Geochemical controls on distributions and speciation of As and Hg in sediments along the Gaoping (Kaoping) Estuary-Canyon system off southwestern Taiwan

Surface and box-cored sediments were collected along the Gaoping (formerly spelled Kaoping) Estuary-Canyon system and analyzed for As and Hg contents and speciation, 210Pb-based sedimentation rates and various geochemical parameters to elucidate the mechanisms that control natural and anthropogenic inputs of As and Hg from the Gaoping (Kaoping) River (KPR). The contents of As and Hg in surface sediments ranged from 1.84 to 20.7 mg kg− 1 and from 0.07 to 2.15 mg kg− 1, respectively, in the estuary and canyon. The concentrations generally decreased from the lower river toward the mixing boundary and then increased toward the estuarine mouth, followed by a slight variation in the canyon. Both As and Hg concentrations correlated strongly with clay, total organic carbon (TOC), Al, Fe and Mn contents in estuarine sediments but not necessary the same cases for canyon surface sediments. The factor analysis of surface sediments shows that the first two factors, which account for 75.6% of the variance, may represent major roles of carriers (clay, Al and Fe-Mn oxides) and TOC in controlling As and Hg distributions, respectively. Accordingly, the spatial patterns of the enrichments of As (1.9-16.2) and Hg (1.8-30.8) with reference to the crust levels follow the individual element's distribution patterns, likely because of deposition variability following inputs from the river. The contents of mobile As and Hg correlated substantially with the contents of both metals that were extracted with 0.1 M HCl. In addition to the major pool in the residual fraction (65-87%), As was relatively abundant in Fe-Mn oxides/hydroxides, whereas Hg was abundant in the organic/sulfide fraction. The deposition and accumulation rates of As and Hg in the canyon clearly decreased as the depth of water increased. The depth distributions of both metals are likely controlled primarily by TOC and Fe-Mn oxides associated factors followed by a contribution from anthropogenic pollution. The metal pollution appears to have increased substantially around 1970, following the economic boom in Taiwan, suggesting that modern sediments in the Gaoping (Kaoping) Canyon were derived from the Gaoping (Kaoping) River (KPR).