Impact of long-term irrigation practices on distribution and speciation of arsenic in agricultural soil.

To better understand the impact of long-term irrigation practices on arsenic (As) accumulation in agricultural soils, 100 soil samples from depths of 0-20 cm were collected from the Datong basin, where the As-contaminated groundwater has been used for irrigation for several decades. Soil samples were analyzed for major elements, trace elements, and As, Fe speciation. Results reveal As content ranging from 4.00 to 14.5 mg/kg, an average of 10.2 ± 2.05 mg/kg, consistent with surveys conducted in 1998 and 2007. Arsenic speciation ranked in descending order as follows: As associated with silicate minerals (As, 29.70 ± 7.53 %) > amorphous Fe-minerals associated As (As, 26.40 ± 3.27 %) > crystalline Fe-minerals associated As (As, 24.02 ± 4.60 %) > strongly adsorbed As (As, 14.29 ± 2.81 %) > As combined with carbonates and Fe-carbonates (As, 2.30 ± 0.44 %) > weakly adsorbed As (As, 2.59 ± 1.00 %). The anomalous negative correlation between As and Fe content reflects the primary influence of soil provenance. Evidence from major element compositions and rare earth element patterns indicates that total As and Fe contents in soils are controlled by parent materials, exhibiting distinct north-south differences (As: higher levels in the north, lower levels in the south; Fe: higher levels in the south, lower levels in the north). Evidence from the Chemical Index of Alteration (CIA) and As/Ti ratio suggests that chemical weathering has led to As enrichment in the central basin. Notably, relationships such as As/Ti, As/Ti with CIA and total Fe content indicate significant influences of irrigation practices on adsorbed As (both weakly and strongly adsorbed) contents, showing a pattern of higher levels in the central basin and lower levels in the Piedmont. However, total As content remained stable after long-term irrigation, potentially due to the re-release of accumulated As via geochemical pathways during non-irrigated periods. These findings demonstrate that the soil systems can naturally remediate exogenous As contamination induced by irrigation practices. Quantitative assessment of the balance between As enrichment and re-release in soil systems is crucial for preventing soil As contamination, highlighting strategies like water-saving techniques and fallow periods to manage As contamination in agricultural areas using As-contaminated groundwater for irrigation.