An integrated hydrogeochemical study is carried out to realize the occurrence of arsenic (As) in a saline aquifer. Saline groundwater was mostly concentrated in the uppermost aquifer and non-saline water was in the lower aquifer in the study area. High As concentrations were found in both uppermost and lower aquifers. No correlation among salination, well depth and As concentration was observed. Both reducing and oxidizing forms of Fe oxyhydroxides were identified in the magnetic fractions, which were concentrated by high gradient magnetic separation (HGMS) technique, revealing that the redox cycling of Fe occurred in the subsurface. High levels of Fe, HCO3-, DOC and NH4+ concentrations accompanying alkaline pH in the As-rich groundwater were consistent with the mechanism triggered by the microbial-mediated reductive dissolution of Fe oxyhydroxides. A threshold value of 50 μg L−1. As concentration was used as an indicator for identification of active proceeding reductive dissolution of As-bearing Fe oxyhydroxides in the saline aquifer. Desorption behaviors of As were relevant to its valence in the sediments and the co-existence of anions. Experimental and numerical results showed that additions of Cl- and SO42-, which represented the main anions of saline water, had minor effect on leaching sedimentary As. Although bicarbonate addition resulted in less As desorption than that of phosphate on a molar basis, the contribution of bicarbonate to the total release of As was greater than phosphate due to the much higher concentration of bicarbonate in groundwater and the associated microbial mediation. Collectively, the chemical effect of saline water on the As-release to groundwater is mild in the coastal aquifer
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