Jakob Santner

Performance Characteristics of Diffusive Gradients in Thin Films Equipped with a Binding Gel Layer Containing Precipitated Ferrihydrite for Measuring Arsenic(V), Selenium(VI), Vanadium(V), and Antimony(V)

Measurements at high spatial resolution by DGT (diffusive gradients in thin films) require a binding agent that is homogeneously distributed in the binding layer. Formation of ferrihydrite by in situ precipitation within a hydrogel has been previously shown to meet these requirements for the measurement of oxyanions by DGT. Here, we report for the first time detailed performance characteristics of the binding gel and associated DGT devices obtained by deployment in known solutions. To allow comparison of measured and theoretical accumulation of As(V), Se(VI), V(V), and Sb(V), their diffusion coefficients were determined using an independent diffusion cell. Theoretical responses were obtained irrespective of ionic strength (1-100 mmol L(-1)) and pH (3-8), except for Se above pH 7.8 and V below pH 5. Calculated detection limits, based on deployment times of 1 day, were lower than those for devices made with a binding gel cast with a ferrihydrite slurry, and the measured capacity of the binding layer was also superior. There was no evidence for interference from other oxyanions, but binding performance showed some deterioration after 38 days of storage. The potential capability for measuring labile forms of these oxyanions in acidic to neutral, fresh to brackish waters was demonstrated.

Innovative methods in soil phosphorus research: A review

Phosphorus (P) is an indispensable element for all life on Earth and, during the past decade, concerns about the future of its global supply have stimulated much research on soil P and method development. This review provides an overview of advanced state-of-the-art methods currently used in soil P research. These involve bulk and spatially resolved spectroscopic and spectrometric P speciation methods (1 and 2D NMR, IR, Raman, Q-TOF MS/MS, high resolution-MS, NanoSIMS, XRF, XPS, (µ)XAS) as well as methods for assessing soil P reactions (sorption isotherms, quantum-chemical modeling, microbial biomass P, enzymes activity, DGT, 33P isotopic exchange, 18O isotope ratios). Required experimental set-ups and the potentials and limitations of individual methods present a guide for the selection of most suitable methods or combinations.

Two decades of chemical imaging of solutes in sediments and soils – a review

The increasing appreciation of the small-scale (sub-mm) heterogeneity of biogeochemical processes in sediments, wetlands and soils has led to the development of several methods for high-resolution two-dimensional imaging of solute distribution in porewaters. Over the past decades, localised sampling of solutes (diffusive equilibration in thin films, diffusive gradients in thin films) followed by planar luminescent sensors (planar optodes) have been used as analytical tools for studies on solute distribution and dynamics. These approaches have provided new conceptual and quantitative understanding of biogeochemical processes regulating the distribution of key elements and solutes including O2, CO2, pH, redox conditions as well as nutrient and contaminant ion species in structurally complex soils and sediments. Recently these methods have been applied in parallel or integrated as so-called sandwich sensors for multianalyte measurements. Here we review the capabilities and limitations of the chemical imaging methods that are currently at hand, using a number of case studies, and provide an outlook on potential future developments for two-dimensional solute imaging in soils and sediments.

Ferrihydrite Containing Gel for Chemical Imaging of Labile Phosphate Species in Sediments and Soils Using Diffusive Gradients in Thin Films

We report on a novel binding gel for phosphate, based on ferrihydrite, and its use in diffusive gradients in thin films (DGT) for measuring labile phosphate species in waters, sediments, and soils. An existing method of binding layer preparation was modified to overcome potential problems with deterioration of ferrihydrite due to conversion to goethite. The gel was characterized regarding its suitability for conventional DGT measurements as well as for measuring two-dimensional distributions of P with high spatial resolution using laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS). The effects of pH, ionic strength and storage time of gels on phosphate binding were investigated and the kinetics of binding and the maximum binding capacity were determined. The gel is shown to have a considerably higher P capacity than the conventional ferrihydrite DGT binding layers. LA-ICPMS analysis of DGT standards with P concentrations ranging from 0.088 ± 0.005 to 4.47 ± 0.16 μg cm(-2) resulted in reproducible calibration curves which could be described using a simple power function. We demonstrate that the new gel is well suited for analyzing small-scale changes of P concentrations in soils. Moreover, the gel can be used as an alternative to conventional DGT gels that incorporate powdered ferrihydrite, with improved characteristics for the determination of labile phosphate.

Localized Flux Maxima of Arsenic, Lead, and Iron around Root Apices in Flooded Lowland Rice

In wetland-adapted plants, such as rice, it is typically root apexes, sites of rapid entry for water/nutrients, where radial oxygen losses (ROLs) are highest. Nutrient/toxic metal uptake therefore largely occurs through oxidized zones and pH microgradients. However, the processes controlling the acquisition of trace elements in rice have been difficult to explore experimentally because of a lack of techniques for simultaneously measuring labile trace elements and O2/pH. Here, we use new diffusive gradients in thin films (DGT)/planar optode sandwich sensors deployed in situ on rice roots to demonstrate a new geochemical niche of greatly enhanced As, Pb, and Fe(II) mobilization into solution immediately adjacent to the root tips characterized by O2 enrichment and low pH. Fe(II) mobilization was congruent to that of the peripheral edge of the aerobic root zone, demonstrating that the Fe(II) mobilization maximum only developed in a narrow O2 range as the oxidation front penetrates the reducing soil. The Fe flux to the DGT resin at the root apexes was 3-fold higher than the anaerobic bulk soil and 27 times greater than the aerobic rooting zone. These results provide new evidence for the importance of coupled diffusion and oxidation of Fe in modulating trace metal solubilization, dispersion, and plant uptake.

Sulfur-aided phytoextraction of Cd and Zn by Salix smithiana combined with in situ metal immobilization by gravel sludge and red mud

As phytoextraction implementation may be limited by metal toxicity and leaching, we investigated the idea of in situ metal immobilization in bulk soil, while increasing metal bioavailability in the rhizosphere. Salix smithiana was grown in a pot experiment on two Cd/Zn polluted soils. Treatments with or without willows included: no additives; gravel sludge + red mud kg(-1); acidification with S to pH 3.5; and metal immobilization combined with soil acidification. Salix smithiana removed up to 0.78 ± 0.06% total Cd and 0.34% (±0.02) total Zn from the non-treated soils. The phytoextraction efficiency in the S treatments was enhanced by up to ~50% in response to metal solubility that was magnified by reductive co-dissolution from Mn (IV) and Fe(III) (oxy)hydroxides during microbial S oxidation in the willow rhizosphere. The proposed technique proved to enhance phytoextraction efficiency while controlling the risk of metal leaching from the root zone and phytotoxicity.

Gel for simultaneous chemical imaging of anionic and cationic solutes using diffusive gradients in thin films.

We report on a novel gel based on diffusive gradients in thin films (DGT) for the simultaneous measurement of cations and anions and its suitability for high resolution chemical imaging by using laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). The new high resolution mixed binding gel (HR-MBG) is based on zirconium-hydroxide and suspended particulate reagent-iminodiacetate (SPR-IDA) as resin materials which are embedded in an ether-based urethane polymer hydrogel. The use of this polymer hydrogel material allows the production of ultrathin, highly stable and tear-proof resin gel layers with superior handling properties compared to existing ultrathin polyacrylamide gels. The gel was characterized regarding its uptake kinetics, the anion and cation capacities, and the effects of pH, ionic strength, and aging on the performance of the HR-MBG. Our results demonstrate the capability of this novel gel for concomitant sampling of anions and cations. The suitability of this new gel type for DGT chemical imaging at submm spatial resolution in soils using LA-ICPMS is shown. 2D images of P, As, Co, Cu, Mn, and Zn distributions around roots of Zea mays L. demonstrate the new opportunities offered by the HR-MBG for high-resolution mapping of solute dynamics in soil and sediment hotspots, such as the rhizosphere, by simultaneous observation of anionic and cationic solute species.

Uncertainty Evaluation of the Diffusive Gradients in Thin Films Technique

Although the analytical performance of the diffusive gradients in thin films (DGT) technique is well investigated, there is no systematic analysis of the DGT measurement uncertainty and its sources. In this study we determine the uncertainties of bulk DGT measurements (not considering labile complexes) and of DGT-based chemical imaging using laser ablation - inductively coupled plasma mass spectrometry. We show that under well-controlled experimental conditions the relative combined uncertainties of bulk DGT measurements are ∼10% at a confidence interval of 95%. While several factors considerably contribute to the uncertainty of bulk DGT, the uncertainty of DGT LA-ICP-MS mainly depends on the signal variability of the ablation analysis. The combined uncertainties determined in this study support the use of DGT as a monitoring instrument. It is expected that the analytical requirements of legal frameworks, for example, the EU Drinking Water Directive, are met by DGT sampling.

First observation of diffusion‐limited plant root phosphorus uptake from nutrient solution

Diffusion towards the root surface has recently been shown to control the uptake of metal ions from solutions. The uptake flux of phosphorus (P) from solutions often approaches the maximal diffusion flux at low external concentrations, suggesting diffusion-controlled uptake also for P. Potential diffusion limitation in P uptake from nutrient solutions was investigated by measuring P uptake of Brassica napus from solutions using P-loaded Al(2) O(3) nanoparticles as mobile P buffer. At constant, low free phosphate concentration, plant P uptake increased up to eightfold and that of passive, diffusion-based samplers up to 40-fold. This study represents the first experimental evidence of diffusion-limited P uptake by plant roots from nutrient solution. The Michaelis constant of the free phosphate ion obtained in unbuffered solutions (K(m) = 10.4 µmol L(-1) ) was 20-fold larger than in the buffered system (K(m) ∼0.5 µmol L(-1) ), indicating that K(m) s determined in unbuffered solutions do not represent the transporter affinity. Increases in the P uptake efficiency of plants by increasing the carrier affinity are therefore unlikely, while increased root surface area or exudation of P-solubilizing compounds are more likely to enhance P uptake. Furthermore, our results highlight the important role natural nanoparticles may have in plant P nutrition.

Localized metal solubilization in the rhizosphere of Salix smithiana upon sulfur application.

A metal-accumulating willow was grown under greenhouse conditions on a Zn/Cd-polluted soil to investigate the effects of sulfur (S0) application on metal solubility and plant uptake. Soil porewater samples were analyzed 8 times during 61 days of growth, while DGT-measured metal flux and O2 were chemically mapped at selected times. Sulfur oxidation resulted in soil acidification and related mobilization of Mn, Zn, and Cd, more pronounced in the rooted compared to bulk soil. Chemical imaging revealed increased DGT-measured Zn and Cd flux at the root-soil interface. Our findings indicated sustained microbial S0 oxidation and associated metal mobilization close to root surfaces. The localized depletion of O2 along single roots upon S0 addition indicated the contribution of reductive Mn (oxy)hydoxide dissolution with Mn eventually becoming a terminal electron acceptor after depletion of O2 and NO3–. The S0 treatments increased the foliar metal concentrations (mg kg–1 dwt) up to 10-fold for Mn, (5810 ± 593), 3.3-fold for Zn (3850 ± 87.0), and 1.7-fold for Cd (36.9 ± 3.35), but had no significant influence on biomass production. Lower metal solubilization in the bulk soils should translate into reduced leaching, offering opportunities for using S0 as environmentally favorable amendment for phytoextraction of metal-polluted soils.