Copper and zinc in vineyard and orchard soils at millimeter vertical resolution

Intensive uses of agrochemicals and soil amendments often cause the elevation of Cu and Zn concentrations in vineyard (VY) and orchard soils. The concentration and speciation of Cu and Zn in the soils at millimeter resolution is critical to understanding the risk of transport of these metals via surface runoff and infiltration. The objective of this study was to investigate the concentration and chemical species of Zn and Cu in VY and persimmon (PS) soils at millimeter vertical resolution. The soils were collected with 5 mm increments down to 5 cm depth and with 5 cm increments down to 25 cm depth. The total concentration and chemical species of Zn and Cu were determined by total digestion and X-ray absorption fine structure (XAFS) spectroscopy, respectively. The Zn concentration of VY soil reached a maximum of 290 mg kg^-1 at the uppermost layer of the profile (0.5-1.0 cm). The Cu concentration of VY soil reached a maximum of 201 mg kg^-1 (10-15 cm). These Zn and Cu concentrations were greater than background levels. Zinc K-edge XAFS spectroscopy determined that the uppermost layer of VY soil (0-0.5 cm) contained 42% Zn associated with humus and lesser extent of Zn associated with gibbsite (37%) and kaolinite (21%). Zinc associated with humus was not observed in the VY soil profiles below 0.5 cm, whereas Zn associated with gibbsite and kaolinite contributed >83% of total Zn species. Copper K-edge XAFS spectroscopy determined the presence of Cu bonded with humus (40-67%) and Cu adsorbed on kaolinite (26-45%) in the entire soil profile. Our study found the remarkable variation of Cu and Zn concentration and speciation within several centimeters from the soil surface in vineyard and orchard landscapes.