Iodine release associated with the transformation of iron minerals in natural sediments

Junxia Lia, X.J. Xiea, M. Siebeckerb and D.L. Sparksc

a School of Environmental Studies, China University of Geosciences, 430074 Wuhan, China

bDepartment of Plant and Soil Science, Texas Tech University, Lubbock, Texas, 79409, United States

c Soil Chemistry Group, Delaware Environmental Institute and Department of Plant and Soil Sciences, University of Delaware, Newark, Delaware 19716, United States

jxli@cug.edu.cn

Iodine is an essential element for thyroid hormone synthesis. According to a recent worldwide survey of median urinary iodine, 11 countries around the world have an excess of iodine intake, which can trigger iodine toxicity disorders (IED) and cause immune responses such as autoimmune thyroiditis. In China, excessive iodine intake is widespread, with approximately 31 million people in 11 provinces affected. Our previous studies found the occurrence of high iodine groundwater in the Datong basin and North China Plain, which increases hypothyroidism risk for residents using the groundwater as the main source of drinking water. However, the current understanding of the hydrochemical cycling of iodine in the groundwater systems is very limited.

Our previous studies found that iodine concentration in groundwater can be up to 1187 µg/L at the Datong basin. In the basin, the iodine-loaded metal (oxy)hydroxides are considered as an primary hosts of soil/sediment iodine, and dissimilatory reduction of metal (oxy)hydroxides would lead to iodine mobilization from sediment into groundwater. Therefore, in order to better understand the iodine mobilization in this groundwater system, a series of batch incubation experiments investigating the transformation of iron minerals were performed under both aerobic and anaerobic conditions.

Two sediment samples of DXZ04 and DXZ147 at depths of 4.35 m and 281 m, respectively, were collected from the iodine-affected area of the Datong basin to perform the batch incubation experiments which involved the iron reducer Shewanella oneidensis MR-1. Iron K-edge X-ray absorption near edge spectroscopy (XANES) and PHREEQC (Version 3, 3.4.0-12927) were used to identify the transformation of Fe phases and iodine species, respectively. The results showed that for the shallow sediment DXZ04, after treatment with the iron reducer MR-1 and Na-lactate (used as an electron donor for MR-1), iodine release from sediment into solution was observed under anaerobic conditions compared with no evident release of iodine under aerobic conditions. The redox-derived transformation of sediment Fe phases from the crystalline Fe to HCl-extractable Fe phases was considered as the main factor causing the iodine release. For the untreated deep sediment DXZ147, a higher ratio of HCl-extractable Fe fraction to natural sediment Fe phases was observed. Consistently, the groundwater from the deep aquifer had the higher iodine concentrations (up to 732 µg/L) than the shallow aquifer, suggesting that the long-term transformation of Fe minerals under the reducing conditions of the deep aquifer led to iodine mobilization from the sediment into the groundwater. In addition, during the iodine release, the transformation of iodine species from organic iodine or iodate to iodide further promotes its mobilization. The evidence gained from this study provides new insights on the genesis of natural high iodine groundwater.

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