In situ observation of localized, sub-mm scale changes of phosphorus biogeochemistry in the rhizosphere.

AIMS: We imaged the sub-mm distribution of labile P and pH in the rhizosphere of three plant species to localize zones and hot spots of P depletion and accumulation along individual root axes and to relate our findings to nutrient acquisition / root exudation strategies in P-limited conditions at different soil pH, and to mobilization pattern of other elements (Al, Fe, Ca, Mg, Mn) in the rhizosphere. METHODS: Sub-mm distributions of labile elemental patterns were sampled using diffusive gradients in thin films and analysed using laser ablation inductively coupled plasma mass spectrometry. pH images were taken using planar optodes. RESULTS: We found distinct patterns of highly localized labile P depletion and accumulation reflecting the complex interaction of plant P acquisition strategies with soil pH, fertilizer treatment, root age, and elements (Al, Fe, Ca) that are involved in P biogeochemistry in soil. We show that the plants respond to P deficiency either by acidification or alkalization, depending on initial bulk soil pH and other factors of P solubility. CONCLUSIONS: P solubilization activities of roots are highly localized, typically around root apices, but may also extend towards the extension / root hair zone.

Spatiotemporal dynamics of phosphorus release, oxygen consumption and greenhouse gas emissions after localised soil amendment with organic fertilisers.

Organic fertilisation inevitably leads to heterogeneous distribution of organic matter and nutrients in soil, i.e. due to uneven surface spreading or inhomogeneous incorporation. The resulting localised hotspots of nutrient application will induce various biotic and abiotic nutrient turnover processes and fixation in the residue sphere, giving rise to distinct differences in nutrient availability, soil oxygen content and greenhouse gas (GHG) production. In this study we investigated the spatiotemporal dynamics of the reaction of manure solids and manure solids char with soil, focusing on their phosphorus (P) availability, as current emphasis on improving societal P efficiency through recycling waste or bio-based fertilisers necessitates a sound understanding of their behaviour. Soil layers amended at a constant P application rate with either pig manure solids or char made from pig manure solids were incubated for three weeks between layers of non-amended, P-depleted soil. Spatial and temporal changes in and around the amendment layers were simultaneously investigated in this study using a sandwich sensor consisting of a planar oxygen optode and multi-element diffusive gradients in thin films (DGT) gels, combined with GHG emission measurements. After three weeks of incubation, the soil containing a layer amended with manure solids had a lower overall O2 content and had emitted significantly more CO2 than the non-amended control or the char-amended soil. The P availability from manure solids was initially higher than that from the char, but decreased over time, whereas from the char-amended layer P availability increased in the same period. In both treatments, increases in P availability were confined to the amended soil layer and did not greatly affect P availability in the directly adjacent soil layers during the three-week incubation. These results highlight the importance of placing organic P fertilisers close to where the plant roots will grow in order to facilitate optimal fertiliser use efficiency.

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.

Numerical evaluation of lateral diffusion inside diffusive gradients in thin films samplers.

Using numerical simulation of diffusion inside diffusive gradients in thin films (DGT) samplers, we show that the effect of lateral diffusion inside the sampler on the solute flux into the sampler is a nonlinear function of the diffusion layer thickness and the physical sampling window size. In contrast, earlier work concluded that this effect was constant irrespective of parameters of the sampler geometry. The flux increase caused by lateral diffusion inside the sampler was determined to be ∼8.8% for standard samplers, which is considerably lower than the previous estimate of ∼20%. Lateral diffusion is also propagated to the diffusive boundary layer (DBL), where it leads to a slightly stronger decrease in the mass uptake than suggested by the common 1D diffusion model that is applied for evaluating DGT results. We introduce a simple correction procedure for lateral diffusion and demonstrate how the effect of lateral diffusion on diffusion in the DBL can be accounted for. These corrections often result in better estimates of the DBL thickness (δ) and the DGT-measured concentration than earlier approaches and will contribute to more accurate concentration measurements in solute monitoring in waters.

Phosphorus uptake by Zea mays L. is quantitatively predicted by infinite sink extraction of soil P.

BACKGROUND AND AIMS: Sink extraction of phosphorus from soils has been utilised to study soil P desorption kinetics and as index of plant availability, but not for quantitative prediction of P uptake by plants. Here we investigate the potential of a modified sink extraction method for determining P desorption kinetics and for quantifying plant available soil P. METHODS: Modified diffusive gradients in thin films samplers were immersed in shaken soil suspensions for long-term extraction of soil P. Results were evaluated in terms of P desorption kinetics and compared to the P uptake of Zea mays L. and standard soil extracts. RESULTS: In contrast to literature reports, four of the six studied soils only showed a rapid, but not a slowly desorbing P fraction. The quantity of P desorbed by long-term sink extraction not only showed the highest correlation to plant P uptake, but also matched plant P uptake quantitatively. CONCLUSIONS: Our data indicates that soils with only a fast desorbing P fraction might exist. Sink extraction methods have the potential to quantitatively predict plant P uptake. Furthermore, they could become valuable research tools for understanding P acquisition and might serve as a benchmark for calibrating soil P tests.

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.

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.