Relationship between enrichment, toxicity, and chemical bioavailability of heavy metals in sediments of the Cai River estuary

This study focuses on heavy metals (HMs) (Cr, Co, Ni, Cu, Zn, and Pb) along with Al, Fe, Mn, organic carbon (TOC), and carbonates (TIC) detected in surface sediments from the River Cai-Nha Trang Bay estuarine system (South China Sea). The enrichment factors (EFAl and EFFe), Geoaccumulation Index (I-geo), Adverse Effect Index (AEI), and toxic units (TUs) were used to assess the HM enrichment and toxicity in the sediments. The selective single-step extraction procedure was applied to determine the chemical forms of HMs in order to assess their potential bioavailability. The EF and I-geo calculations suggest that sedimentary Fe, Mn, Cr, Co, Ni, and Cu are derived mainly from natural sources (EFAl and EFFe < 1.5 and I-geo < 0 at all sampling sites), while the moderate Pb enrichment (EFAl and EFFe >= 2 and I-geo >= 1 at all sampling sites) may indicate a moderate contamination. Cr, Cu, and Zn suggest low potential toxicity, while both Ni and Pb show above threshold AEI levels (AEI >= 1) and contribute up to 30-40% to the sum of toxic units ( n-ary sumation TUs) at all sampling sites. According to their comparative ability to mobilize metals from the sediments, the single extractants applied were arranged in descending order: acetic acid > ammonium oxalate >> sodium pyrophosphate. All single-step extractants mobilized substantive amounts of Pb (7-30% of total content, on average) from sediments, indicating considerable potential bioavailability. Among HMs studied, the percentage of acid-soluble Pb (23-35%) significantly exceeded the respective ranges in the sediments of other coastal regions. Pearson's correlation and PCA analyses revealed that among HMs studied, Cr, Ni, and Co enrichment is positively associated with the salinity gradient due to the accumulation of the most fine-grained Fe-rich aluminosilicate host minerals in the bay zone, while sediments in the transitional zone are mainly enriched in Cu, Zn, and Pb due to the local accumulation of metal-rich detrital heavy minerals. The percentages of bioavailable forms of most of the HMs are negatively associated with the salinity gradient due to the preferential accumulation with fluvial Fe/Mn oxyhydroxides in the frontal and transitional zones. Generally, distribution of the enrichment indices of most of the HMs is not associated or even negatively associated with the percentage of the bioavailable forms. The intensity of monsoonal precipitation is shown to be an essential factor in the natural enrichment of estuarine sediments with bioavailable metals. Determining the local geochemical background of HMs and Pb, in particular, is a major goal for future study.