Chemical speciation of sulfur compounds in surface sediments from three bays (Fresnaye, Seine and Authie) in northern France, and identification of some factors controlling their generation

Abstract

The determination of total reduced sulfur, elemental sulfur, sulfide, thiosulfate and sulfite in porewaters — which were previously extracted from surface sediments collected in three bays, i.e. Seine, Fresnaye and Authie located in northern France — has been undertaken using different electroanalytical techniques (linear sweep cathodic stripping voltammetry (LSCSV), square wave cathodic stripping voltammetry (SWCSV) and differential pulse cathodic stripping voltammetry (DPCSV)) at a static mercury drop electrode. Furthermore, the analyses of sulfur solids present in these sediments have been performed by sequential extraction procedures. Overall, the description of speciation of dissolved sulfur compounds and reduced sulfur solids has shown that the availability of sulfate and reactive iron, the sedimentation rate and probably even the nature and content of organic matter are important factors for controlling the sulfidisation and pyritisation processes involved in the different sedimentary systems studied. Thus, in the Seine-bay sediments, it has been found that reactive iron scavenges the most part of the generated sulfide as a result of a particularly activated sulfate reduction by bacterial activities; as a consequence, this precipitation limits the accumulation in the porewaters of reduced sulfur compounds such as elemental sulfur and polysulfides which ought to be generated in the redox boundary (where the oxydants, viz. oxygen, nitrate and metal oxides exist abundantly) through a partial oxidation of the H 2S and HS − species. This process is further accentuated by a sedimentation rate measured in the Seine estuary. Conversely, in the Authie bay and, to a lesser extent, in the Fresnaye bay the contribution of the sedimentation rate and/or reactive iron scavenging to the sedimentary sulfur processes is weaker. This explains the increase of the built-up of dissolved reduced sulfur in the interstitial waters as well as the existence of elemental sulfur and polysulfides that permit the conversion of FeS into FeS 2.