyphosate (GLY), sodium linear dodecylbenzene sulphonate (LAS), fluoranthene (FLT) or 4-n-nonylphenol (NP) was composted with green waste and the fate of the (14)C-micropollutant residues remaining after composting was assessed after the compost application to the soil. (14)C-residues were mineralised in the soil and represented after 140d 20-32% of the initial activity for LAS, 16-25% for GLY, 6-9% for FLT and 4-7% for NP. The (14)C-residues at the end of composting that could not be extracted with methanol or ammonia were minimally remobilised or even increased for FLT. After 140d, non-extractable residues represented 38-52% of all of the (14)C-residues remaining in the soil for FLT, 50-67% for GLY, 91-92% for NP and 94-97% for LAS and in most cases, less than 1% of the (14)C-residues were water soluble, suggesting a low direct availability for leaching and microbial or plant assimilation. FLT was identified as the main compound among the methanol-extractable (14)C-residues that may be potentially available. The fate of the (14)C-organic pollutant residues in composts after application to soil could be assessed through a sequential chemical extraction scheme and depended on the chemical nature of the pollutant.

Factors affecting metribuzin retention in Algerian soils and assessment of the risks of contamination.

Metribuzin is a widely used herbicide around the world but it could lead to soil and water contamination. Metribuzin retention on a silty-clay agricultural soil of Algeria was studied in laboratory batch experiments to assess the contamination risk of the groundwater. Factors conditioning the fate of metribuzin were investigated: soil nature, metribuzin formulation, NPK fertilizer, and soil pH. Freundlich sorption isotherms gave the coefficients K F between 1.2 and 4.9 and 1/n a between 0.52 and 0.93. The adsorption is directly dependent on organic and clay soil contents. Formulated metribuzin (Metriphar) reduces the adsorption (K F = 1.25) compared to pure metribuzin (K F = 2.81). The addition of an NPK fertilizer decreases the soil pH (6.67 for the soil without fertilizer and 5.86 for 2 % of fertilizer) and increases metribuzin adsorption (K F is 4.83 for 2 % of fertilizer). The pH effect on the adsorption is corroborated in experiments changing the soil pH between 5 (K F is 4.17) and 8 (K F is 1.57) under controlled conditions. Desorption isotherms show a hysteresis and only 30 to 40 % of the initially adsorbed metribuzin is released. The estimated GUS index is ≥ 2.8 for a DT50 ≥ 30 days. K F values and the hysteresis show that metribuzin is little but strongly retained on the soil. Formulated metribuzin and addition of fertilizer affect the retention. However, the GUS index indicates a high mobility and a significant risk of leaching. The most appropriate risk management measure would be an important increase in organic matter content of the soil by addition of organic amendments.

Analyzing the spatial distribution of PCB concentrations in soils using below-quantification limit data.

Polychlorinated biphenyls (PCBs) are highly toxic environmental pollutants that can accumulate in soils. We consider the problem of explaining and mapping the spatial distribution of PCBs using a spatial data set of 105 PCB-187 measurements from a region in the north of France. A large proportion of our data (35%) fell below a quantification limit (QL), meaning that their concentrations could not be determined to a sufficient degree of precision. Where a measurement fell below this QL, the inequality information was all that we were presented with. In this work, we demonstrate a full geostatistical analysis-bringing together the various components, including model selection, cross-validation, and mapping-using censored data to represent the uncertainty that results from below-QL observations. We implement a Monte Carlo maximum likelihood approach to estimate the geostatistical model parameters. To select the best set of explanatory variables for explaining and mapping the spatial distribution of PCB-187 concentrations, we apply the Akaike Information Criterion (AIC). The AIC provides a trade-off between the goodness-of-fit of a model and its complexity (i.e., the number of covariates). We then use the best set of explanatory variables to help interpolate the measurements via a Bayesian approach, and produce maps of the predictions. We calculate predictions of the probability of exceeding a concentration threshold, above which the land could be considered as contaminated. The work demonstrates some differences between approaches based on censored data and on imputed data (in which the below-QL data are replaced by a value of half of the QL). Cross-validation results demonstrate better predictions based on the censored data approach, and we should therefore have confidence in the information provided by predictions from this method.

Dissipation pathways of organic pollutants during the composting of organic wastes.

The organic pollutants (OPs) present in compostable organic residues can be recovered in the final composts leading to environmental impacts related to their use in agriculture. However, the composting process may contribute to their partial dissipation that is classically evaluated through the concentration decrease in extractable OPs, without identification of the responsible mechanisms as mineralization or stabilization of OP as non-extractable residues (NER) or bound residues. The dissipation of four (14)C-labeled OPs (fluoranthene; 4-n-nonylphenol, NP; sodium linear dodecylbenzene sulfonate, LAS; glyphosate) was assessed during composting of sewage sludge and green waste. The dissipation of LAS largely resulted from its mineralization (51% of initial LAS), whereas mineralization was intermediate for NP (29%) and glyphosate (24%), and negligible for fluoranthene. The NER pathway mostly concerned NP and glyphosate, with 45% and 37% of the recovered (14)C being found as NER at the end of composting, respectively. In the final composts, the proportions of water soluble residues of OPs considered as readily available were <11% of recovered (14)C-OPs. However, most fluoranthene remained solvent extractable (72%) and potentially available, whereas only 18% of glyphosate and less than 7% of both NP and LAS remained solvent extractable in the final compost.

Effect of glucose on the fatty acid composition of Cupriavidus necator JMP134 during 2,4-dichlorophenoxyacetic acid degradation: implications for lipid-based stable isotope probing methods.

Combining lipid biomarker profiling with stable isotope probing (SIP) is a powerful technique for studying specific microbial populations responsible for the degradation of organic pollutants in various natural environments. However, the presence of other easily degradable substrates may induce significant physiological changes by altering both the rate of incorporation of the target compound into the biomass and the microbial lipid profiles. In order to test this hypothesis, Cupriavidus necator JMP134, a 2,4-dichlorophenoxyacetic acid (2,4-D)-degrading bacterium, was incubated with [(13)C]2,4-D, [(13)C]glucose, or mixtures of both substrates alternatively labeled with (13)C. C. necator JMP134 exhibited a preferential use of 2,4-D over glucose. The isotopic analysis showed that glucose had only a small effect on the incorporation of the acetic chain of 2,4-D into the biomass (at days 2 and 3) and no effect on that of the benzenic ring. The addition of glucose did change the fatty acid methyl ester (FAME) composition. However, the overall FAME isotopic signature reflected that of the entire biomass. Compound-specific individual isotopic analyses of FAME composition showed that the (13)C-enriched FAME profiles were slightly or not affected when tracing the 2,4-D acetic chain or 2,4-D benzenic ring, respectively. This batch study is a necessary step for validating the use of lipid-based SIP methods in complex environments.

Which persistent organic pollutants can we map in soil using a large spacing systematic soil monitoring design? A case study in Northern France.

Persistent organic pollutants (POPs) impact upon human and animal health and the wider environment. It is important to determine where POPs are found and the spatial pattern of POP variation. The concentrations of 90 molecules which are members of four families of POPs and two families of herbicides were measured within a region of Northern France as part of the French National Soil Monitoring Network (RMQS: Réseau de Mesures de la Qualité des Sols). We also gather information on five covariates (elevation, soil organic carbon content, road density, land cover and population density) which might influence POP concentrations. The study region contains 105 RMQS observation sites arranged on a regular square grid with spacing of 16 km. The observations include hot-spots at sites of POP application, smaller concentrations where POPs have been dispersed and observations less than the limit of quantification (LOQ) where the soil has not been impacted by POPs. Fifty nine of the molecules were detected at less than 50 sites and hence the data were unsuitable for spatial analyses. We represent the variation of the remaining 31 molecules by various linear mixed models which can include fixed effects (i.e. linear relationships between the molecule concentrations and covariates) and spatially correlated random effects. The best model for each molecule is selected by the Akaike Information Criterion. For nine of the molecules, spatial correlation is evident and hence they can potentially be mapped. For four of these molecules, the spatial correlation cannot be wholly explained by fixed effects. It appears that these molecules have been transported away from their application sites and are now dispersed across the study region with the largest concentrations found in a heavily populated depression. More complicated statistical models and sampling designs are required to explain the distribution of the less dispersed molecules.