Collaborative determination of trace element mass fractions and isotope ratios in AQUA-1 drinking water certified reference material.

The Isotrace CNRS workgroup in collaboration with National Research Council of Canada has characterized a number of trace element mass fractions and isotope ratios currently not certified in AQUA-1 natural drinking water reference material (NRC Canada). This survey further expands the use of this material as a tool for environmental quality control, method validation, and method development tool for the international community. Simultaneously, the SLRS-6 river water was analyzed as quality control and also in order to compare both water characteristics, which were sampled in the same area but having undergone different treatment. Mass fractions for B, Cs, Li, Ga, Ge, Hf, Nb, P, Rb, Rh, Re, S, Sc, Se, Si, Sn, Th, Ti, Tl, W, Y, Zr, REEs, and six isotopic ratios are proposed for Sr and Pb. Measurements were mostly performed using ICP-MS with various calibration approaches. The results are reported as consensus or indicative values depending on the number of available datasets, with their associated uncertainties.

Agricultural groundwater with high nitrates and dissolved salts given to pregnant mice alters brain development in the offspring.

Groundwater is the main source of drinking water for a significant portion of the human population. In many agricultural areas, diffuse pollution such as high levels of total dissolved salts including nitrate, puts the quality of this resource at risk. However, the effect of exposure to these water contaminants on brain development is currently poorly understood. Here we characterised water from a borewell located in an intensely cultivated area (agricultural) or water from a borewell located in a nearby pristine forest. The agricultural borewell water was rich in nitrates with high total dissolved salts. We then studied the consequence of drinking the agricultural water on mouse brain development. For this, the agricultural borewell water or forest water was given to mice for 6 weeks before and during pregnancy and lactation. The brains of the offspring born to these dams were analysed at postnatal day (P)5 and P21 and compared using immunohistochemistry for changes in glial cells, neurons, myelin, and cell death across many brain regions. Brains from offspring born to dams who had been given agricultural water (versus forest control water) were significantly smaller, and at P21 had a significant degeneration of neurons and increased numbers of microglia in the motor cortex, had fewer white matter astrocytes and an increase in cell death, particularly in the dentate gyrus. This study shows that brain development is sensitive to water composition. It points to the importance of assessing neurodevelopmental delays when considering the effect of water contaminated with agricultural run offs on human health. MAIN FINDING: Pregnant and lactating mice were given borewell water from intensely cultivated land. Offspring brains reveal degeneration of neurons and a loss of astrocytes, increase in microglial cells and cell death, pointing to neurodevelopmental problems.

Chemical weathering and CO2 consumption in the upper Nyong Basin rivers (Central Africa): Insights on climatic and anthropogenic forcing in humid tropical environments.

A hydrological and hydrochemical database (produced by the M-TROPICS critical zone observatory) in the upper Nyong Basin from 1998 to 2017 was used to evaluate the river's response to climatic and anthropogenic forcing and examine chemical weathering processes. SiO2 and HCO3- constitute about 85 % of the Total dissolved solids (TDS) load, equivalent to 0.12 × 109 kg. y-1. Electrical conductivity (EC), Total dissolved solids (TDS), major cations, major anions (except F- and NO3-) and alkalinity (Alk) vary seasonally and follow a predictable model with discharge. Atlantic Meridional Mode oscillation controls the long-term water chemistry. Atmospheric input and silicate weathering are the main factors influencing the Nyong rivers chemistry. However, several indices supported the progressive water quality deterioration by human activities, namely: the excess of Cl- and SO42- after the substraction of atmospheric inputs, the basic pH observed for specific samples, long-term increase in the values of pH, EC, TDS, EC, Mg2+, Ca2+, F-, NO3-, HCO3-, Alk, SiO2 and Dissolved Organic Carbon. Runoff and physical erosion have an important control on chemical erosion in the upper Nyong Basin rivers. The chemical erosion rate (3.3 t.km-2.y-1) equals the silicate weathering rate. The CO2 consumption rate, in the Nyong rivers, is lower than the global average (98× 103 for silicate weathering and 246 × 103 mol.km-2.y-1 for chemical erosion) and estimated at 52.3 × 103 for silicate weathering and 54.1 × 103 mol.km-2.y-1 for chemical erosion. At Olama, the most downstream location of the monitoring setup, the Nyong River Basin consumed 1 × 109 mol.y-1 of CO2 by chemical erosion.

Tailor-made biochar systems: Interdisciplinary evaluations of ecosystem services and farmer livelihoods in tropical agro-ecosystems.

Organic matter management is key to sustain ecosystem services provided by soils. However, it is rarely considered in a holistic view, considering local resources, agro-environmental effects and harmonization with farmers' needs. Organic inputs, like compost and biochar, could represent a sustainable solution to massive current challenges associated to the intensification of agriculture, in particular for tropical regions. Here we assess the potential of agricultural residues as a resource for farmer communities in southwestern India to reduce their dependency on external inputs and sustain ecosystem services. We propose a novel joint evaluation of farmers' aspirations together with agro-environmental effects of organic inputs on soils. Our soil quality evaluation showed that biochar alone or with compost did not improve unilaterally soils in the tropics (Anthroposol, Ferralsol and Vertisol). Many organic inputs led to an initial decrease in water-holding capacities of control soils (-27.3%: coconut shell biochar with compost on Anthroposol). Responses to organic matter inputs for carbon were strongest for Ferralsols (+33.4% with rice husk biochar), and mostly positive for Anthroposols and Vertisols (+12.5% to +13.8% respectively). Soil pH responses were surprisingly negative for Ferralsols and only positive if biochar was applied alone (between -5.6% to +1.9%). For Anthroposols and Vertisols, highest increases were achieved with rice husk biochar + vermicomposts (+7.2% and +5.2% respectively). Our socio-economic evaluation showed that farmers with a stronger economical position showed greater interest towards technology like biochar (factor 1.3 to 1.6 higher for farmers cultivating Anthroposols and/or Vertisols compared to Ferralsols), while poorer farmers more skepticism, which may lead to an increased economical gap within rural communities if technologies are not implemented with long-term guidance. These results advocate for an interdisciplinary evaluation of agricultural technology prior to its implementation as a development tool in the field.

Multielementary (Cd, Cu, Pb, Zn, Ni) Stable Isotopic Exchange Kinetic (SIEK) method to characterize polymetallic contaminations.

A new method is proposed to precisely and simultaneously quantify the exchangeable pool of metals in soils and to describe its reactivity at short- and long-term. It is based on multielementary Stable Isotopic Exchange Kinetics (multi-SIEK), first validated by a comparison between two monoelementary radioactive ((109)Cd*, (65)Zn*) IEK experiments, a mono- ((106)Cd) and multi- ((62)Ni, (65)Cu, (67)Zn, (106)Cd, (204)Pb) SIEK. These experiments were performed on a polluted soil located near the Zn smelter plant of Viviez (Lot watershed, France). The IEK results obtained for Cd and Zn were consistent across the experiments. (109)Cd*, (65)Zn* IEK, and multi-SIEK were then applied on 3 non- and moderate impacted soils that also provided consistent results for Cd and Zn. Within these experimental conditions, it can be concluded that no competition occurs between Cd, Zn, and the other metals during SIEK. Multi-SIEK results indicate that the isotopically exchangeable pool of Ni, Zn, and Cu are small (E(Ni), E(Zn), and E(Cu) values up to 17%) whatever the pollution degree of the soils considered in this study and whatever the duration of the interaction. On the contrary, Cd displays the highest E values (from 35% to 61% after 1 week), and E(Pb) displays a maximum value of 26% after 1 week. The multi-SIEK provides useful information on metal sources and reactivity relationship. Ni would be located in stable pedogenic phases according to its very low enrichment factor. The low E(Zn) and E(Cu) are consistent with location of Zn and Cu in stable phases coming from tailings erosion. Though Pb enrichments in soils may also be attributed to tailings particles, its larger exchangeable pool suggests that the Pb-bearing phases are more labile than those containing Zn and Cu. The high mobility of Cd in upstream soils indicates that it has been mostly emitted as reactive atmospheric particles during high temperature ore-treatment.

Potash fertilizer promotes incipient salinization in groundwater irrigated semi-arid agriculture.

Incipient groundwater salinization has been identified in many arid and semi-arid regions where groundwater is increasingly used for irrigation, but the dominant processes at stake in such context are yet uncertain. Groundwater solutes originates from various sources such as atmospheric inputs, rock dissolution and fertilizer residues, and their concentration is controlled by hydrological processes, in particular evapotranspiration. Here, we propose a deconvolution method to identify the sources and processes governing the groundwater Chloride concentration in agricultural catchments, using the relative variations of Sodium and Chloride and using a neighbouring pristine catchment as a reference for the release rate of Na by weathering. We applied the deconvolution method to the case of the Kabini Critical Zone Observatory, South India, where groundwater was sampled in 188 farm tubewells in the semi-arid catchment of Berambadi and in 5 piezometers in the pristine catchment of Mule Hole. In Berambadi, groundwater composition displayed a large spatial variability with Cl contents spanning 3 orders of magnitude. The results showed that the concentration factor due to evapotranspiration was on average about 3 times more than in the natural system, with higher values in the valley bottoms with deep Vertisols. Linked with this process, large concentration of Chloride originating from rain was found only in these areas. At the catchment scale, about 60 percent of the Chloride found in groundwater originates from fertilizer inputs. These results show that Potassium fertilization as KCl is an important source of groundwater salinization in semi-arid context, and stress that identifying dominant drivers is crucial for designing efficient mitigation policies.

Groundwater resource vulnerability and spatial variability of nitrate contamination: Insights from high density tubewell monitoring in a hard rock aquifer.

Agriculture has been increasingly relying on groundwater irrigation for the last decades, leading to severe groundwater depletion and/or nitrate contamination. Understanding the links between nitrate concentration and groundwater resource is a prerequisite for assessing the sustainability of irrigated systems. The Berambadi catchment (ORE-BVET/Kabini Critical Zone Observatory) in Southern India is a typical example of intensive irrigated agriculture and then an ideal site to study the relative influences of land use, management practices and aquifer properties on NO3 spatial distribution in groundwater. The monitoring of >200 tube wells revealed nitrate concentrations from 1 to 360mg/L. Three configurations of groundwater level and elevation gradient were identified: i) NO3 hot spots associated to deep groundwater levels (30-60m) and low groundwater elevation gradient suggest small groundwater reserve with absence of lateral flow, then degradation of groundwater quality due to recycling through pumping and return flow; ii) high groundwater elevation gradient, moderate NO3 concentrations suggest that significant lateral flow prevented NO3 enrichment; iii) low NO3 concentrations, low groundwater elevation gradient and shallow groundwater indicate a large reserve. We propose that mapping groundwater level and gradient could be used to delineate zones vulnerable to agriculture intensification in catchments where groundwater from low-yielding aquifers is the only source of irrigation. Then, wells located in low groundwater elevation gradient zones are likely to be suitable for assessing the impacts of local agricultural systems, while wells located in zones with high elevation gradient would reflect the average groundwater quality of the catchment, and hence should be used for regional mapping of groundwater quality. Irrigation with NO3 concentrated groundwater induces a "hidden" input of nitrogen to the crop which can reach 200kgN/ha/yr in hotspot areas, enhancing groundwater contamination. Such fluxes, once taken into account in fertilizer management, would allow optimizing fertilizer consumption and mitigate high nitrate concentrations in groundwater.

Controls of Soil Spatial Variability in a Dry Tropical Forest.

We examined the roles of lithology, topography, vegetation and fire in generating local-scale (<1 km2) soil spatial variability in a seasonally dry tropical forest (SDTF) in southern India. For this, we mapped soil (available nutrients, Al, total C, pH, moisture and texture in the top 10 cm), rock outcrops, topography, all native woody plants ≥1 cm diameter at breast height (DBH), and spatial variation in fire frequency (times burnt during the 17 years preceding soil sampling) in a permanent 50-ha plot. Unlike classic catenas, lower elevation soils had lesser moisture, plant-available Ca, Cu, Mn, Mg, Zn, B, clay and total C. The distribution of plant-available Ca, Cu, Mn and Mg appeared to largely be determined by the whole-rock chemical composition differences between amphibolites and hornblende-biotite gneisses. Amphibolites were associated with summit positions, while gneisses dominated lower elevations, an observation that concurs with other studies in the region which suggest that hillslope-scale topography has been shaped by differential weathering of lithologies. Neither NO3(-)-N nor NH4(+)-N was explained by the basal area of trees belonging to Fabaceae, a family associated with N-fixing species, and no long-term effects of fire on soil parameters were detected. Local-scale lithological variation is an important first-order control over soil variability at the hillslope scale in this SDTF, by both direct influence on nutrient stocks and indirect influence via control of local relief.

Geochemical behaviour of dissolved trace elements in a monsoon-dominated tropical river basin, Southwestern India.

The study presents a 3-year time series data on dissolved trace elements and rare earth elements (REEs) in a monsoon-dominated river basin, the Nethravati River in tropical Southwestern India. The river basin lies on the metamorphic transition boundary which separates the Peninsular Gneiss and Southern Granulitic province belonging to Archean and Tertiary-Quaternary period (Western Dharwar Craton). The basin lithology is mainly composed of granite gneiss, charnockite and metasediment. This study highlights the importance of time series data for better estimation of metal fluxes and to understand the geochemical behaviour of metals in a river basin. The dissolved trace elements show seasonality in the river water metal concentrations forming two distinct groups of metals. First group is composed of heavy metals and minor elements that show higher concentrations during dry season and lesser concentrations during the monsoon season. Second group is composed of metals belonging to lanthanides and actinides with higher concentration in the monsoon and lower concentrations during the dry season. Although the metal concentration of both the groups appears to be controlled by the discharge, there are important biogeochemical processes affecting their concentration. This includes redox reactions (for Fe, Mn, As, Mo, Ba and Ce) and pH-mediated adsorption/desorption reactions (for Ni, Co, Cr, Cu and REEs). The abundance of Fe and Mn oxyhydroxides as a result of redox processes could be driving the geochemical redistribution of metals in the river water. There is a Ce anomaly (Ce/Ce*) at different time periods, both negative and positive, in case of dissolved phase, whereas there is positive anomaly in the particulate and bed sediments. The Ce anomaly correlates with the variations in the dissolved oxygen indicating the redistribution of Ce between particulate and dissolved phase under acidic to neutral pH and lower concentrations of dissolved organic carbon. Unlike other tropical and major world rivers, the effect of organic complexation on metal variability is negligible in the Nethravati River water.