Copper (Cu) has been used to treat vines for a long time, which has led to its accumulation in vineyard soils. In the present work, the mobilization of copper from these soils and its transport, and diffusion outside the plots by drain water were investigated. For this, the distribution of copper between the dissolved and colloidal phases, and within the colloidal phase, of these waters was determined using an investigation strategy based on the coupling between a size separation technique, asymmetric flow field-flow fractionation, and several detectors. First, the total copper concentrations in water from different drains were monitored over a period of 2 years: Cu was mainly found in the fraction of < 450 nm. Then, the distribution of copper on the size continuum was more closely studied in water from one of the drains, sampled over a winter period. Between 45 and 75% of Cu was found in the 2–450 nm colloidal fraction. The <450 nm colloidal phase of the drain waters was found to be mainly composed of humic acids (~15 to 60 mg L−1) and clay-rich particles (~100 to 650 mg (Al) L−1). These particles also contained (hydr)oxides of iron and manganese. The concentrations of Fe and Mn were approximately 100 to 200 times lower than those of Al. The majority of humic acids had an apparent molar mass of ≤ 10 kDa. They were distributed along the size continuum: (i) in a population with an average size of ~20 nm, probably consisting of supramolecular entities, and (ii) associated with clay-rich particles with a size of ~120–200 nm. Copper was found to be complexed with humic acids and associated with clays via clay-humic complexes. Copper mobilization from the soil to the water and its transport to the drain water appeared governed by the soil humidity level and the rainfall.

Ag is a rare, non-essential metal with many applications in different forms, including nanoparticles (Ag-NPs). Its release into the soil environment can represent a risk, due to the toxicity of silver. This study is based on the analysis of samples from the two sampling campaigns of the Soil Quality Measurement Network, RMQS1 and RMQS2, to establish the spatial distribution and origin of Ag in the soils of southwestern France (area of 90,293 km2). Given the progress of the second campaign (completion in 2027), we chose to do a cokriging to estimate the spatial distribution, with Pb, Cd or Cu as potential secondary variables. The results of the analyzes of the 35 samples of the RMQS2 indicate a range of Ag concentration in the soils going from 0.015 to 0.222 mg kg-1 and a median of 0.081 mg kg -1. Correlations were found between the concentrations of Ag Cd, Cu and Pb, and also between Ag concentrations and distance to Pb mines and deposits (r = 0.62). This suggests a common origin for Ag and Pb linked to historical exploitations of argentiferous galena. No link could be demonstrated between the concentration of Ag and the high density of anti-hail ground generators in the region. The analysis of the (auto-) variograms showed that Pb is the most relevant variable compared to Cd and Cu to achieve a cokriging. Thus, based on Ag concentrations from RMQS2 and Pb concentrations from RMQS1 (356 samples), a linear co -regionalization model was established and the co-kriging of Ag concentrations in soils calculated. Compared to ordinary kriging, cokriging improved the quality of the interpolation (decrease in the root mean square error).

Since the fifties, organochlorine pesticides (OCPs) had been used in agriculture to protect vegetables. Two decades after their ban by the Stockholm convention in 2001, OCPs are still present in agricultural soils inducing vegetable contamination with concentrations above Maximum Residue Level (MRL). This is a major concern for a 5 km2 peri-urban vegetable growing valley located in the south west of France. In the present work, the sampling method was developed to clarify the spatial distribution of one OCP, Dieldrin, and its relationship with soil properties at the scale of study area. A total of 99 soil samples was collected for physicochemical analyses and Dieldrin concentrations. Results show Dieldrin concentrations in soils up to 204 mu g kg(-1). The horizontal distribution of this pesticide is heterogeneous at the study area scale but homogeneous in each reference plot studied. About 85% of the contamination was located in the top soil layers (0-40 cm depth), but Dieldrin may still be quantified at a depth of 80 cm. Among all soil physicochemical parameters analysed, SOM was the most significantly related (P < 10(-4)) with Dieldrin concentrations, once different grain size fractions were considered. Moreover, results indicate a 33 times higher Dieldrin concentration and/or extractability for coarse sand than for other grain size fractions. These results show that the developed sampling method is adapted for the study area scale as it helps understanding the factors influencing the spatial distribution of Dieldrin. Historical amendments are the predominant factor for the horizontal contamination and deep ploughing for the vertical contamination. Also, the variations of coarse sand repartition in soils prevents identification of relationships between SOM and Dieldrin contamination in bulk soil. Further investigation is required to explain these relationships but these results highlight why no clear relationship between OCPs and SOM was previously identified.

Wildfires can promote changes in soil organic carbon pools (SOCp) mainly as consequence of the input of ashes and charred materials from the scorched vegetation; and/or the removal of litter layer and organic matter from the upper soil centimetres affected by high temperatures. Moreover, post-fire management practices can also cause changes in the different forms of organic carbon in the soil (from the most labile to the most recalcitrant). In the REMAS project, a methodology to study the different SOCp is proposed to assess the effects of the application of different management post-fire practices over the burned areas: (1) cut and remove burned trunks, (2) shrub clearing letting the masticated debris on the soil carried out 6-8 years after the fires and, (3) no intervention treatment. The SOCp analysed include hot-water extractable C, particulate organic C, associated to the mineral fraction and total organic C. The study areas include diverse forest ecosystems from France (Pinus pinaster Ait.), Portugal (Quercus suber L.) and Spain (Pinus halepensis Mill.and Pinus sylvestris L.). Results show variable effects of the management practices on the different organic C pools, mainly over the most labile ones. Acknowledgements: The REMAS project SOE3/P4/E0954 is co-financed by the Interreg Sudoe Program through the European Regional Development Fund (ERDF).

Platinum group elements (PGE: Ru, Rh, Pd, Os Ir, Pt) are rare metals with low abundance in the continental crust. The elements of the palladium subgroup of PGE (PPGE: Pt, Pd, Rh) have been exploited more and more over the last thirty years for their physicochemical properties such as high melting point, high resistance to corrosion, mechanical strength and ductility. This led to emerging environmental contamination in different media such as air, road dust, soil, sediment, vegetation, and snow. The aim of this review is to summarize the available data on soil contamination by PPGE and its potential environmental impact. In this paper, the environmental issue of PPGE is discussed with regard to their anthropogenic emission and fate, which includes speciation, possible transformations into bioavailable forms and toxicity. Soil contamination by PPGE is described taking into account urban and non-urban areas. The analytical determination process is also discussed. (C) 2021 Elsevier Ltd. All rights reserved.

The contamination of soils by trace elements is a major concern for soil quality. This study is based on the analysis of 356 samples from the RMQS soil monitoring network to establish the spatial distribution and origin of six trace elements (As, Cd, Cu, Cr, Ni, Pb) in soils of south-western region of France (area of 90,293 km2). An exploratory and multivariate statistical analysis, and geostatistics combined with a geographic information system (GIS) were used to identify and characterize any concentration anomalies in trace elements. For all the trace elements studied, the exploratory analysis shows that there are more anomalies in this region than in the rest of the country. Analysis of the semivariograms shows that the six elements are spatially auto correlated. The spatial structure of As highlights anisotropic behaviour with a direction that corresponds to the gold deposit and mining activities of the region. This indicates a dual origin anthropogenic and geogenic for As. The correlation between Cd and inherent features of calcareous soil (pH, CaCO3 and cation exchange capacity) suggest a mainly geogenic origin for this element; Cd origin is confirmed by its spatial distribution associated with the Jurassic limestone bedrock. The correlations between Cr, Ni and clays highlight a geogenic origin for these elements, as weathered parent material rich in clays is also rich in Cr and Ni. The high Cu concentrations are of anthropogenic origin, linked to viticulture and the spreading of Bordeaux mixture as a fungicide. Locally high Pb concentrations are associated with mining activities and automobile emissions in large cities in the region.

Platinum group elements (PGE: Ru, Rh, Pd, Os Ir, Pt) are rare metals with low abundance in the continental crust. The elements of the palladium subgroup of PGE (PPGE: Pt, Pd, Rh) have been exploited more and more over the last thirty years for their physicochemical properties such as high melting point, high resistance to corrosion, mechanical strength and ductility. This led to emerging environmental contamination in different media such as air, road dust, soil, sediment, vegetation, and snow. The aim of this review is to summarize the available data on soil contamination by PPGE and its potential environmental impact. In this paper, the environmental issue of PPGE is discussed with regard to their anthropogenic emission and fate, which includes speciation, possible transformations into bioavailable forms and toxicity. Soil contamination by PPGE is described taking into account urban and non-urban areas. The analytical determination process is also discussed.

This study aims to answer the question about the chelating capacity of Chelex-100 resin according to the size of grains obtained after different grindings of a 200–400 mesh powder. Optical microscopy was used for size characterization of different new sub-types of resin obtained after grinding. The copper chelating capacity was evaluated using inductively coupled plasma−mass spectrometry. Grinding enables copper to be chelated by all iminodiacetate groups of the resin. Thus, the copper chelating capacity increases by 17% compared to unground resin and is more repeatable from one aliquot to another (1% RSD with optimal grinding versus 3% without grinding).

Soil is a key component of the terroir concept for wine production. Indeed, the soil provides water and nutrients to the vine plants depending on its properties and environmental conditions. A part of the complexity in the production of high-quality wines is the adaptation of the winegrowing practices to soil conditions variability in space and time. Then, a deep understanding of the environmental conditions that modulate soil-plant system functioning and control the production of quality wine is crucial for future global change adaptation. This study aimed to identify environmental factors controlling red wine quality by merging both winemaker and scientist knowledge. This work was performed on a vineyard in Saint-Emilion Grand Cru appellation, France. First, we conducted field investigations for micro-terroir scale soil mapping in 2017, based on pedological prospections (pits and auger borings) and both water table levels and main meteorological parameters monitoring (from November 2017 to November 2018). Additionally, we collected for each vineyard plot the corresponding wine quality rank established each year since 2012 and based on wine tasting sessions supervised by the winemakers. Subsequently we investigated both nutrients and water availability for the vine. This was achieved through correlative analysis using soil description, roots observation and water table level, stratified according to both soil functional units and wine quality ranks maps. Results show that the water table dynamic and the soil texture have a major impact on the root pattern of vines. Our study suggests that explanatory factors for wine quality are interactions between soil-water and roots during vine crop season. Here, best soils for fine wines could be observed for both non-severe water deficit and no-limited nutrient conditions.

Dune pattern, grain-size gradients and geochemistry were used to investigate the sources and dynamics of aeolian deposition during the last glacial in southwest France. The coversands form widespread fields of low-amplitude ridges (zibars), whereas Younger Dryas parabolic dunes mainly concentrate in corridors and along rivers. Spatial modelling of grain-size gradients combined with geochemical analysis points to a genetic relationship between coversands and loess, the latter resulting primarily from dust produced by aeolian abrasion of the coversands. The alluvium of the Garonne river provided also significant amounts of dust at a more local scale. The geochemical composition of loess shows much lower scattering than that of coversands, due to stronger homogenisation during transport in the atmosphere. Overall, sandy loess and loess deposits decrease in thickness away from the coversands. Dune orientation and grain-size gradients suggest that the efficient winds blew respectively from the W to the NW during the glacial, and the W-SW during the Younger Dryas. A comparison between the wind directions derived from the proxy data and those provided by palaeoclimatic simulations suggests a change of the main transport season. Ground surface conditions and their evolution throughout the year, i.e. the length of the season with snow and frozen or moist topsoil, and the seasonal distribution of wind speeds able to cause deflation are thought to have been the main factors that controlled the transport season in the study area.

Terroir effect on vine vigour, must composition and wine quality was investigated for Cabernet Sauvignon during a rainy vintage in a top estate of the Medoc area (Bordeaux, France). Soil was the only variable in this survey. Vine water status was determined by means of leaf water potential. Mild water deficits were observed only on a gravelly soil with a shallow root zone. Vine nitrogen status was determined by total must nitrogen content. Nitrogen status varied from deficient to unlimited. Nitrogen deficiency reduced vine vigour to a greater extent than did mild water deficits. The smallest berries, as well as the highest phenolic content for both must and wine, were observed under nitrogen deficiency. Both early mild water deficits and a nitrogen deficiency throughout the growth period were demonstrated to have beneficial effects on the phenolic content of berries and on wine quality. 1\vo combinations of vine water status and vine nitrogen status led to the most highly appreciated wines: a low nitrogen status without water deficits and a medium nitrogen status accompanied by mild water deficits.

A new passive sampler was designed and characterized for the determination of free copper ion (Cu(2+)) concentration in aqueous solution. Each sampling device was composed of a set of about 30 diffusive milligel (DMG) beads. Milligel beads with incorporated cation exchange resin (Chelex) particles were synthetized using an adapted droplet-based millifluidic process. Beads were assumed to be prolate spheroids, with a diameter of 1.6 mm and an anisotropic factor of 1.4. The milligel was controlled in chemical composition of hydrogel (monomer, cross-linker, initiator and Chelex concentration) and characterized in pore size. Two types of sampling devices were developed containing 7.5% and 15% of Chelex, respectively, and 6 nm pore size. The kinetic curves obtained demonstrated the accumulation of copper in the DMG according to the process described in the literature as absorption (and/or adsorption) and release following the Fick's first law of diffusion. For their use in water monitoring, the typical physico-chemical characteristics of the samplers, i.e. the mass-transfer coefficient (k0) and the sampler-water partition coefficient (Ksw), were determined based on a static exposure design. In order to determine the copper concentration in the samplers after their exposure, a method using DMG bead digestion combined to Inductively Coupled Plasma - Atomic Emission Spectrometry (ICP-AES) analysis was developed and optimized. The DMG devices proved to be capable to absorb free copper ions from an aqueous solution, which could be accurately quantified with a mean recovery of 99% and a repeatability of 7% (mean relative uncertainty).

Soil physical properties influence vineyard behaviour; therefore, the knowledge of their spatial variability is essential for making vineyard management decisions. Little work has been conducted at high spatial resolution on soil properties at depths lower than 0.30m which is of special relevance to perennial crops. The objectives of this work were to (i) analyse the spatial and vertical variability of soil depth, particle size fractions and water-holding capacity (WHC) by geostatistical techniques; (ii) study the causes of the variability, with additional information from classical soil sampling; and (iii) assess the significance of WHC through its relationship with vine vigour. The work was carried out in a vineyard of eight hectares within the D.O.Ca. Rioja (northern Spain). Soil variability was determined via grid sampling at three depth ranges (0-0.30, 0.30-0.60 and 0.60-0.90m). A conventional soil survey provided additional information on soil variability. Clay, sand and silt fractions, soil organic matter content, WHC and pruning weight were determined. Most soil properties had strong or moderate spatial dependence, with the exceptions of sand at 0.30-0.60m and silt in the topsoil. Topography and soil erosion caused the spatial variability of soil depth and contributed to the spatial distribution of particle size fractions in the topsoil, while the heterogeneity of parent material influenced the spatial pattern of soil properties at 0.60-0.90m. The WHC and soil depth spatial distributions related well to that of vine vigour, demonstrating the importance of knowing the spatial variability of these soil properties.

The methodological approach used to robustly optimize the characterization of the polydisperse colloidal phase of drain water samples is presented. The approach is based on asymmetric flow field-flow fractionation coupled to online ultraviolet/visible spectrophotometry, multi-angle light scattering, and inductively coupled plasma mass spectrometry. Operating factors such as the amount of sample injected and the ratio between main-flow and cross-flow rates were considered. The evaluation of the injection and fractionation steps was performed considering the polydispersity index and the contribution to the polydispersity of the plate height, the recovery, the retention ratio and the size range of the fractionated colloids. This approach allows the polydispersity of natural colloid samples to be taken into consideration to achieve the most efficient and representative fractionation. In addition to the size characterization, elemental analysis was also evaluated using the recovery, precision, and limits of detection and quantification relative to a trace element of interest (copper) in drain water. To complete this investigation, the potential application of the methodology was assessed using several independent drain water samples from different soils. The contribution of the polydispersity to the plate height ranges from 4.8 to 8.9 cm with a mean precision of 6 %. The mean colloidal recovery was 81 ± 3 %, and the mean retention ratio was 0.043–0.062. The limits of detection and quantification for copper were 0.6 and 1.8 μg L−1, respectively.