The Chemical Nature of Mercury and Copper Sulfides and Its Implication for Bioavailability Assessments in Sediments

Sulfur chemistry plays an important role in regulating the bioavailability of heavy metals (HMs) because HM sulfides are extremely insoluble in sediments. However, quantifying HM sulfides in sediments has been difficult because they are considered acid-extractable (AE). Previous studies also found that Hg and Cu behaved differently from other HMs in sediments. This study investigated the chemical nature of Hg and Cu sulfides and the causes of Hg and Cu anomalies in sediments. The results indicated that Hg and Cu sulfides are not mono-sulfides (HS− or S=) but bi-sulfides (S2=), which are non-acid-extractable (NAE) under nitrogen. These results explain the Hg and Cu anomalies compared to other HMs and facilitate a procedure to quantify Hg and Cu sulfides in sediments. We analyzed the AE and NAE fractions of Hg, Cu, and Zn under nitrogen in the sediments of Apalachicola Bay, North Florida. Zn was included for comparison because Zn sulfide is mono-sulfide. The NAE Hg and Cu were, on average, 97.9 ± 2.7% and 84.6%, respectively, of the total, much higher than that of Zn (24.3% of the total) in the sediments, as expected. The NAE fractions of Hg and Cu were sulfides and thus could be excluded from the bioavailability assessments.