Abstract

The biogeochemistry of multi-elements, such as sulfur (S), phosphorus (P) and arsenic (As), is interlinked especially at interfaces of soil/sediment–water and plant rhizosphere. To explore the biogeochemical behavior of multi-elements such as S-P-As at interfaces, an in situ and high-resolution technology is required. In this study, we developed an in situ probe (LDHs-DGT) based on the diffusive gradients in thin-films technique using a single binding layer to realize the co-measurement of multi-elements including sulfide and oxyanions. Mg-Al layered double hydroxides (LDHs) were synthesized and incorporated into the probe’s binding layer. Laboratorial characterization showed that the LDHs-DGT probe had a high capacity for sulfide, phosphate and arsenate and can effectively determine their levels across a wide range of solution conditions, i.e., pH from 5 to 8 and ionic strengths from 0.005–0.01 mol L−1 NaNO3. The application potential of the LDHS-DGT probe in capturing the concentration profiles of sulfide and oxyanions across the soil/sediment–water interface at a centimeter scale was demonstrated. The synchronous co-variations of labile sulfide and phosphate were observed along an intact river sediment core, demonstrating the redox driven behaviors of oxyanions at aerobic–anaerobic transition zones. Moreover, the LDHS-DGT probe was further used to acquire the dynamic distributions of multi-elements in the plant rhizosphere at a two-dimensional millimeter scale. Compared to treatments of sodium sulfate and mercaptopygorskite fertilization, the addition of elementary S promoted the reduction of sulfate to sulfide along the whole growth stage and thus inhibited the activation of toxic metals in the rice rhizosphere. Collectively, this study provides a tool for convenient measurement of nutrients and metal(loid)s across soil–water/root interfaces at high resolution and thus, a broad application prospect of the tool in sustainable agriculture is expected.

Highlights

  • For sustainable agriculture, it is important to keep the balance of mineral elements in soils, and to control the uptake and accumulation of toxic metal(loid)s in crops [1,2]

  • The results show that LDHS-Diffusive gradients in thin films (DGT) is able to capture the dynamic processes of multi-elements in the rice rhizosphere at a millimeter-scale high spatio-resolution

  • This work provides a useful tool based on DGT technique for co-measurement of multi-elements, i.e., sulfides (S(-II)) and oxyanions (phosphate, As(V))

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Summary

Introduction

It is important to keep the balance of mineral elements in soils, and to control the uptake and accumulation of toxic metal(loid)s in crops [1,2]. The biogeochemical cycling of mineral elements and toxic metal(loid)s in the environment is highly interlinked. Sulfide may immobilize As by inducing co-precipitation of iron sulfide minerals (e.g., pyrite) and arsenic sulfide (dioecious and realgar) [6,7]. The distribution of elements in agricultural soils, especially at the crop rhizosphere, are highly uneven at both spatial and temporal scales. It is strongly necessary to develop in situ high-resolution tools for co-measurement of nutrients and metal(loid)s at the soil/sediment–water interface and crop rhizosphere

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