Identification of the sources of metals and arsenic in river sediments by multivariate analysis and geochemical approaches

Frequent mining activities and higher background values in soil have led to the contamination of the sediments of some rivers in southwest China by several metals and arsenic (As). This study combined multivariate analysis with geochemical approaches to differentiate mining activity from other sources, which may aid to evaluate the effectiveness of reducing mining release. Sixteen sediment samples were collected along the Yuan River, China. The total concentrations of lead (Pb), zinc (Zn), copper (Cu), cadmium (Cd), chromium (Cr), mercury (Hg), and As were measured by inductively coupled plasma-atomic emission spectrometer (ICP-AES). The Pb isotopic composition was measured using a thermal ionization mass spectrometer (TIMES). Both geochemical approaches and multivariate statistical analysis were used to identify the sources of these metals. The fractionation of Pb was determined through a Community Bureau of Reference (BCR) sequential extraction procedure to aid the identification of the sources. The concentrations and enrichment factors (EFs) of Pb, Zn, Cu, Cd, and As in the middle reach of the river were higher than those at the other sites, indicating anthropogenic sources. The factor analysis (FA) extracted mining and smelting, mixture of anthropogenic and natural, and natural factors. The Pb isotope composition of metal ores was similar (Pb-206/Pb-207 < 1.190 and Pb-208/Pb-206 > 2.023) to that found in the sediments in the middle reach, indicating anthropogenic sources of mining activities. Compared with the narrow ranges of the delta S-34 ratios in the bedrock (+8.5 to +9.3 aEuro degrees) and the metal ores (-1.4 to +1.9 aEuro degrees), the sediment samples presented a relatively wide range of delta S-34 ratios from -2.6 to +9.2 aEuro degrees with a mean of +2.6 aEuro degrees, which suggests a mixed composition. The BCR sequential extraction procedure revealed that the proportion of the extractable fraction in the sediments in the middle reach was higher than that in other sites, suggesting anthropogenic sources as the cause of contamination in the study area. Lead, Zn, Cu, Cd, Cr, Hg, and As are mainly derived from natural materials in the upstream region. In the middle reach, these elements are the result of anthropogenic activities, particularly activities associated with the mining industry. In the downstream region, the origin of these elements is considered to be a mixture of anthropogenic and natural sources. In addition to geochemical approaches and multivariate statistical analysis, the BCR sequential extraction method is an effective procedure for the identification of the anthropogenic sources of sediment-associated metals.