Simultaneous measurement of aqueous redox-sensitive elements and their species across the soil-water interface

The redox-sensitive elements, such as iron, manganese, sulfur, phosphorus, and arsenic, shift their speciation every millimeter (mm) across the soil-water interface in the flooded soil environments. Monitoring of element speciation at this high-resolution (HR) within the SWI is still difficult. The key challenge lies in obtaining sufficient porewater samples at specific locations along the soil gradient for downstream analysis. Here with an optimized inductively coupled plasma mass spectrometry (ICP-MS) method and a HR porewater sampler, we demonstrate mm-scale element profiles mapping across the SWI in paddy soils. High-concentrations of iron and manganese (> 10 mg/L) were measured by ICP-MS in an extended dynamic range mode to avoid signal overflow. The iron profile along the SWI generated by the ICP-MS method showed no significant difference (p < 0.05) compared to that measured independently using a colorimetric method. Furthermore, four arsenic (arsenite, arsenate, monomethylarsonic and dimethylarsinic acid), two phosphorus (phosphite and phosphate) and two sulfur (sulfide and sulfate) species were separated in 10 min by ion chromatography -ICP-MS with the NH₄HCO₃ mobile phase. We verified the technique using paddy soils collected from the field, and present the mm-scale profiles of iron, manganese, and arsenic, phosphorus, sulfur species (relative standard deviation < 8%). The technique developed in this study will significantly promote the measurement throughput in limited samples (e.g. 100 μL) collected by HR samplers, which would greatly facilitate redox-sensitive elements biogeochemical cycling in saturated soils.