Pedogenic controls of soil organic carbon stocks and stability beneath montane Norway spruce forests along a precipitation gradient.

Reliable data on SOC stocks in forest soils is required in the context of climate change and soil health assessments but still limited by input data availability (e.g., bulk density) and methods used for stock calculation. Relatively few studies have investigated the stability of SOC in forest soils. We investigated SOC stocks and fractionation in soils beneath Norway spruce forests and grasslands in the montane zone along a gradient of mean annual precipitation (MAP). We sampled soil cores volumetrically to 40 cm depth and measured SOC in the fractions <2 mm (fine earth), >200 µm and 200-20 µm (coarse and fine POM), and <20 µm (MAOM) along with potential pedogenic controls. Total SOC stocks beneath forests in the study region, calculated by the equivalent soil mass (ESM) approach to 40 cm depth, amount to 79.0 ± 29.9 (mean ± standard deviation) Mg ha-1 (n = 20) in the mineral soil, and to 92.9 ± 30.6 Mg ha-1 including the litter layer, with a share of 55 % associated with POM. MAOM makes up ∼41 % of SOC in the uppermost mineral layer (0-5 cm) and increases to 71 % in the subsoil (20-40 cm). Multiple regression models show that MAOM is largely controlled by ammonium oxalate extractable Al (Alo) in the forest subsoils (20-40 cm), and increases with MAP in the topsoil layers (0-20 cm). Soils on carbonate rock stand out with ∼80-100 % larger shares of MAOM in the uppermost soil layers (0-10 cm) which is likely connected to higher soil pH and MAP, supporting microbial transformation and subsequent stabilisation of organic matter, which is reflected in narrower C:N ratios in MAOM and SOC. Including the litter layers, ESM-based total SOC stocks in forest soils tend to exceed those beneath grassland (80.2 ± 21.9 Mg ha-1; n = 31) by 16 %, but only by 6.4 % if calculated by the conventional fixed-depth (FD) approach. In contrast to the forest soils, SOC stocks beneath grasslands are dominated by MAOM (75.6 %). We conclude that (coniferous) forest soils are a poor reference for establishing sequestration potentials for stable SOC. The observed large proportion of POM in forest topsoils and its increase with declining MAP (indicating water availability) suggests a risk of SOC losses in response to increasing droughts due to climate change.

Chemical imaging reveals environmental risk of minor tungsten and lead shotgun pellet constituents during weathering in soil.

Tungsten (W)-based shots are considered more environmentally safe than lead (Pb)-based shots, but knowledge about the W-shot fate in the soil environment is still limited, especially in terms of minor constituents such as iron, copper, and nickel (Ni). Contaminant behaviour in soil strongly depends on pH; in turn, the corrosion of metal composites may affect the pH locally. The aim of this study was to compare Pb- and W-shot weathering dynamics in soil (silt loam, pH 6.3) and reveal the interplay of shot weathering-induced pH-changes on the mobility of elements using in situ chemical imaging (Diffusive gradients in thin films for labile elements, planar optodes for soil pH) and batch incubation experiments over time (16 months). Despite our expectation to find acidification due to W oxidation, we observed a pH increase by 0.2 units in extracted soil solutions and by 0.6 units in the soil around W-shots as Ni dissolved from the binder phase of the shot. After 10 weeks, release of labile Ni was 3-times higher compared to W despite the low Ni content in the shot (7 %, m/m). Pb-shot oxidation increased soil solution pH by 0.5 units which likely supported mobility of Pb-shot-derived antimony (Sb). Steep gradients of labile W and Pb and soil solution concentrations <0.8 µmol L-1 indicated that transfer from shot to soil was low. Contrastingly, labile Ni and Sb were found up to ~4 mm from the shot surface and in higher soil solution concentrations as suggested by the shot constitution, indicating higher mobility of minor as compared to major shot constituents. After 16 months, 36 % of total Ni were dissolved in the soil solution highlighting the environmental relevance of minor shot constituents in Pb-shot alternatives after short term weathering in soil.

In situ spatiotemporal solute imaging of metal corrosion on the example of magnesium.

Visualization and quantification of corrosion processes is essential in materials research. Here we present a new approach for 2D spatiotemporal imaging of metal corrosion dynamics in situ. The approach combines time-integrated Mg2+ flux imaging by diffusive gradients in thin films laser ablation inductively coupled plasma mass spectrometry (DGT LA-ICP-MS) and near real-time pH imaging by planar optodes. The parallel assessment of Mg2+ flux and pH distributions on a fine-structured, bare Mg alloy (b-WE43) showed intense Mg dissolution with Mg2+ flux maxima up to 11.9 ng cm-2 s-1 and pH increase >9 during initial corrosion (≤15 min) in aqueous NaNO3 solution (c = 0.01 mol L-1). The techniques visualized the lower initial corrosion rate in buffered synthetic body fluid (Hank's balanced salt solution; pH 7.6) compared to unbuffered NaNO3 (pH 6.0), but precise localization of Mg corrosion remains challenging under these conditions. To further demonstrate the capability of DGT LA-ICP-MS for spatiotemporal metal flux imaging at the microscale, a coated Mg alloy (c-WE43) with lower reactivity was deployed for ≤120 min. The high spatial resolution (∼10 µm × 80 µm) and low limits of detection (≤0.04 ng cm-2 s-1, t = 60 min) enabled accurate in situ localization and quantification (Urel = 20%, k = 2) of distinct Mg2+ flux increase, showing micro-confined release of Mg2+ from surface coating defects on c-WE43 samples. The presented approach can be extended to other metal species and applied to other materials to better understand corrosion processes and improve material design in technological engineering.

Tandem Probe Analysis Mode for Synchrotron XFM: Doubling Throughput Capacity.

Synchrotron-based X-ray fluorescence microscopy (XFM) analysis is a powerful technique that can be used to visualize elemental distributions across a broad range of sample types. Compared to conventional mapping techniques such as laser ablation inductively coupled plasma mass spectrometry or benchtop XFM, synchrotron-based XFM provides faster and more sensitive analyses. However, access to synchrotron XFM beamlines is highly competitive, and as a result, these beamlines are often oversubscribed. Therefore, XFM experiments that require many large samples to be scanned can penalize beamline throughput. Our study was largely driven by the need to scan large gels (170 cm2) using XFM without decreasing beamline throughput. We describe a novel approach for acquiring two sets of XFM data using two fluorescence detectors in tandem; essentially performing two separate experiments simultaneously. We measured the effects of tandem scanning on beam quality by analyzing a range of contrasting samples downstream while simultaneously scanning different gel materials upstream. The upstream gels were thin (<200 µm) diffusive gradients in thin-film (DGT) binding gels. DGTs are passive samplers that are deployed in water, soil, and sediment to measure the concentration and distribution of potentially bioavailable nutrients and contaminants. When deployed on soil, DGTs are typically small (2.5 cm2), so we developed large DGTs (170 cm2), which can be used to provide extensive maps to visualize the diffusion of fertilizers in soil. Of the DGT gel materials tested (bis-acrylamide, polyacrylamide, and polyurethane), polyurethane gels were most suitable for XFM analysis, having favorable handling, drying, and analytical properties. This gel type enabled quantitative (>99%) transmittance with minimal (<3%) flux variation during raster scanning, whereas the other gels had a substantial effect on the beam focus. For the first time, we have (1) used XFM for mapping analytes in large DGTs and (2) developed a tandem probe analysis mode for synchrotron-based XFM, effectively doubling throughput. The novel tandem probe analysis mode described here is of broad applicability across many XFM beamlines as it could be used for future experiments where any uniform, highly transmissive sample could be analyzed upstream in the "background" of downstream samples.

Improving the prediction of fertilizer phosphorus availability to plants with simple, but non-standardized extraction techniques.

In the framework of the circular economy, new P fertilizers produced from diverse secondary raw materials are being developed using various technologies. Standard extraction methods (neutral ammonium citrate (NAC) and H2O) provide limited information about the agronomic efficiency of these often heterogenous new products. Here, we compared these extractions with two alternative methods: 0.5 mol L-1 NaHCO3 and a sink extraction driven by phosphate adsorption onto ferrihydrite ("Iron Bag") on 79 recycled and mineral reference fertilizers. We compared their capacity to predict shoot biomass and P content of rye (S. cereale L.) grown in a greenhouse on three soils of contrasting pH with a subset of 42 fertilizers. The median extracted P (% of total P) was H2O (1%) < NaHCO3 (25%) < Iron Bag (67%) < NAC (85%). The NaHCO3 extraction stood out as a cost-effective and reliable method to predict plant shoot biomass and P content (R2 ranging between 0.65 and 0.86 in the slightly acidic and alkaline soil). Notwithstanding, the other methods provide complementary information for a more detailed characterization of how P solubility may be impacted by e.g. soil pH, granulation, or time. The implications of this work are therefore significant for fertilizer production, regulation, and use.

Metal accumulation and rhizosphere characteristics of Noccaea rotundifolia ssp. cepaeifolia.

This work aimed to investigate the metal accumulation characteristics as well as biogeochemical changes in the rhizosphere and root foraging strategies of this plant species. Previous reports suggested that Noccaea rotundifolia ssp. cepaeifolia is a Zn, Cd and Pb hyperaccumulator. We used hydroponic, rhizobox and split-pot experiments for studying metal accumulation and related rhizosphere processes. Although this species accumulated up to 1250 mg Pb kg-1 and 27,000 mg Zn kg-1 in shoots, translocation factors <1 do not meet the hyperaccumulation criteria. Substantial increases in Ca(NO3)2-extractable metals in the N. rotundifolia rhizosphere of a metal-spiked soil can be explained by proton release from N. rotundifolia roots to maintain the charge balance during excessive metal uptake; this was not observed for the non-spiked, moderately contaminated control soil. Specific rhizosphere mechanisms targeting the alleviation of metal toxicity in N. rotundifolia rhizosphere were not detected. Generally, N. rotundifolia had larger total root and shoot mass in soils with heterogeneous distribution of Zn and Pb relative to homogeneous treatments, associated with less root mass placed in metal-enriched patches. However, the avoidance strategy was not reflected by low shoot metal concentrations. Metal accumulation rates and translocation factors do not meet the criteria for hyperaccumulation. Changes of pH and DOC in N. rotundifolia rhizosphere were apparently not involved in targeted immobilisation or detoxification of Pb, Zn and Cd. Avoidance of metal-rich patches in soil is a major tolerance strategy of N. rotundifolia.

Response of tungsten (W) solubility and chemical fractionation to changes in soil pH and soil aging.

A thorough understanding of the geochemical behavior of W in soils is crucial for environmental risk assessment. Soil pH is known as master variable of element solubility and bioavailability in soils. Here we report on effects of soil pH (modified by liming and acid - base additions) and soil aging on the environmental availability of W in soil using W solubility and chemical fractionation as indicators. Experimental soils included two naturally acidic soils with contrasting soil texture (SAND, CLAY), at native pH or limed with 2.5% CaCO3, and spiked with increasing concentration of W. Our results showed that W was significantly more labile in alkaline compared to acidic soils, confirming the validity of results of pure-mineral studies for more heterogeneously composed soils. While labile W was generally greater in the SAND compared to the CLAY soil, the reverse trend was observed in the limed soils at the highest W addition (5000 mg kg-1). Combining our results with previous mechanistic reports suggests that clay edge sorption sites significantly contributed to W retention in treatments with low to medium W additions, resulting in lower environmental availability for W in the CLAY soil. At high W concentrations and high pH, the stronger W retention in the SAND was attributed to continuous formation of W surface polymers on the more abundant metal (oxyhydr)oxides, a process that has been previously reported to occur even under alkaline conditions. A first comparison of various soil chemical methods (Bray & AB-DTPA extractions, soil solution centrifugation CL, diffusion-based DGT) to predict W phytoavailability in soil also revealed a strong pH dependency challenging the identification of a suitable method. This study is one of the first demonstrating the pH dependence of W in natural soils and delivers evidence for increased risk of W mobilization in W polluted, alkaline soil environments.

Arsenic redox transformations and cycling in the rhizosphere of Pteris vittata and Pteris quadriaurita.

Pteris vittata (PV) and Pteris quadriaurita (PQ) are reported to hyperaccumulate arsenic (As) when grown in Asrich soil. Yet, little is known about the impact of their unique As accumulation mechanisms on As transformations and cycling at the soil-root interface. Using a combined approach of two-dimensional (2D), sub-mm scale solute imaging of arsenite (AsIII), arsenate (AsV), phosphorus (P), manganese (Mn), iron (Fe) and oxygen (O2), we found localized patterns of AsIII/AsV redox transformations in the PV rhizosphere (AsIII/AsV ratio of 0.57) compared to bulk soil (AsIII/AsV ratio of ≤0.04). Our data indicate that the high As root uptake, translocation and accumulation from the As-rich experimental soil (2080 mg kg-1) to PV fronds (6986 mg kg-1) induced As detoxification via AsV reduction and AsIII root efflux, leading to AsIII accumulation and re-oxidation to AsV in the rhizosphere porewater. This As cycling mechanism is linked to the reduction of O2 and MnIII/IV (oxyhydr)oxides resulting in decreased O2 levels and increased Mn solubilization along roots. Compared to PV, we found 4-fold lower As translocation to PQ fronds (1611 mg kg-1), 2-fold lower AsV depletion in the PQ rhizosphere, and no AsIII efflux from PQ roots, suggesting that PQ efficiently controls As uptake to avoid toxic As levels in roots. Analysis of root exudates obtained from soil-grown PV showed that As acquisition by PV roots was not associated with phytic acid release. Our study demonstrates that two closely-related As-accumulating ferns have distinct mechanisms for As uptake modulating As cycling in As-rich environments.

Functional Recycling of Biobased, Borate-Stabilized Insulation Materials As B Fertilizer.

Boron is a finite resource, which has been listed as a critical raw material in the EU since 2014. Glass, frits and ceramics production, as well as fertilizers are among the major uses of B. Moreover, about 50 000 t B have been applied as fire retardant and pest repellent in cellulose fiber insulation (CFI) in Europe since the 1980s. Here we propose the end-of-life utilization of borated CFI as B fertilizer, to decrease societal B consumption and to avoid costly and potentially environmentally harmful CFI incineration and deposition in landfills. In a case study, we show that CFI biochar can provide substantial amounts of B to rapeseed and sunflower, with the B plant-availability being comparable to sodium tetraborate, a conventional B fertilizer. The annual B fertilizer consumption of the EU is estimated at ∼4000 t B yr-1, which could be sustained by the B currently installed as CFI for >10 years. In addition, the annual use of B in CFI of 1100 t B yr-1 could cover ∼25% of the annual B fertilizer demand of the EU. Hence, conversion of CFI to B fertilizer provides a meaningful end-of-life strategy, which would contribute to a more resource-efficient and sustainable economy and to several of the UN Sustainable Development Goals.

Combined effects of carbonaceous-immobilizing agents and subsequent sulphur application on maize phytoextraction efficiency in highly contaminated soil.

The establishment of phytoextraction crops on highly contaminated soils can be limited by metal toxicity. A recent proposal has suggested establishing support crops during the critical initial phase by metal immobilization through soil amendments followed by subsequent mobilization using elemental sulphur to enhance phytoextraction efficiency. This 'combined phytoremediation' approach is tested for the first time in a pot experiment with a highly contaminated soil. During a 14-week period, relatively metal-tolerant maize was grown in a greenhouse under immobilization (before sulphur (S) application) and mobilization (after S application) conditions with soil containing Cd, Pb and Zn contaminants. Apart from the control (C) sample, the soil was amended with activated carbon (AC), lignite (Lig) or vermicompost (VC) all in two different doses (dose 1~45 g additive kg-1 soil and dose 2~90 g additive kg-1 soil). Elemental S was added as a mobilization agent in these samples after 9 weeks. Biomass production, nutrient and metal bioavailability in the soil were determined, along with their uptake by plants and the resulting remediation factors. Before S application, Cd and Zn mobility was reduced in all the AC, Lig and VC treatments, while Pb mobility was increased only in the Lig1 and VC1 treatments. Upon sulphur application, Fe, Mn, Cd, Pb and Zn mobility was not significantly affected in the C, AC and VC treatments, nor total Cd, Pb and Zn contents in maize shoots. Increased sulphate, Mn, Cd, Pb and Zn mobilities in soil together with related higher total S, Mn, Pb and Zn contents in shoots were observed in investigated treatments in the last sampling period. The highest biomass production and the lowest metal toxicity were seen in the VC treatments. These results were associated with effective metal immobilization and showed the trend of steady release of some nutrients. The highest remediation factors and total elemental content in maize shoots were recorded in the VC treatments. This increased phytoremediation efficiency by 400% for Cd and by 100% for Zn compared to the control. Considering the extreme metal load of the soil, it might be interesting to use highly metal-tolerant plants in future research. Future investigations could also explore the effect of carbonaceous additives on S oxidation, focusing on the specific microorganisms and redox reactions in the soil. In addition, the homogeneous distribution of the S rate in the soil should be considered, as well as longer observation times.

Silicon Availability from Chemically Diverse Fertilizers and Secondary Raw Materials.

Crops may require Si fertilization to sustain yields. Potential Si fertilizers include industrial byproducts (e.g., steel slags), mined minerals (CaSiO3), fused Ca-Mg-phosphates, biochar, ash, diatomaceous earth, and municipal sewage sludge. To date, no extraction method was shown to accurately predict plant availability of Si from such chemically diverse Si fertilizers. We tested a wide range of products in greenhouse experiments and related the plant Si content to Si extracted by several common Si fertilizer tests: 5-day extraction in Na2CO3-NH4NO3, 0.5 mol L-1 HCl, and Resin extraction. In addition, we tested a novel sink extraction approach for Si(OH)40 that utilizes a dialysis membrane filled with ferrihydrite ("Iron Bag"). Wheat straw biochars and ash exhibited equivalent or marginally higher Si solubility and availability compared to wheat straw. Thermo-chemically treated municipal sewage sludge, as well as diatomaceous earth, did not release substantial amounts of Si. The Resin and the Iron Bag extraction methods gave the best results to predict plant availability of Si. These methods better reproduce the conditions of fertilizer dissolution in soil and around the root by (1) buffering the pH close to neutral and (2) extracting the dissolved Si(OH)40 with ferrihydrite (Iron Bag method) for maximum quantitative extraction.

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.

Integrating chemical imaging of cationic trace metal solutes and pH into a single hydrogel layer.

Gel-based, two-dimensional (2D) chemical imaging techniques are versatile methods for investigating biogeochemically active environments at high spatial resolution (sub-mm). State-of-the-art solute imaging techniques, such as diffusive gradients in thin films (DGT) and planar optodes (PO), employ passive solute sampling or sensing. Combining these methods will provide powerful tools for studying the biogeochemistry of biological niches in soils and sediments. In this study we aimed at developing a combined single-layer gel for direct pH imaging using PO and sampling of anionic and cationic solutes by DGT, with subsequent analysis of the bound solutes by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). We tested three ultra-thin (<100 µm) polyurethane-based gels, incorporating anion and cation binding materials and the fluorescent pH indicator DCIFODA (2',7'-dichloro-5(6)-N-octadecyl-carboxamidofluorescein). Results showed that PO-based pH sensing using DCIFODA was impossible in the presence of the anion binding materials due to interferences with DCIFODA protonation. One gel, containing only a cation binding material and DCIFODA, was fully characterized and showed similar performance characteristics as comparable DGT-only gels (applicable pH range: pH 5-8, applicable ionic strength range: 1-20 mmol L-1, cation binding capacity ∼24 µg cm-2). The dynamic range for PO-based pH mapping was between pH 5.5 and 7.5 with t90 response time of ∼60 min. In a case study we demonstrated the gel's suitability for multi-analyte solute imaging and mapped pH gradients and concurrent metal solubility patterns in the rhizosphere of Salix smithiana. pH decreases in the rooted soil were co-localized with elevated solute fluxes of Al3+, Co2+, Cu2+, Fe, Mn2+, Ni2+ and Pb2+, indicating pH-induced metal solubilisation.

Waste or substrate for metal hyperaccumulating plants - The potential of phytomining on waste incineration bottom ash.

Phytomining could represent an innovative low-cost technology for the selective recovery of valuable trace elements from secondary resources. In this context the potential of phytomining from waste incineration bottom ash was tested in a pot experiment. Fresh bottom ash was acidified, leached to reduce salinity and amended with organic material to obtain a suitable substrate for plant growth. Two hyperaccumulator species, Alyssum serpyllifolium subsp. lusitanicum and Sedum plumbizincicola as well as three metal tolerant species, Brassica napus, B. juncea and Nicotiana tabacum were tested for their phytomining potential on the pre-treated and amended bottom ashes from municipal solid waste and hazardous waste incineration. The hyperaccumulators had severe difficulties to establish on the bottom ash and to produce sufficient biomass, likely due to salinity and Cu toxicity. Nevertheless, concentrations of Ni in A. serpyllifolium and Zn in S. plumbizincicola were high, but total metal removal was limited by the low biomass production and was clearly less than on metalliferous soils. The Brassica species proved to be more tolerant to salinity and high Cu concentrations and produced considerably higher biomass, but total metal removal was limited by rather low shoot concentrations. The observed limitations of the phytomining process along with currently low market prices of Ni and Zn suggest that further optimisation of the process is required in order to make phytomining economically feasible on the tested waste incineration bottom ashes.

Diffusive gradients in thin films measurement of sulfur stable isotope variations in labile soil sulfate.

A diffusive gradient in thin films (DGT) technique, based on a strongly basic anion exchange resin (Amberlite IRA-400), was successfully tested for 34S/32S analysis in labile soil sulfate. Separation of matrix elements (Na, K, and Ca) that potentially cause non-spectral interferences in 34S/32S analysis by MC ICP-MS (multi-collector inductively coupled plasma-mass spectrometry) during sampling of sulfate was demonstrated. No isotopic fractionation caused by diffusion or elution of sulfate was observed below a resin gel disc loading of ≤79 µg S. Above this threshold, fractionation towards 34S was observed. The method was applied to 11 different topsoils and one mineral soil profile (0-100 cm depth) and compared with soil sulfate extraction by water. The S amount and isotopic ratio in DGT-S and water-extractable sulfate correlated significantly (r 2 = 0.89 and r 2 = 0.74 for the 11 topsoils, respectively). The systematically lower 34S/32S isotope ratios of the DGT-S were ascribed to mineralization of organic S.

Environmental impact assessment of wood ash utilization in forest road construction and maintenance--A field study.

The ever increasing use of wood material as fuel for green energy production requires innovative, environmentally safe strategies for recycling of the remaining wood ash. Utilizing wood ash in forest road construction and maintenance to improve mechanical stability has been suggested as a feasible recycling option. To investigate the environmental impact of wood ash application in forest road maintenance, a two-year field experiment was conducted at two Austrian forest sites (Kobernausserwald (KO) (soil pH 5.5) and Weyregg (WE) (pH 7.7)) differing in their soil chemical properties. Two different ashes, one produced by grate incineration (GA) and the other by fluidized bed incineration in a mixture with 15 vol% burnt lime (FBA), were incorporated in repeated road sections at a 15:85% (V/V) ash-to-soil rate. Leaching waters from the road body were collected and analyzed for 32 environmentally relevant parameters over two years. Upon termination of the experiment, sub-road soil samples were collected and analyzed for ash-related changes in soil chemistry. Even though a larger number of parameters was affected by the ash application at the alkaline site (WE), we observed the most pronounced initial increases of pH as well as Al, As, Fe, Mn, Ni, Co, Cu, Mo, and NO2(−) concentrations in leachates beneath GA-treated road bodies at Kobernausserwald due to the lower soil buffer capacity at this site. Despite the observed effects our results indicate that, when specific requirements are met (i.e. appropriate ash quality, sufficient soil buffer capacity below the road body, and single time-point ash incorporation within several decades), wood ash application in forest road construction is generally environmentally acceptable.

O2 dynamics in the rhizosphere of young rice plants (Oryza sativa L.) as studied by planar optodes.

BACKGROUND AND AIMS: Radial O2 loss (ROL) strongly affect the O2 availability in the rhizosphere of rice. The ROL create an oxic zone around the roots, protecting the plant from toxic reduced chemical species and regulates the redox chemistry in the soil. This study investigates the spatio-temporal variability in O2 dynamics in the rice rhizosphere. METHOD: Applying high-resolution planar optode imaging, we investigated the O2 dynamics of plants grown in water saturated soil, as a function of ambient O2 level, irradiance and plant development, for submerged and emerged plants. RESULTS: O2 leakage was heterogeneously distributed with zones of intense leakage around roots tips and young developing roots. While the majority of roots exhibited high ROL others remained surrounded by anoxic soil. ROL was affected by ambient O2 levels around the plant, as well as irradiance, indicating a direct influence of photosynthetic activity on ROL. At onset of darkness, oxia in the rhizosphere was drastically reduced, but subsequently oxia gradually increased, presumably as root and/or soil respiration declined. CONCLUSION: The study demonstrates a high spatio-temporal heterogeneity in rhizosphere O2 dynamics and difference in ROL between different parts of the rhizosphere. The work documents that spatio-temporal measurements are important to fully understand and account for the highly variable O2 dynamics and associated biogeochemical processes and pathways in the rice rhizosphere.

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.

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 (S(0)) 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 S(0) oxidation and associated metal mobilization close to root surfaces. The localized depletion of O2 along single roots upon S(0) 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 S(0) 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 S(0) as environmentally favorable amendment for phytoextraction of metal-polluted soils.