Humic sulfur in eutrophic bay sediments: Characterization by sulfur stable isotopes and K-edge XANES spectroscopy

• Both HA- and FA-S are mixtures of biosynthetic and diagenetic OS.
• FA-S burial has been enhanced by eutrophication to some extent.
• Pyritization has not inhibited OM sulfurization to a significant extent.
• Sulfurization enhanced the fractions of strongly reduced S in FA-S.
• Both oxidized and strongly reduced OS are important compounds in humic S.

Organic sulfur (OS) is an important sedimentary sulfur pool in marine sediments and chemical extractions are often used for quantification of various OS pools, however, OS sources and mechanisms of OS formation are not well understood. In this study, sulfur stable isotope and sulfur X-ray absorption near edge structure (XANES) spectroscopy were combined to investigate the sources and speciation of humic-acid sulfur (HA-S) and fulvic-acid sulfur (FA-S) in sediments of eutrophic Jiaozhou Bay. Whilst there may be some indication that eutrophication has enhanced FA-S burial in the sediment, this has not substantially modified the characteristically low humic sulfur (i.e., HA-S + FA-S) contents of the sediments. Sulfur isotopic compositions indicate that both HA-S and FA-S are mixtures of diagenetic and biosynthetic OS in origin; HA-S is dominated by biosynthetic sulfur and FA-S by diagenetic source. Sulfur isotopic compositions and contents of pyrite and diagenetic OS indicate that inhibition of sulfurization by pyrite formation, if any, appears insignificant. XANES analysis suggests that the contents of high oxidized OS (i.e., sulfones and ester-sulfates) and strongly reduced OS species are comparable in the HA-S, whereas the FA-S is dominated by strongly reduced OS as a result of enhanced sulfurization.