GEMAS: Phosphorus in European agricultural soil - sources versus sinks at the continental-scale - the geological perspective.

Phosphorus (P) is one of the essential elements for life on Earth. As a major nutrient it is needed for healthy growth both in plants and living organisms. Although the abundance of P in the Earth's upper continental crust is relatively high (655 mg/kg), many soil types are poor in available phosphorus. The main natural factors controlling the availability of P in soil are pH, mineralogy, and formation of insoluble complexes with Al and Fe under acidic, and with Ca and Mg under alkaline soil conditions. Superimposed weathering processes and climate contribute strongly to P mobility and availability. Additionally, a large fraction of total soil P is in organic forms, which are not directly available to plants. Phosphorus is a major component in fertilisers and thus a significant source of anthropogenic P in soil and water. In the agricultural soil samples that were collected during the Geochemical Mapping of Agricultural and grazing land Soil (GEMAS) project, the total P concentrations (XRF, median 786 m/kg) are only slightly higher than those extracted by hot aqua regia (AR, median 653 mg/kg), while the median concentration in the weak MMI® cold extraction is as low as 4.1 mg/kg. The AR results show very low P concentrations over the coarse-grained sandy sediments of the last glaciation in central and northern Europe and in calcareous soil. The southern limit of the last glaciation is visible as a concentration break on the geochemical maps. In general, north-eastern and north-western Europe are marked by high P values, probably related to cold and humid climate and enrichment in humus-rich coastal soil. The spatial distribution of P at the continental-scale is dominated by geogenic and climatic factors, and the anthropogenic influence is difficult to assess and quantify.

How the EU Soil Observatory contributes to a stronger soil erosion community.

New policy developments have emerged in relation to soil conservation after 2020. The Common Agricultural Policy (CAP) 2023-2027, the proposal for a Soil Monitoring Law and the mission 'A Soil Deal for Europe' have shaped a new policy framework at EU level, which requires updated assessments on soil erosion and land degradation. The EU Soil Observatory (EUSO) successfully organised a scientific workshop on 'Soil erosion for the EU' in June 2022. The event has seen the participation of more than 330 people from 63 countries, addressing important topics such as (i) management practices, (ii) large scale modelling, (iii) the importance of sediments in nutrient cycle, (vi) the role of landslides and (v) laying the foundations for early career scientists. As a follow up, among the 120 abstracts submitted in the workshop, we received fifteen manuscripts, out of which nine were selected for publication in the present special issue. In this editorial, we summarize the major challenges that the soil erosion research community faces in relation to supporting the increasing role of soils in the EU Green Deal.

Lithium isotopic fingerprints of sources and processes in surface waters of the Ebro River Basin (Spain).

The Ebro River in north-eastern Spain is among the largest contributors of freshwater to the Mediterranean Sea and ends in the Ebro delta, one of the major wetlands in Europe. The bedrock of the Ebro River basin mainly consists of carbonate rocks and evaporites of Palaeozoic and Mesozoic age, and the river flows through several large cities, and agricultural and industrial areas. The Ebro outlet at Amposta was sampled once a month for a year (2006), and a field campaign in April of the same year sampled the Ebro along its main course as well as its principal tributaries. In the present study, the behaviour of Li and its isotopes was investigated at basin scale, with the objective of elucidating the processes controlling the lithium-isotope signatures of a large river draining mostly sedimentary bedrock. δ7Li values show a narrow range from +17.1 ‰ to +18.3 ‰ along the Ebro main stream, and between +16.3 and +18.9 ‰ at the outlet. In the major tributaries, the δ7Li values ranged from +12.9 ‰ to +20.9 ‰, with bedrock values ranging from +0.5 to +29.3 ‰. Comparing Li concentrations with Cl and SO4 ones, it appears that evaporite weathering plays an important role in controlling Li concentrations, but no anthropogenic agricultural or industrial influence on Li concentrations was detected. The Na/Li, Cl/Li and SO4/Li ratios clearly reflect the role of halite dissolution for some tributaries (Gallego, Ega and Aragon), gypsum dominating others (Guadalope, Matarrana, Huerva and Segre), and little influence of carbonate in all tributaries, the Ebro itself being a mixture of all tributaries. We tentatively applied the simple Rayleigh fractionation model, but most δ7Li values of the Ebro water samples plotted away from the fractionation line, reinforcing the major role of mixing processes in the Ebro basin, rather than fractionation processes during water/rock interactions. A comparison of δ7Li values and 87Sr/86Sr ratios further demonstrates the role of gypsum/anhydrite and limestone in the Ebro and its tributaries. Sr-isotopes show a non-negligible role of carbonate dissolution, generally considered to be weak in the control of the lithium cycle in catchments.

U-Th signatures of agricultural soil at the European continental scale (GEMAS): Distribution, weathering patterns and processes controlling their concentrations.

Agricultural soil (Ap-horizon, 0-20cm) samples were collected in Europe (33 countries, 5.6millionkm2) as part of the GEMAS (GEochemical Mapping of Agricultural and grazing land Soil) soil-mapping project. The GEMAS survey area includes diverse groups of soil parent materials with varying geological history, a wide range of climate zones, and landscapes. The soil data have been used to provide a general view of U and Th mobility at the continental scale, using aqua regia and MMI® extractions. The U-Th distribution pattern is closely related to the compositional variation of the geological bedrock on which the soil is developed and human impact on the environment has not concealed these genuine geochemical features. Results from both extraction methods (aqua regia and MMI®) used in this study support this general picture. Ternary plots of several soil parameters have been used to evaluate chemical weathering trends. In the aqua regia extraction, some relative Th enrichment-U loss is related to the influence of alkaline and schist bedrocks, due to weathering processes. Whereas U enrichment-Th loss characterizes soils developed on alkaline and mafic bedrock end-members on one hand and calcareous rock, with a concomitant Sc depletion (used as proxy for mafic lithologies), on the other hand. This reflects weathering processes sensu latu, and their role in U retention in related soils. Contrary to that, the large U enrichment relative to Th in the MMI® extraction and the absence of end-member parent material influence explaining the enrichment indicates that lithology is not the cause of such enrichment. Comparison of U and Th to the soil geological parent material evidenced i) higher capability of U to be weathered in soils and higher resistance of Th to weathering processes and its enrichment in soils; and, ii) the MMI® extraction results show a greater affinity of U than Th for the bearing phases like clays and organic matter. The comparison of geological units with U anomalies in agricultural soil at the country scale (France) enables better understanding of U sources in the surficial environment and can be a useful tool in risk assessments.

An innovative application of stable isotopes (δ2H and δ18O) for tracing pollutant plumes in groundwater.

The identification of the sources of contaminants present in groundwater at industrial sites is primordial to address environmental and industrial issues. However, available tools are often inadequate or expensive. Here, we present the data of stable isotopes (δ18O and δ2H) of the water molecule at an industrial site where electrochemistry plant occurs impacting the groundwater quality. High ClO3 and ClO4 contents and 2H enrichment have been measured in groundwater. Recharge of aquifer relates to infiltration of rainwater and by subsurface inflow. On-site, industrial products are generated by electrolysis. We show that the electrolysis process leads to a large 2H enrichment (+425‰) in solutions. In the absence of hydrothermal water input containing H2S, we demonstrate that the relationship between δ18O and δ2H can be easily used in a way to trace the origin of the ClO3 and ClO4 in groundwater. Isotopes evidenced first a leakage from end-product storage tanks or during the production process itself. Then, an accumulation and release of ClO3 and ClO4 from soil is demonstrated. Our study successfully shows that stable isotopes are a powerful and low cost tool for tracing pollutant plumes in an industrial context using electrolysis process.

Coastal groundwater salinization: Focus on the vertical variability in a multi-layered aquifer through a multi-isotope fingerprinting (Roussillon Basin, France).

The Roussillon sedimentary Basin (South France) is a complex multi-layered aquifer, close to the Mediterranean Sea facing seasonally increases of water abstraction and salinization issues. We report geochemical and isotopic vertical variability in this aquifer using groundwater sampled with a Westbay System® at two coastal monitoring sites: Barcarès and Canet. The Westbay sampling allows pointing out and explaining the variation of water quality along vertical profiles, both in productive layers and in the less permeable ones where most of the chemical processes are susceptible to take place. The aquifer layers are not equally impacted by salinization, with electrical conductivity ranging from 460 to 43,000µS·cm(-1). The δ(2)H-δ(18)O signatures show mixing between seawater and freshwater components with long water residence time as evidenced by the lack of contribution from modern water using (3)H, (14)C and CFCs/SF6. S(SO4) isotopes also evidence seawater contribution but some signatures can be related to oxidation of pyrite and/or organically bounded S. In the upper layers (87)Sr/(86)Sr ratios are close to that of seawater and then increase with depth, reflecting water-rock interaction with argillaceous formations while punctual low values reflect interaction with carbonate. Boron isotopes highlight secondary processes such as adsorption/desorption onto clays in addition to mixings. At the Barcarès site (120m deep), the high salinity in some layers appear to be related neither to present day seawater intrusion, nor to Salses-Leucate lagoonwater intrusion. Groundwater chemical composition thus highlights binary mixing between fresh groundwater and inherited salty water together with cation exchange processes, water-rock interactions and, locally, sedimentary organic matter mineralisation probably enhanced by pyrite oxidation. Finally, combining the results of this study and those of Caballero and Ladouche (2015), we discuss the possible future evolution of this aquifer system under global change, as well as the potential management strategies needed to preserve quantitatively and qualitatively this water resource.

Sulfur and oxygen isotope tracing in zero valent iron based In situ remediation system for metal contaminants.

In the present study, controlled laboratory column experiments were conducted to understand the biogeochemical changes during the microbial sulfate reduction. Sulfur and oxygen isotopes of sulfate were followed during sulfate reduction in zero valent iron incubated flow through columns at a constant temperature of 20±1°C for 90 d. Sulfur isotope signatures show considerable variation during biological sulfate reduction in our columns in comparison to abiotic columns where no changes were observed. The magnitude of the enrichment in δ(34)S values ranged from 9.4‰ to 10.3‰ compared to initial value of 2.3‰, having total fractionation δS between biotic and abiotic columns as much as 6.1‰. Sulfur isotope fractionation was directly proportional to the sulfate reduction rates in the columns. Oxygen isotopes in this experiment seem less sensitive to microbial activities and more likely to be influenced by isotopic exchange with ambient water. A linear relationship is observed between δ(34)S and δ(18)O in biotic conditions and we also highlight a good relationship between δ(34)S and sulfate reduction rate in biotic columns.

Influence of methane addition on selenium isotope sensitivity and their spectral interferences.

The measurements of stable selenium (Se) isotopic signatures by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) are very challenging, due to the presence of spectral interferences and the low abundance of Se in environmental samples. We systematically investigated the effect of methane addition on the signal of Se isotopes and their interferences. It is the first time that the effect of methane addition has been assessed for all Se isotopes and its potential interferences using hydride generator multi-collector inductively coupled plasma mass spectrometry (HG-MC-ICP-MS). Our results show that a small methane addition increases the sensitivity. However, the response differs between a hydride generator and a standard introduction system, which might be related to differences in the ionization processes. Both argon and hydrogen-based interferences, the most common spectral interferences on selenium isotopes in HG-MC-ICP-MS, decrease with increasing methane addition. Therefore, analyte-interference ratios and precision are improved. Methane addition has thus a high potential for the application to stable Se isotopes ratios by HG-MC-ICP-MS.

Chemical and strontium isotope characterization of rainwater in France: influence of sources and hydrogeochemical implications.

Strontium isotope ratios and Ca2+, Na+, K+, Mg2+, Cl-, SO4(2-), NO3- and Sr2+ concentrations were measured in rainwater samples collected in four stations in France (Brest, Dax, Orleans and Clermont-Ferrand) over a period of 1 year. Each sample represented a monthly series of rain events. The chemical composition and the 87Sr/86Sr ratios of the rainwater samples varied considerably. Using Na concentrations as an indicator of marine origin, the proportion of marine and crustal elements was estimated from elemental ratios. Strontium isotopes were used to characterize the different sources using data from the four stations and the literature. Such sources include sea salts, crustal sources (carbonates, silicates and volcanic rocks) and anthropogenic sources (fertilizers, automobile exhausts, incinerators and urban heating).

Influence of hydropower dams on the composition of the suspended and riverbank sediments in the Danube.

Large hydropower dams have major impacts on flow regime, sediment transport and the characteristics of water and sediment in downstream rivers. The Gabcikovo and Iron Gate dams divide the studied Danube transect (rkm 1895-795) into three parts. In the Gabcikovo Reservoir (length of 40km) only a part of the incoming suspended sediments were deposited. Contrary to this, in the much larger Iron Gate backwater zone and reservoir (length of 310km) all riverine suspended sediments were deposited within the reservoir. Subsequently, suspended sediments were transported by tributaries into the Iron Gate backwater zone. Here they were modified by fractional sedimentation before they transgressed downstream via the dams. Compared with undammed Danube sections, Iron Gate reservoir sediment and suspended matter showed higher clay contents and different K/Ga and Metal/Ga ratios. These findings emphasize the importance of reservoir-river sediment-fractionation.

Tracking the sources of nitrate in groundwater using coupled nitrogen and boron isotopes: a synthesis.

Nitrate (NO3) is one of the world's major pollutants of drinking water resources. Although recent European Directives have reduced input from intensive agriculture, NO3 levels in groundwater are approaching the drinking water limit of 50 mg L(-1) almost everywhere. Determining the sources of groundwater contamination is an important first step toward improving its quality by emission control. It is with this aim that we review here the benefit of using a coupled isotopic approach (delta15N and delta11B), in addition to conventional hydrogeological analyses, to trace the origin of NO3 in water. The studied watersheds include both fractured bedrock and alluvial (subsurface and deep) hydrogeological contexts. The joint use of nitrogen and boron isotope systematics in each context deciphers the origin of NO3 in the groundwater and allows a semi-quantification of the contributions of the respective pollution sources (mineral fertilizers, wastewater, and animal manure).

Boron isotope fractionation in groundwaters as an indicator of past permafrost conditions in the fractured crystalline bedrock of the fennoscandian shield.

The Fennoscandian Shield has been subjected to several glaciations over the past million years, the last of which (Weichselian Ice Age) ended only at about 10Ka. Here we used boron isotopes and B contents to (a) establish the degree of water-rock interaction (WRI) and (b) clarify freezing processes within groundwaters from the Aspo site in Sweden and from various sites in Finland. The high delta(11)B values recorded by all groundwaters (up to 51.9 per thousand) including diluted, boron-poor, inland groundwaters suggest selective uptake of (10)B into ice related to freezing processes under permafrost conditions. According to co-existing ice and residual brines in a Canadian frozen mine, this fractionation process, enhanced by Rayleigh fractionation, can generate a natural field of isotopic variation around 60 per thousand and provides a new application of B isotope that makes possible to easily characterise groundwaters that underwent past permafrost conditions.

Investigating the sources of the labile fraction in sediments from silicate-drained rocks using trace elements, and strontium and lead isotopes.

Elemental concentrations of the trace elements Rb, Sr, Th, Pb, Zn, Cu, Ni, Cd and Sb, as well as Sr and Pb isotopic compositions, were determined on the labile fraction (called acid-extracted matter AEM, Négrel et al., Chem. Geol. 166 (2000) 271-85) of soil and sediment along two small rivers located in the centre of France, one flowing from basalt, the other one on granite-gneiss. Oxide-mineral form in AEM (i.e. Fe-Mn oxides), acts as the main carrier phase. Analysis of the relationships between the trace elements, and lead and strontium isotopes allows the origin of the elements (i.e. natural and anthropogenic) and their history, both in the sediment and soil from the small watersheds to be assessed. Lead-isotope compositions in AEM display large fluctuation in the two watersheds and show a large scatter between natural input (basalt and granite), atmospheric input from gasoline, and input from past mining activities. On the basaltic watershed, Pb and other trace elements like Sb deriving from past mining waste are mainly related to atmospheric origin, while on the granitic terrain Pb originates from mineralization. The Sr-isotope compositions of AEM, water and residues are similar in the watershed draining basalt. On the watershed draining granite, AEM and streamwater shows 87Sr/86Sr ratios similar in the upstream part of the watershed and a divergence between the two ratios appears in the downstream part of the watershed implying that oxides have precipitated upstream and are not re-equilibrated during their transport downstream.