The sequestration of sulfur within sedimentary pyrite is a major sink in the global biogeochemical sulfur cycle and has consequent impacts on the related cycles of carbon and oxygen. In many sedimentary environments, a zone exists which releases H 2 S if treated with acid. The materials that produce this sulfide are described as acid volatile sulfides or AVS and the sulfide which is evolved and collected by this treatment is called acid volatile sulfide (AVS-S). In this research review we show that AVS represents part of a complex and dynamic biogeochemical system which is not defined simply by the analysis of AVS-S. During the 40 years since R.A. Berner first defined the concept of acid volatile sulfide, a number of scientific myths have developed regarding the nature and composition of AVS and its role in the global sulfur cycle. We show that: • AVS is not equivalent to FeS and solid FeS phases have rarely been identified in marine sediments. AVS is a complex and variable component which does not represent any singular or simple group of sediment components. • The commonly used extraction methods do not quantitatively extract AVS minerals (mackinawite and greigite) without also significantly releasing sulfide from pyrite. • AVS varies geographically and AVS is not the same component or set of components wherever it is found. • The solubilities of FeS and Fe 3 S 4 in neutral to alkaline systems are presently poorly constrained and pore water saturation state calculations cannot be used to support the presence of specific AVS minerals. • The colored zone in sediments does not reflect the distribution of AVS. • AVS is not always a minor fraction of total reduced sulfide (TRS) which dominantly occurs near the sediment–water interface. AVS minerals are not required precursors for pyrite formation. A better understanding of the sedimentary sulfur system, including its nature, formation and transformations, is a key component in understanding the evolution of the Earth and its future development. However, some basic parameters, such as the solubility and composition of the metastable iron sulfide solids, are still not constrained. Even the presence of these minerals in most sedimentary systems remains equivocal. Aqueous FeS clusters appear to be ubiquitous and appear to have significant geochemical and biological roles. The roles of organisms, especially in modifying rates and products, remain a key area of research. Although AVS may have served its purpose in the earlier exploratory days of the study of sedimentary sulfides, the concept is now probably more of a hindrance than a help in advancing this field. It is reasonable to question if it is not time to simply do away with the AVS concept altogether and get on with the business of trying to deal more directly with the behavior of the more important components known to fall within the group of sulfide species that contribute to sulfide that is volatilized when acid is added to a sediment.
Marine Chemistry – Elsevier
Published: Dec 20, 2005
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