Stable Isotope Fractionation of Metals and Metalloids in Plants: A Review.

This work critically reviews stable isotope fractionation of essential (B, Mg, K, Ca, Fe, Ni, Cu, Zn, Mo), beneficial (Si), and non-essential (Cd, Tl) metals and metalloids in plants. The review (i) provides basic principles and methodologies for non-traditional isotope analyses, (ii) compiles isotope fractionation for uptake and translocation for each element and connects them to physiological processes, and (iii) interlinks knowledge from different elements to identify common and contrasting drivers of isotope fractionation. Different biological and physico-chemical processes drive isotope fractionation in plants. During uptake, Ca and Mg fractionate through root apoplast adsorption, Si through diffusion during membrane passage, Fe and Cu through reduction prior to membrane transport in strategy I plants, and Zn, Cu, and Cd through membrane transport. During translocation and utilization, isotopes fractionate through precipitation into insoluble forms, such as phytoliths (Si) or oxalate (Ca), structural binding to cell walls (Ca), and membrane transport and binding to soluble organic ligands (Zn, Cd). These processes can lead to similar (Cu, Fe) and opposing (Ca vs. Mg, Zn vs. Cd) isotope fractionation patterns of chemically similar elements in plants. Isotope fractionation in plants is influenced by biotic factors, such as phenological stages and plant genetics, as well as abiotic factors. Different nutrient supply induced shifts in isotope fractionation patterns for Mg, Cu, and Zn, suggesting that isotope process tracing can be used as a tool to detect and quantify different uptake pathways in response to abiotic stresses. However, the interpretation of isotope fractionation in plants is challenging because many isotope fractionation factors associated with specific processes are unknown and experiments are often exploratory. To overcome these limitations, fundamental geochemical research should expand the database of isotope fractionation factors and disentangle kinetic and equilibrium fractionation. In addition, plant growth studies should further shift toward hypothesis-driven experiments, for example, by integrating contrasting nutrient supplies, using established model plants, genetic approaches, and by combining isotope analyses with complementary speciation techniques. To fully exploit the potential of isotope process tracing in plants, the interdisciplinary expertise of plant and isotope geochemical scientists is required.

Immobilization of molybdenum by alternative cementitious binders and synthetic C-S-H: An experimental and numerical study.

Excavation operations during construction produce millions of tons of soil sometimes with high leachable molybdenum (Mo) contents, that can lead to risks for both human health and the environment. It is therefore necessary to immobilize the Mo in excavated soils to reduce pollution and lower the costs of soil disposal. This paper studies the immobilization of Mo by three cementitious binders. To this end, one Ordinary Portland cement (OPC), one binder composed of 90% ground granulated blast furnace slag (GGBS) and 10% OPC, and one supersulfated GGBS binder were spiked with sodium molybdate at six different Mo concentrations from 0.005 wt% to 10 wt% before curing. In addition, to gain mechanistic insights, the capacity of synthetic calcium silicate hydrates (C-S-H) to immobilize Mo was studied. This study was completed by thermodynamic modeling to predict the immobilization of Mo at low Mo concentrations (<0.005 wt%). Paste leaching tests results showed that more than 74% of the initial Mo spike was immobilized by the three binders. The supersulfated GGBS binder consistently showed the highest retention levels (92.0 to 99.7%). The precipitation of powellite (CaMoO4) was the dominant mechanism of Mo retention in all binders and most leaching solutions were oversaturated with respect to powellite. Also, in C-S-H syntheses, Mo was largely immobilized (>95%) by the coprecipitation of powellite. Thermodynamic modeling was in good agreement with measured values when the equilibrium constant of powellite was modified to LogK = -7.2. This suggested that powellite is less stable in cementitious environments than would be expected from thermodynamic databases. Moreover, modeling showed that, for a solution at equilibrium with portlandite or C-S-H, the Mo concentration is limited to 1.7 mg/L by powellite precipitation. In contrast, for a solution saturated with respect to ettringite, the threshold concentration for powellite precipitation is 6.5 mg/L.

Stable Cu Isotope Ratios Show Changes in Cu Uptake and Transport Mechanisms in Vitis vinifera Due to High Cu Exposure.

Even though copper (Cu) is an essential plant nutrient, it can become toxic under certain conditions. Toxic effects do not only depend on soil Cu content, but also on environmental and physiological factors, that are not well understood. In this study, the mechanisms of Cu bioavailability and the homeostasis of Vitis vinifera L. cv. Tannat were investigated under controlled conditions, using stable Cu isotope analysis. We measured Cu concentrations and δ65Cu isotope ratios in soils, soil solutions, roots, and leaves of grapevine plants grown on six different vineyard soils, in a 16-week greenhouse experiment. The mobility of Cu in the soil solutions was controlled by the solubility of soil organic matter. No direct relationship between Cu contents in soils or soil solutions and Cu contents in roots could be established, indicating a partly homeostatic control of Cu uptake. Isotope fractionation between soil solutions and roots shifted from light to heavy with increasing Cu exposure, in line with a shift from active to passive uptake. Passive uptake appears to exceed active uptake for soil solution concentrations higher than 270 µg L-1. Isotope fractionation between roots and leaves was increasingly negative with increasing root Cu contents, even though the leaf Cu contents did not differ significantly. Our results suggest that Cu isotope analysis is a sensitive tool to monitor differences in Cu uptake and translocation pathways even before differences in tissue contents can be observed.

Total organic carbon concentrations in ecosystem solutions of a remote tropical montane forest respond to global environmental change.

The response of organic carbon (C) concentrations in ecosystem solutions to environmental change affects the release of dissolved organic matter (DOM) from forests to surface and groundwaters. We determined the total organic C (TOC) concentrations (filtered <1-7 µm) and the ratios of TOC/dissolved organic nitrogen (DON) concentrations, electrical conductivity (EC), and pH in all major ecosystem solutions of a tropical montane forest from 1998 to 2013. The forest was located on the rim of the Amazon basin in Ecuador and experienced increasing numbers of days with >25°C, decreasing soil moisture, and rising nitrogen (N) deposition from the atmosphere during the study period. In rainfall, throughfall, mineral soil solutions (at the 0.15- and 0.30-m depths), and streamflow, TOC concentrations and fluxes decreased significantly from 1998 to 2013, while they increased in stemflow. TOC/DON ratios decreased significantly in rainfall, throughfall, soil solution at the 0.15-m depth, and streamflow. Based on Δ14 C values, the TOC in rainfall and mineral soil solutions was 1 year old and that of litter leachate was 10 years old. The pH in litter leachate decreased with time, that in mineral soil solutions increased, while those in the other ecosystem solutions did not change. Thus, reduced TOC solubility because of lower pH values cannot explain the negative trends in TOC concentrations in most ecosystem solutions. The increasing TOC concentrations and EC in stemflow pointed at an increased leaching of TOC and other ions from the bark. Our results suggest an accelerated degradation of DOM, particularly of young DOM, associated with the production of N-rich compounds simultaneously to changing climatic conditions and increasing N availability. Thus, environmental change increased the CO2 release to the atmosphere but reduced DOM export to surface and groundwater.

Soil chemistry and meteorological conditions influence the elemental profiles of West European wines.

Elemental profiles of wines have been used successfully to distinguish their geographical provenience around the world; however, underlying mechanisms are poorly understood. In this study, Ba, Ca, Mg, Mn and Sr contents were determined in 215 wines from several West European wine-growing areas using an easy-to-perform analysis based on ICP-OES. Major environmental and wine-making parameters (soil type as "calcareous" or not, rainfall, temperature and wine color) were used to explain variations within the dataset. The combined effects of wine-making processes (expressed by wine color) and soil type explained 28.5% of total variance. The effect of climatic conditions explained 24.1% of variance and could be interpreted as intensity of drought stress. Finally, carbonate occurrence in soils and climatic conditions systematically influenced the elemental composition of the wines. These findings provide insights into the mechanisms underlying elemental fingerprinting and allow prediction of which wine-growing regions can easily be distinguished based on elemental profiles as a marker of the terroir in viticulture.