Leaching and degradation of S-Metolachlor in undisturbed soil cores amended with organic wastes.

Organic waste (OW) reuse in agriculture is a common practice fostered by benefits in terms of waste recycling and crop production. However, OW amendments potentially affect the fate of pesticide spread on fields to protect the crops from pests and weeds. The influence of OW on the sorption, degradation, and leaching of pesticides is generally studied for each mechanism separately under artificial laboratory conditions. Our study aims at evaluating the balance of these mechanisms under more realistic conditions to clarify the influence of three common OW amendments on the fate, in soil, of the widely used herbicide S-Metolachlor. We performed leaching experiments in large undisturbed soil cores amended with raw sewage sludge, composted sludge, and digested pig slurry (digestate), respectively. We monitored S-Metolachlor and its two main metabolites MET-OA and MET-ESA in the leachates during a succession of 10 rainfall events over 126 days. We also quantified the remaining S-Metolachlor and metabolites in the soil at the end of the experiments. S-Metolachlor leaching didn't exceed 0.1% of the applied dose with or without OW amendment. Despite a soil organic carbon increase of 3 to 32%, OW amendments did not significantly affect the amount of S-Metolachlor that leached through the soil (0.01 to 0.1%) nor its transformation rate (6.0 to 8.6%). However, it affected the degradation pathways with an increase of MET-OA relative to MET-ESA formed after OW amendment (28 to 54%) compared to the controls (8%). Concentration of S-Metolachlor and metabolites in the leachates of all treatments greatly exceeded the regulatory limit for groundwater intended for human consumption in Europe. These high concentrations were probably the consequence of preferential macropore flow. Colloids had comparable levels in the leachates after S-Metolachlor application. Dissolved organic carbon was also comparable in the controls, digestate, and sludge treatments but was 65% higher in the compost-amended cores. These results, along with a great variability among replicates inherent to experiments performed under realistic conditions, partly explain the limited impact of OW on the transport of S-Metolachlor.

Adsorption and degradation of the herbicide nicosulfuron in a stagnic Luvisol and Vermic Umbrisol cultivated under conventional or conservation agriculture.

The main goals of conservation agriculture are to enhance soil fertility and reduce soil degradation, especially through erosion. However, conservation agriculture practices can increase the risk of contamination by pesticides, mainly through vertical transfer via water flow. Better understanding of their sorption and degradation processes is thus needed in conservation agriculture as they control the amount of pesticide available for vertical transfer. The purpose of our study was to investigate the sorption and degradation processes of nicosulfuron in soil profiles (up to 90 cm deep) of a Vermic Umbrisol and a Stagnic Luvisol managed either in conventional or in conservation agriculture. Two laboratory sorption and incubation experiments were performed. Low sorption was observed regardless of the soil type, agricultural management or depth, with a maximum value of 1.3 ± 2.0 L kg-1. By the end of the experiment (91 days), nicosulfuron mineralisation in the Vermic Umbrisol was similar for the two types of agricultural management and rather depended on soil depth (29.0 ± 2.3% in the 0-60-cm layers against 7.5 ± 1.4% in the 60-90 cm). In the Stagnic Luvisol, nicosulfuron mineralisation reached similar value in every layer of the conservation agriculture plot (26.5% ± 0.7%). On the conventional tillage plot, mineralisation decreased in the deepest layer (25-60 cm) reaching only 18.4 ± 6.9% of the applied nicosulfuron. Regardless of the soil type or agricultural management, non-extractable residue formation was identified as the main dissipation process of nicosulfuron (45.1 ± 8.5% and 50.2 ± 7.0% under conventional and conservation agriculture respectively after 91 days). In our study, nicosulfuron behaved similarly in the Vermic Umbrisol regardless of the agricultural management, whereas the risk of transfer to groundwater seemed lower in the Stagnic Luvisol under conservation agriculture.

Influence of agroforestry plant species on the infiltration of S-Metolachlor in buffer soils.

Agroforestry practices have been acknowledged for reducing pesticide losses while maintaining land productivity. Pesticide removal from overland flow results from great infiltration capacities of the buffer soils. This can in turn threaten the quality of groundwater in case of poor pesticide sorption and degradation in the root-influenced zone. These mechanisms and their balance are likely to be influenced by plant species. However, little is known about the role of agroforestry species in the infiltration of herbicides. The aim of this study was thereby to evaluate how popular agroforestry species modulate the infiltration of water and of a widely used herbicide. We established large buffer microcosms by planting Brome grass, Black walnut, Pin oak and Poplar trees in repacked soil columns. After a growth season of 4 months, we performed ponded infiltration experiments with bromide and S-Metolachlor. We used then the HYDRUS 1D model to compare the hydrodynamic properties and S-Metolachlor transport patterns between the microcosms. In addition, we compared the sorption properties of the rhizosphere and bulk soils. We found that the tree species increased the sorption of S-Metolachlor in soil with Kd being 3 times greater than in the un-vegetated and Brome grass microcosms. Poplar trees increased the hydraulic conductivity (Ksat) compared to the control and was associated to a low retardation of S-metolachlor, which increases the risk of groundwater contamination. With slightly reduced Ksat and retardation factor in the root zone, 1.6 to 1.8 times greater than in the control treatment, Black walnut appears as an optimal species for mitigating S-Metolachlor. The Brome grass and oak microcosms had the lowest Ksat of all treatments and S-Metolachlor retardation factors were equal and slightly increased compared to the control, respectively. These results show that agroforestry buffer's efficiency can be optimized by selecting appropriate species.

Soil aggregates as biogeochemical reactors: Not a way forward in the research on soil-atmosphere exchange of greenhouse gases.

The goal of this comment is to show that the "aggregate reactor" framework recently proposed in an article published in this journal is severely limited by two kinds of indeterminacy. The first is related to the size of aggregates, which is not defined precisely. The second issue is with the impossibility to replicate boundary conditions that are identical to what chunks of soils would have experienced in their natural state. We suggest that the study of GHG release in undisturbed soil samples is a better way to proceed forward.

Emergent Properties of Microbial Activity in Heterogeneous Soil Microenvironments: Different Research Approaches Are Slowly Converging, Yet Major Challenges Remain.

Over the last 60 years, soil microbiologists have accumulated a wealth of experimental data showing that the bulk, macroscopic parameters (e.g., granulometry, pH, soil organic matter, and biomass contents) commonly used to characterize soils provide insufficient information to describe quantitatively the activity of soil microorganisms and some of its outcomes, like the emission of greenhouse gasses. Clearly, new, more appropriate macroscopic parameters are needed, which reflect better the spatial heterogeneity of soils at the microscale (i.e., the pore scale) that is commensurate with the habitat of many microorganisms. For a long time, spectroscopic and microscopic tools were lacking to quantify processes at that scale, but major technological advances over the last 15 years have made suitable equipment available to researchers. In this context, the objective of the present article is to review progress achieved to date in the significant research program that has ensued. This program can be rationalized as a sequence of steps, namely the quantification and modeling of the physical-, (bio)chemical-, and microbiological properties of soils, the integration of these different perspectives into a unified theory, its upscaling to the macroscopic scale, and, eventually, the development of new approaches to measure macroscopic soil characteristics. At this stage, significant progress has been achieved on the physical front, and to a lesser extent on the (bio)chemical one as well, both in terms of experiments and modeling. With regard to the microbial aspects, although a lot of work has been devoted to the modeling of bacterial and fungal activity in soils at the pore scale, the appropriateness of model assumptions cannot be readily assessed because of the scarcity of relevant experimental data. For significant progress to be made, it is crucial to make sure that research on the microbial components of soil systems does not keep lagging behind the work on the physical and (bio)chemical characteristics. Concerning the subsequent steps in the program, very little integration of the various disciplinary perspectives has occurred so far, and, as a result, researchers have not yet been able to tackle the scaling up to the macroscopic level. Many challenges, some of them daunting, remain on the path ahead. Fortunately, a number of these challenges may be resolved by brand new measuring equipment that will become commercially available in the very near future.

Microscale Heterogeneity of the Spatial Distribution of Organic Matter Can Promote Bacterial Biodiversity in Soils: Insights From Computer Simulations.

There is still no satisfactory understanding of the factors that enable soil microbial populations to be as highly biodiverse as they are. The present article explores in silico the hypothesis that the heterogeneous distribution of soil organic matter, in addition to the spatial connectivity of the soil moisture, might account for the observed microbial biodiversity in soils. A multi-species, individual-based, pore-scale model is developed and parameterized with data from 3 Arthrobacter sp. strains, known to be, respectively, competitive, versatile, and poorly competitive. In the simulations, bacteria of each strain are distributed in a 3D computed tomography (CT) image of a real soil and three water saturation levels (100, 50, and 25%) and spatial heterogeneity levels (high, intermediate, and low) in the distribution of the soil organic matter are considered. High and intermediate heterogeneity levels assume, respectively, an amount of particulate organic matter (POM) distributed in a single (high heterogeneity) or in four (intermediate heterogeneity) randomly placed fragments. POM is hydrolyzed at a constant rate following a first-order kinetic, and continuously delivers dissolved organic carbon (DOC) into the liquid phase, where it is then taken up by bacteria. The low heterogeneity level assumes that the food source is available from the start as DOC. Unlike the relative abundances of the 3 strains, the total bacterial biomass and respiration are similar under the high and intermediate resource heterogeneity schemes. The key result of the simulations is that spatial heterogeneity in the distribution of organic matter influences the maintenance of bacterial biodiversity. The least competing strain, which does not reach noticeable growth for the low and intermediate spatial heterogeneities of resource distribution, can grow appreciably and even become more abundant than the other strains in the absence of direct competition, if the placement of the resource is favorable. For geodesic distances exceeding 5 mm, microbial colonies cannot grow. These conclusions are conditioned by assumptions made in the model, yet they suggest that microscale factors need to be considered to better understand the root causes of the high biodiversity of soils.

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.

Transport of organic contaminants in subsoil horizons and effects of dissolved organic matter related to organic waste recycling practices.

Compost amendment on agricultural soil is a current practice to compensate the loss of organic matter. As a consequence, dissolved organic carbon concentration in soil leachates can be increased and potentially modify the transport of other solutes. This study aims to characterize the processes controlling the mobility of dissolved organic matter (DOM) in deep soil layers and their potential impacts on the leaching of organic contaminants (pesticides and pharmaceutical compounds) potentially present in cultivated soils receiving organic waste composts. We sampled undisturbed soil cores in the illuviated horizon (60-90 cm depth) of an Albeluvisol. Percolation experiments were made in presence and absence of DOM with two different pesticides, isoproturon and epoxiconazole, and two pharmaceutical compounds, ibuprofen and sulfamethoxazole. Two types of DOM were extracted from two different soil surface horizons: one sampled in a plot receiving a co-compost of green wastes and sewage sludge applied once every 2 years since 1998 and one sampled in an unamended plot. Results show that DOM behaved as a highly reactive solute, which was continuously generated within the soil columns during flow and increased after flow interruption. DOM significantly increased the mobility of bromide and all pollutants, but the effects differed according the hydrophobic and the ionic character of the molecules. However, no clear effects of the origin of DOM on the mobility of the different contaminants were observed.

Impact of long-term organic residue recycling in agriculture on soil solution composition and trace metal leaching in soils.

Recycling composted organic residues in agriculture can reduce the need of mineral fertilizers and improve the physicochemical and biological properties of cultivated soils. However, some trace elements may accumulate in soils following repeated applications and impact other compartments of the agrosystems. This study aims at evaluating the long-term impact of such practices on the composition of soil leaching water, especially on trace metal concentrations. The field experiment QualiAgro started in 1998 on typical loess Luvisol of the Paris Basin, with a maize-wheat crop succession and five modalities: spreading of three different urban waste composts, farmyard manure (FYM), and no organic amendment (CTR). Inputs of trace metals have been close to regulatory limits, but supplies of organic matter and nitrogen overpassed common practices. Soil solutions were collected from wick lysimeters at 45 and 100 cm in one plot for each modality, during two drainage periods after the last spreading. Despite wide temporal variations, a significant effect of treatments on major solutes appears at 45 cm: DOC, Ca, K, Mg, Na, nitrate, sulphate and chloride concentrations were higher in most amended plots compared to CTR. Cu concentrations were also significantly higher in leachates of amended plots compared to CTR, whereas no clear effect emerged for Zn. The influence of amendments on solute concentrations appeared weaker at 1 m than at 45 cm, but still significant and positive for major anions and DOC. Average concentrations of Cu and Zn at 1m depth lied in the ranges [2.5; 3.8] and [2.5; 10.5 µg/L], respectively, with values slightly higher for plots amended with sewage sludge compost or FYM than for CTR. However, leaching of both metals was less than 1% of their respective inputs through organic amendments. For Cd, most values were <0.05 µg/L. So, metals added through spreading of compost or manure during 14 years may have increased metal concentrations in leachates of amended plots, in spite of increased soil organic matter, factor of metal retention. Indeed, DOC, also increased by amendments, favours the mobility of Cu; whereas pH variations, depending on treatments, influence negatively the solubility of Zn. Generic adsorption functions of these variables partly explain the variations of trace metal concentrations and helped to unravel the numerous processes induced by regular amendments with organic waste products.

Modeling the effect of soil structure on water flow and isoproturon dynamics in an agricultural field receiving repeated urban waste compost application.

Transport processes in soils are strongly affected by heterogeneity of soil hydraulic properties. Tillage practices and compost amendments can modify soil structure and create heterogeneity at the local scale within agricultural fields. The long-term field experiment QualiAgro (INRA-Veolia partnership 1998-2013) explores the impact of heterogeneity in soil structure created by tillage practices and compost application on transport processes. A modeling study was performed to evaluate how the presence of heterogeneity due to soil tillage and compost application affects water flow and pesticide dynamics in soil during a long-term period. The study was done on a plot receiving a co-compost of green wastes and sewage sludge (SGW) applied once every 2 years since 1998. The plot was cultivated with a biannual rotation of winter wheat-maize (except 1 year of barley) and a four-furrow moldboard plow was used for tillage. In each plot, wick lysimeter outflow and TDR probe data were collected at different depths from 2004, while tensiometer measurements were also conducted during 2007/2008. Isoproturon concentration was measured in lysimeter outflow since 2004. Detailed profile description was used to locate different soil structures in the profile, which was then implemented in the HYDRUS-2D model. Four zones were identified in the plowed layer: compacted clods with no visible macropores (Δ), non-compacted soil with visible macroporosity (Γ), interfurrows created by moldboard plowing containing crop residues and applied compost (IF), and the plow pan (PP) created by plowing repeatedly to the same depth. Isoproturon retention and degradation parameters were estimated from laboratory batch sorption and incubation experiments, respectively, for each structure independently. Water retention parameters were estimated from pressure plate laboratory measurements and hydraulic conductivity parameters were obtained from field tension infiltrometer experiments. Soil hydraulic properties were optimized on one calibration year (2007/08) using pressure head, water content and lysimeter outflow data, and then tested on the whole 2004/2010 period. Lysimeter outflow and water content dynamics in the soil profile were correctly described for the whole period (model efficiency coefficient: 0.99) after some correction of LAI estimates for wheat (2005/06) and barley (2006/07). Using laboratory-measured degradation rates and assuming degradation only in the liquid phase caused large overestimation of simulated isoproturon losses in lysimeter outflow. A proper order of magnitude of isoproturon losses was obtained after considering that degradation occurred in solid (sorbed) phase at a rate 75% of that in liquid phase. Isoproturon concentrations were found to be highly sensitive to degradation rates. Neither the laboratory-measured isoproturon fate parameters nor the independently-derived soil hydraulic parameters could describe the actual multiannual field dynamics of water and isoproturon without calibration. However, once calibrated on a limited period of time (9 months), HYDRUS-2D was able to simulate the whole 6-year time series with good accuracy.

Metribuzin transport in undisturbed soil cores under controlled water potential conditions: experiments and modelling to evaluate the risk of leaching in a sandy loam soil profile.

BACKGROUND: Mobility of pesticides in soils is often evaluated and characterised in the surface soil layers rather than at different depths where soil characteristics such as soil organic matter, microbial biomass or clay contents can strongly change pesticide behaviour. The objective of this work was to characterise the reactivity of the herbicide metribuzin in three main soil horizons found in the 0-80 cm profile of an alluvial soil of southern Norway under dynamic transport conditions. RESULTS: A laboratory infiltrometer was used to perform percolation experiments in soil cores sampled in the three horizons Ap, Bw and Bw/C, at a fixed matric potential of -10 cm, thus preventing pores of equivalent radii higher than 0.015 cm from contributing to water flow. The physical equilibrium transport model correctly described the transport of water tracer (bromide). The distribution coefficient K(d) values were estimated to be 0.29, 0.17 ± 0.02 and 0.15 ± 0.00 L kg(-1) for horizons Ap, Bw and Bw/C respectively, in close agreement with batch sorption data. Degradation was found only for the surface horizon with a short half-life of about 5 days, in disagreement with longer half-lives found in batch and field degradation data. CONCLUSION: For all horizons, a kinetic sorption model was needed for better description of metribuzin leaching. Chemical non-equilibrium was greatest in the Bw horizon and lowest in the Bw/C horizon. Overall, metribuzin exhibited a greater mobility in the deeper horizons. The risk of metribuzin transfer to groundwater in such alluvial soils should therefore be considered.