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Given the diverse physico-chemical properties of elements, we hypothesize that their incoherent distribution across the leaf tissues, combined with the distinct resistance to degradation that each tissue exhibits, leads to different turnover rates among elements. Moreover, litter layers of varying ages produce diverse chemical signatures in solution during the wet degradation. To verify our hypothesis, Na, K, Mg, Mn, Ca, Pb, Al and Fe were analysed together with the rare earth elements (REE) in the solid fractions and in the respective leachates of fresh leaves and different litter layers of two forested soils developed under Pseudotsuga menziesii and Fagus sylvatica L. trees. The results from the leaching experiment were also compared with the in situ REE composition of the soil solutions to clarify the impact that the litter degradation processes may have on soil solution chemical composition. Both tree species showed similar biogeochemical processes dominating the element dynamics during litter degradation. REE, Al, Fe and Pb were preferentially retained in the solid litter material, in comparison with the other cations, and their concentrations increased over time during the degradation. Accordingly, different litter fractions produced different yields of elements and REE patterns in the leachates, indicating that the tree species and the age of the litter play a role in the chemical release during degradation. In particular, the evolution of the REE patterns, relative to the age of the litter layers, allowed us to deliver new findings on REE fractionation and mobilization during litter decay. Specifically, the degradation of the litter was characterized by a decrease in the Y/Ho ratio and an increase in the LaN/YbN ratio. The relationship between these ratios provided information on the litter species-specific resistance to degradation, with Douglas-fir litter material showing a lower resistance. During the litter degradation of the two tree species, two main differences were highlighted with the help of the REE: (i) in Pseudotsuga menziesii the behaviour of Eu appeared to be linked to Ca during leaf senescence and (ii) species-specific release of organic acids during litter degradation leads to a more pronounced middle REE (MREE) enrichment in the Fagus sylvatica leachates. Finally, we showed the primary control effect that white fungi may have in Ce enrichment of soil solutions, which appears to be associated with the dissolution and/or direct transport of Ce-enriched MnO2 accumulated on the surface of the old litter due to the metabolic functioning of these microorganisms. Similar MREE and heavy REE (HREE) enrichments were also found in the leachates and the soil solutions, probably due to the higher affinity of these elements for the organic acids, which represent the primary products of organic matter degradation.

Within the critical zone, regolith plays a key role in the fundamental hydrological functions of water collection, storage, mixing and release. Electrical resistivity tomography (ERT) is recognized as a remarkable tool for characterizing the geometry and properties of the regolith, overcoming limitations inherent to conventional borehole-based investigations. For exploring shallow layers, a small electrode spacing (ES) will provide a denser set of apparent resistivity measurements of the subsurface. As this option is cumbersome and time-consuming, larger ES – albeit offering poorer shallow apparent resistivity data – is often preferred for large horizontal ERT surveys. To investigate the negative trade-off between larger ES and reduced accuracy of the inverted ERT images for shallow layers, we use a set of synthetic “conductive–resistive–conductive” three-layered soil–saprock/saprolite–bedrock models in combination with a reference field dataset. Our results suggest that an increase in ES causes a deterioration of the accuracy of the inverted ERT images in terms of both resistivity distribution and interface delineation and, most importantly, that this degradation increases sharply when the ES exceeds the thickness of the top subsurface layer. This finding, which is obvious for the characterization of shallow layers, is also relevant even when solely aiming for the characterization of deeper layers. We show that an oversized ES leads to overestimations of depth to bedrock and that this overestimation is even more important for subsurface structures with high resistivity contrast. To overcome this limitation, we propose adding interpolated levels of surficial apparent resistivity relying on a limited number of ERT profiles with a smaller ES. We demonstrate that our protocol significantly improves the accuracy of ERT profiles when using large ES, provided that the top layer has a rather constant thickness and resistivity. For the specific case of large-scale ERT surveys the proposed upgrading procedure is cost-effective in comparison to protocols based on small ES.

Hydromorphodynamic models are powerful tools for predicting the potential mobilization and transport of sediment in river ecosystems. Recent studies have shown that they are able to predict suspended sediment matter concentration in small river systems satisfactorily. However, hydro-sedimentary modelling exercises often neglect suspended sediment properties (e.g. sediment densities and grain-size distribution), which are known to directly control sediment dynamics in the water column during flood events. The main objective of this study is to assess whether a better representation of such properties leads to an improved performance in the model. The modelling approach utilizes a fully coupled hydromorphodynamic model based on TELEMAC-3D (v7p1) and an enhanced version of the sediment transport module SISYPHE (based on v7p1), which allows for a refined sediment representation (i.e. 10-class sediment mixtures instead of 2-class mixtures and distributed sediment density instead of uniform). The proposed developments of the SISYPHE model enable us to evaluate and discuss the added value of sediment representation refinement for improving sediment transport and riverbed evolution predictions. To this end, we used several model set-ups to evaluate the influence of sediment grain-size distribution, sediment density, and suspended sediment concentration at the upstream boundary on model predictions. As a test case, we simulated a flood event in a small-scale river, the Orne river in north-eastern France. Depending on the model set-up, the results show substantial discrepancies in terms of simulated bathymetry evolutions. Moreover, the model based on an enhanced configuration of the sediment grain-size distribution (10 classes of particle sizes) and with distinct densities per class outperforms the standard SISYPHE configuration, with only two sediment grain-size classes, in terms of simulated suspended sediment concentration.

For more than two decades, research groups in hydrology, ecology, soil science, and biogeochemistry have performed cryogenic water extractions (CWEs) for the analysis of δ2H and δ18O of soil water. Recent studies have shown that extraction conditions (time, temperature, and vacuum) along with physicochemical soil properties may affect extracted soil water isotope composition. Here we present results from the first worldwide round robin laboratory intercomparison. We test the null hypothesis that, with identical soils, standards, extraction protocols, and isotope analyses, cryogenic extractions across all laboratories are identical. Two standard soils with different physicochemical characteristics along with deionized (DI) reference water of known isotopic composition were shipped to 16 participating laboratories. Participants oven-dried and rewetted the soils to 8 and 20 % gravimetric water content (WC), using the deionized reference water. One batch of soil samples was extracted via predefined extraction conditions (time, temperature, and vacuum) identical to all laboratories; the second batch was extracted via conditions considered routine in the respective laboratory. All extracted water samples were analyzed for δ18O and δ2H by the lead laboratory (Global Institute for Water Security, GIWS, Saskatoon, Canada) using both a laser and an isotope ratio mass spectrometer (OA-ICOS and IRMS, respectively). We rejected the null hypothesis. Our results showed large differences in retrieved isotopic signatures among participating laboratories linked to soil type and soil water content with mean differences compared to the reference water ranging from +18.1 to −108.4 ‰ for δ2H and +11.8 to −14.9 ‰ for δ18O across all laboratories. In addition, differences were observed between OA-ICOS and IRMS isotope data. These were related to spectral interferences during OA-ICOS analysis that are especially problematic for the clayey loam soils used. While the types of cryogenic extraction lab construction varied from manifold systems to single chambers, no clear trends between system construction, applied extraction conditions, and extraction results were found. Rather, observed differences in the isotope data were influenced by interactions between multiple factors (soil type and properties, soil water content, system setup, extraction efficiency, extraction system leaks, and each lab's internal accuracy). Our results question the usefulness of cryogenic extraction as a standard for water extraction since results are not comparable across laboratories. This suggests that defining any sort of standard extraction procedure applicable across laboratories is challenging. Laboratories might have to establish calibration functions for their specific extraction system for each natural soil type, individually.

In rural areas, nitrate concentrations in surface waters most often originate from the leaching of excess N fertilizer in agricultural lands, whereas forested catchments often have good water quality. However, Douglas-fir plantations may induce nitrogen cycle unbalances which may lead to an excess of nitrate production in the soil. We hypothesize that the excess of production of nitrate in the soil and nitrate leaching to streamwater is greater in catchments planted with Douglas fir. We used paired catchments in both France and Luxembourg with different land covers (Douglas-fir, Spruce, Deciduous, Grassland and clearcut) which were monitored over a 3-5 year period in order to assess the effect of Douglas-fir plantations on the chemical composition of surface water. Nitrate concentration in the soil and groundwater were also monitored. The results show that nitrate concentrations in streams draining Douglas-fir catchments were two to ten times higher than in streams draining other land covers, but were similar to the clearcut catchment. Nitrate concentrations under Douglas-fir in groundwater (up to 50 mg L -1 ) and in the soil were also higher than under all other land covers. Soil nitrate concentration was related to stream nitrate concentration. This suggests that soil processes, through excessive nitrate production under Douglas-fir, are driving the nitrate concentration in the stream water and our hypothesis of a transfer of a fairly large proportion of this excessive production from the soil to the stream is supported. This study also shows that nitrate concentrations in surface and ground waters in rural areas could also originate from Douglas fir forested catchments. The impact of Douglas-fir is nevertheless reduced downstream through a dilution effect: mixing tree species at the catchment scale could thus be a solution to mitigate the effect of Douglas-fir on nitrate concentration in surface waters., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

Understanding the possible consequences of anthropogenic activities on REY environmental fate and adverse effects on biota requires a detailed knowledge of their distribution between the particulate, colloidal and dissolved fractions. Such information is practically non-existent for peri-urban rivers having heavily populated basins and suffering from direct impacts from various human activities. The present study compared the distribution of REY among the particulate (>1000 nm), coarse colloidal (1000 nm - 220 nm), small colloidal (220 nm - 10 kDa) and dissolved (<10 kDa) water fractions in two peri-urban river basins having contrasted land uses (agricultural vs urban/industrial) under low and high flow conditions. Regardless of hydrological conditions, most of the REY were in the particulate fraction for both catchments. These results suggest erosion of soils as the main source of particulate REY in the two rivers, although a Nd anomaly of industrial origin occurred in the particulate and coarse colloidal fractions of the industrialized river basin. During low flow, the REY patterns of the dissolved fraction displayed marked Gd and Eu anomalies and a fractionation between Light REY and Heavy REY. Both characteristics reflect the influence of wastewater treatment plant effluents on the dissolved REY patterns in the two rivers. During high flow, the dissolved fraction acquired a less fractionated, more natural Light REY and Middle REY pattern, including much lower Gd and Eu positive anomalies. The REY fractionation of the coarse colloidal fraction was close to the particulate, while small colloids were depleted in Light REY and more similar to the dissolved fraction. These different patterns suggest a difference in the nature of REY bearing phases between the two colloidal fractions. The available results collectively show that a complete understanding of REY environmental fate and anomalies cannot be achieved from the sole study of filterable water fractions (typically <0.45 μm)., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

The recycling of biogas residues resulting from the anaerobic digestion of organic waste on agricultural land is among the means to reduce chemical fertilizer use and combat climate change. This in sacco decomposition study investigates (1) the potential of the granulated biogas residue fraction to provide nutrients and enhance soil carbon sequestration when utilized as exogenous organic matter in grassland soils, and (2) the impact of different nitrogen fertilizers on the organic matter decomposition and nutrient release processes. The experiment was conducted in two permanent grasslands of the Greater Region over one management period using rooibos tea as a comparator material. The decomposition and chemical changes of the two materials after incubation in the soil were assessed by measuring the mass loss, total carbon and nitrogen status, and fibre composition in cellulose, hemicellulose and lignin. Overall, after the incubation period, granulated biogas residue maintained up to 68% of its total mass, organic matter and total carbon; increased its content in recalcitrant organic matter by up to 45% and released 45% of its total nitrogen. Granulated biogas residue demonstrated resilience and a higher response uniformity when exposed to different nitrogen fertilizers, as opposed to the comparator material of rooibos tea. However, the magnitude of fertilizer-type effect varied, with ammonium nitrate and the combinatorial treatment of raw biogas residue mixed with urea leading to the highest organic matter loss from the bags. Our findings suggest that granulated biogas residue is a biofertilizer with the potential to supply nutrients to soil biota over time, and promote carbon sequestration in grassland soils, and thereby advance agricultural sustainability while contributing to climate change mitigation., (Copyright © 2021. Published by Elsevier Ltd.)

The main land use/land cover changes (LULCC) have been associated with population growth and energy policies in the São Paulo State, Brazil, since 1970. The LULCC can alter the behavior of trace elements in different environmental systems, with the riverbed sediments being the main reservoirs or sinks for trace elements, and thus become a valuable environmental archive on temporal changes. Thus, the main purpose of the study was to apply a multi-tracer analysis to estimate the historical evolution of pollution in riverbed sediment of a subtropical watershed, the lower course of the Piracicaba River, São Paulo, Brazil. 210 Pb measurements done on river sediment core samples allowed estimating a sedimentation rate of 9 mm yr -1 between 1971 and 2001. Zn was the most abundant trace element in the sediment core, followed by Cr, Cu, Ni, Pb, Sc and Cd. The total concentrations of Cd, Cr, Ni, Sc and Pb presented practically no variations in the sediment core, with a continuous excess of ca. 0.27 μg g -1  yr -1 of Cu and of ca. 0.54 μg g -1  yr -1 of Zn between 1971 and 2001. The excess of Cu and Zn was associated with labile fractions, in particular with carbonate bound to Zn and organic matter bound to Cu. The assessment of trace metal pollution indicated that most of the trace elements were of geogenic origin, except for Cu and Zn. According to the sediment quality guidelines used in Brazil, Pb showed no potential toxic effect, Cu, Cr and Zn were intermediate to Threshold Effect Level (TEL) and Probable Effect Level (PEL) and the Cd and Ni concentrations were above the PEL limits. The elemental and isotopic analysis of C and N and the C/N ratio indicated that the anthropogenic origin of POM found in the sediment core is related mainly to domestic sewage., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

To provide sufficient quantities of food and feed, farming systems have to overcome limiting factors such as the nutrient depletion of arable soils. Nitrogen being the main mineral element required for plant growth, has led to the extensive use of chemical fertilizers causing nitrogen pollution of the ecosystems. This field study investigates the use of biogas residues (BRs) as biofertilizers and their contribution to the mitigation of nitrate leaching in agricultural soils, while also demonstrating the polluting nature of chemical fertilizers. Nine different fertilization treatments classified in three schemes and two nitrogen doses were tested for three consecutive years on a grassland in the Walloon Region of Belgium. Residual soil mineral nitrogen, percentage contribution of treatments in residual nitrate and agronomic performance were assessed for each fertilization treatment. The results obtained showed significant differences on treatment and scheme level regarding nitrate accumulation in the soil, with chemical fertilizers posing the highest nitrate leaching risk. BRs did not cause nitrate accumulation in the soil, and were N rate and rainfall independent, while the chemical treatments indicated a cumulative tendency under high N rate and low precipitation. Forage yield did not demonstrate statistical differences on treatment and scheme level but varied with changing precipitation, while the maximum application rate suggested a plateau. Aboveground nitrogen content was significantly higher after the application of chemical fertilizers only in the first year, while all the chemical treatments indicated a dilution effect under elevated annual rainfall. Finally, the partial substitution of chemical fertilizers by raw digestate reduced the concentration of NO 3 - in the soil without having a negative impact on the yield and N content of the biomass. These results strongly advocate for the environmental benefits of BRs over chemical fertilizers and underline their suitability as biofertilizers and substitutes for chemical fertilizers in similar agricultural systems., (Copyright © 2019. Published by Elsevier B.V.)

Approximately 40% of the volume of domestic sewage generated in the São Paulo State is untreated and released into water bodies, causing serious pollution problems that affect the water quality and especially the suspended sediments transported by rivers. Thus, this paper investigates the seasonal influence on the origin and fluxes of Cu, Co, Cr, Zn, Cd, Ni, Sc and particulate organic matter (POM) in sediments transported by a disturbed watershed in the São Paulo State, i.e. the Sorocaba River basin. POM was characterized using particulate organic carbon, particulate organic nitrogen, C:N ratio and δ 13 C and δ 15 N stable isotopic composition. Eight sample collections of fine suspended sediments (FSS) were carried out at the mouth of the Sorocaba River from July 2009 to May 2010. During the study period, the discharge rate followed the seasonal variation trend of the past 25 years. Zn was the most abundant trace element in the FSS, followed by Cr, Cu, Ni, Co, Sc and Cd. There was a higher concentration of trace elements during the dry season, except for Sc and Co, which did not vary seasonally. The POM showed the same trend, with higher concentrations during the dry season. The calculated enrichment factors and geoaccumulation index indicated that most of the trace elements are of geogenic origin, except for Zn, which showed significant anthropogenic contributions (55%). The elemental and isotopic analysis of C and N and C:N ratio indicated that the anthropogenic origin of POM found in the FSS is related mainly to domestic sewage (97%), while the significant correlation found between the concentrations of Zn and POM indicates that the main anthropogenic source of Zn is related to this domestic sewage. The FSS load transported during the study period was of 373,194 t y -1 , of which 87% occurred during the rainy season., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

In order to precisely quantify the contribution of anthropogenic activities and geogenic sources to the dissolved and suspended loads of rivers we have combined for the first time Rare Earth Element (REE) concentrations with Sr-Nd-Pb isotope ratios. We observed enrichments in Anthropogenic Rare Earth Elements (AREE) for dissolved (Gd) and suspended (Ce and Nd) loads of river water. During flood events, AREE anomalies progressively disappeared and gave way to the geogenic chemical signature of the basin in both dissolved and suspended loads. The isotopic data confirm these observations and shed new light on the trace elements sources. On the one hand, dissolved loads have peculiar isotopic characteristics and carry mainly limestone-derived and anthropogenic Sr and Nd as well as significant amounts of anthropogenic Pb. On the other hand, the results clearly indicate that anthropogenic contributions impact the suspended loads in all hydrological conditions. This study demonstrates that anthropogenic contributions to the river may change not only Pb but also Sr and Nd isotopic compositions in both dissolved and suspended loads. This is of importance for future provenance studies.

Trace metal atmospheric contamination was assessed in one of the oldest European industrial sites of steel production situated in the southern part of the Grand-Duchy of Luxembourg. Using elemental ratios as well as Pb, Sr, and Nd isotopic compositions as tracers, we found preliminary results concerning the trace metal enrichment and the chemical/isotopic signatures of the most important emission sources using the lichen Xanthoria parietina sampled at 15 sites along a SW-NE transect. The concentrations of these elements decreased with increasing distance from the historical and actual steel-work areas. The combination of the different tracers (major elements, Rare Earth Element ratios, Pb, Sr and Nd isotopes) enabled us to distinguish between three principal sources: the historical steel production (old tailings corresponding to blast-furnace residues), the present steel production (industrial sites with arc electric furnace units) and the regional background (baseline) components. Other anthropogenic sources including a waste incinerator and major roads had only weak impacts on lichen chemistry and isotopic ratios. The correlation between the Sr and Nd isotope ratios indicated that the Sr-Nd isotope systems represented useful tools to trace atmospheric emissions of factories using scrap metal for steel production.

Total atmospheric Hg contamination in a French mountainous catchment upstream from a chlor-alkali industrial site was assessed using Hg concentrations in the deepest soil horizon, in the stream bottom sediments, in river waters and in bryophytes. The natural background level of Hg content deriving from rock weathering was estimated to 32 ng g(-1) in the deepest soil layers. The soils appear to be Hg contaminated in two stages: atmospheric deposition and leaching through the soil profiles of Hg-organic matter complexes. The Hg enrichment factor (EF(Hg)(Sc)) which could be calculated by normalization to a conservative element like Sc, allows to estimate the major contribution (63% to 95%) of the atmospheric inputs, even in the upper part of the basin. This contribution may be attributed to diffuse regional atmospheric deposition of Hg and is mainly due to the geographic location of the chlor-alkali plant. This study shows for the first time that the mercury enrichment is proportional to the carbon content indicating that most of the atmospheric mercury deposition is trapped by the organic matter contained in the soils and in the stream sediments. The Hg stock in the soils of the upper catchment and the soil erosion contribution to the riverine Hg fluxes are estimated for the first time and allow to assess the Hg residence time. It indicates that Hg is trapped in the soils of such a polluted catchment for probably several thousand years.

River bottom sediments and soils were collected from the industrialized Thur River basin (north-eastern France) to assess mercury contamination. The regional geochemical background level of total mercury was evaluated to calculate mercury contamination factors (Fc) in soils and river bottom sediments. Our estimate of the mean background mercury levels in river sediments and soils, not affected by human activities, was 232 ng x g(-1) (range: 27-406 ng x g(-1)). Sediments contaminated by the effluent from a chlor-alkali plant yielded the highest contamination factors (Fc=1784). Contamination factors of surficial soils within 1 km of the industrial site range from 6.3 to 43.6. This contamination is attributed to diffuse atmospheric deposition from this local plant. However, even upstream from this industrial area elevated contamination factors were recorded for river bottom sediments (Fc=3.2 to 26.4) and for one alluvial soil profile (Fc=10). This is possibly due to past pollution resulting from waste water discharges. Mercury contamination in the different horizons of alluvial soils is not correlated with soil organic carbon content, but may be the result of occasional accidental pollution arising from the introduction of contaminated suspended particulate matter by the Thur River during periods of flooding.