Partitioning and (im)mobilization of arsenic associated with iron in arsenic-bearing deep subsoil profiles from Hong Kong

• Published in: Environmental pollution (1987) Vol. 308; p. 119527
• Main Authors: Cui, Jin-li, Yang, Jinsu, Zhao, Yanping, Chan, Tingshan, Xiao, Tangfu, Tsang, Daniel C.W., Li, Xiangdong
• Format: Journal Article
• Language: English
• Published: England Elsevier Ltd 01.09.2022
• Subjects: Arsenic; Groundwater; Iron oxide; Soil profile; Speciation and mobilization; XANES; Speciation and mobilization; Iron oxide; Arsenic; Groundwater; Soil profile; XANES
• ISSN: 0269-7491; 1873-6424
• DOI: 10.1016/j.envpol.2022.119527

Understanding the arsenic (As) enrichment mechanisms in the subsurface environment relies on a systematic investigation of As valence species and their partitioning with the Fe (oxyhydr)oxide phases in the subsoil profile. The present study explored the distribution, speciation, partitioning, and (im)mobilization of As associated with Fe in four subsoil cores (∼30 m depth) from Hong Kong using sequential chemical extraction and X-ray absorption near edge spectroscopy. The subsoil profiles exhibited relatively high concentrations of As at 26.1–982 mg/kg (median of 112 mg/kg), and the As was dominated by As(V) (85–96%) and primarily associated with the residual fraction (50.7–94.7%). A small amount of As (0.002–13.2 mg/kg) was easily mobilized from the four subsoil profiles, and a concentration of water-soluble As higher than 100 μg/L was observed for only some subsoil layers. The molar ratios of As:Fe in the oxalate-extractable Fe fraction ranged from 1.2 to 76.5 mmol/mol (median of 11.1 mmol/mol), revealing the participation of poorly crystalline Fe (oxyhydr)oxides in immobilizing most of the high geogenic As. The primary phases of ferric (oxyhydr)oxides were characterized as ferrihydrite (16–53%), lepidocrocite (0–32%), and goethite (0–62%), and these phases contributed to the sufficient ability of the subsoil to sequester 45.3–100% (median of 98.8%) of the exogenous As(V) (1.0 mg/L) in adsorption experiments. In contrast to As(V), exogenous As(III) showed a lower removal percentage (3.9–79.1%, median of 45.1%). The study revealed that the chemical speciation of As and Fe in the subsoil profiles is useful for predicting the immobilization of high geogenic As in the region, which is also helpful for the safe utilization of As-containing soil during land development worldwide. [Display omitted] •Partitioning of geogenic As and Fe was unraveled within deep subsoil cores.•High As was considered stable due to large residual fraction and dominance of As(V).•Sufficient amount of amorphous Fe phases in soils are crucial for As stabilization.•Insufficient adsorption sites in some subsoil layer might lead to As release to water.