Size-resolved distribution of trace elements in lysimeter soil solutions under contrasting long-term agricultural...

The chemical species of trace elements (TEs) in agricultural soils is highly variable under diverse conditions, requiring tools with clear resolution and minimal disturbance for exploration. A novel surgical (316L) stainless steel (SS) lysimeter with a 5 μm pore size was developed to collect field soil solutions. The size-resolved distribution of TEs were characterized into total (nitric acid digestion), particulate (0.45-5 μm), dissolved (<0.45 μm), colloidal (1 kDa to 0.45 μm), and mainly ionic (<1 kDa) fractions in the lysimeter soil solutions. Total concentrations of TEs (dry weight basis) in acid digested Gray Luvisolic soils were analyzed. Most TEs in lysimeter soil solutions were present in particulate phases, relevant to their geochemical affinities and occurrences in soil minerals. Among dissolved fractions, As, Ba, Co, Li, Mn, Tl, and V existed as mainly ionic species in the soil solutions. Copper, Pb, Al, Th, and U showed variable associations with dissolved organic matter (DOM) and/or inorganic colloids among agricultural treatments. Inorganic NPKS or NKS fertilizer applications with lower pH (5.25-5.74) enhanced mobility and potential bioavailability of Ba, Co, Li, Mn, and Pb present in mainly ionic species, compared with other locations (pH 5.82-6.37). Manure application exhibited a dual effect, potentially increasing bioavailability for As, Tl, and V due to probably enhanced cation exchange capacity (CEC), while also facilitating specific adsorption of Cu and U on DOM, potentially reducing their bioavailability depending on DOM molecular weight. Colloidal and ionic Al and Th concentrations were higher in forest soils than agricultural soils, with extremely low potential bioavailability of Th attributed to strong precipitation with inorganic colloids and adsorption on DOM. The lysimeter sampling and size fractionation method provided a clear insight into agricultural effects on TE distributions and enhancing understanding of agricultural soil health in terms of TE bioavailability in situ.