Depth profiles of dissolved sulfide and sulfate in the pore water of hydrocarbon seep sediments offshore Pakistan

The interaction between fluid seepage, bottom water redox, and chemosynthetic communities was studied at cold seeps across one of the world's largest oxygen minimum zones (OMZ) located at the Makran convergent continental margin. Push cores were obtained from seeps within and below the core-OMZ with a remotely operated vehicle. Extracted sediment pore water was analyzed for sulfide and sulfate concentrations. Depending on oxygen availability in the bottom water, seeps were either colonized by microbial mats or by mats and macrofauna. The latter, including ampharetid polychaetes and vesicomyid clams, occurred in distinct benthic habitats, which were arranged in a concentric fashion around gas orifices. At most sites colonized by microbial mats, hydrogen sulfide was exported into the bottom water. Where macrofauna was widely abundant, hydrogen sulfide was retained within the sediment. Numerical modeling of pore water profiles was performed in order to assess rates of fluid advection and bioirrigation. While the magnitude of upward fluid flow decreased from 11 cm yr**-1 to <1 cm yr**-1 and the sulfate/methane transition (SMT) deepened with increasing distance from the central gas orifice, the fluxes of sulfate into the SMT did not significantly differ (6.6-9.3 mol m**-2 yr**-1). Depth-integrated rates of bioirrigation increased from 120 cm yr**-1 in the central habitat, characterized by microbial mats and sparse macrofauna, to 297 cm yr**-1 in the habitat of large and few small vesicomyid clams. These results reveal that chemosynthetic macrofauna inhabiting the outer seep habitats below the core-OMZ efficiently bioirrigate and thus transport sulfate down into the upper 10 to 15 cm of the sediment. In this way the animals deal with the lower upward flux of methane in outer habitats by stimulating rates of anaerobic oxidation of methane (AOM) with sulfate high enough to provide hydrogen sulfide for chemosynthesis. Through bioirrigation, macrofauna engineer their geochemical environment and fuel upward sulfide flux via AOM. Furthermore, due to the introduction of oxygenated bottom water into the sediment via bioirrigation, the depth of the sulfide sink gradually deepens towards outer habitats. We therefore suggest that - in addition to the oxygen levels in the water column, which determine whether macrofaunal communities can develop or not - it is the depth of the SMT and thus of sulfide production that determines which chemosynthetic communities are able to exploit the sulfide at depth. We hypothesize that large vesicomyid clams, by efficiently expanding the sulfate zone down into the sediment, could cut off smaller or less mobile organisms, as e.g. small clams and sulfur bacteria, from the sulfide source.

Reconsidering the use of photosynthetic bacteria for removal of sulfide from wastewater

The feasibility of using photosynthetic sulfide-oxidizing bacteria to remove sulfide from wastewater in circumstances where axenic cultures are unrealistic has been completely reconsidered on the basis of known ecophysiological data, and the principles of photobioreactor and chemical reactor engineering. This has given rise to the development of two similar treatment concepts relying on biofilms dominated by green sulfur bacteria (GSB) that develop on the exterior of transparent surfaces suspended in the wastewater. The GSB are sustained and selected for by radiant energy in the band 720 - 780 nm, supplied from within the transparent surface. A model of one of these concepts was constructed and with it the reactor concept was proven. The dependence of sulfide-removal rate on bulk sulfide concentration has been ascertained. The maximum net areal sulfide removal rate was 2.23 g m(-2) day(-1) at a bulk sulfide concentration of 16.5 mg L-1 and an incident irradiance of 1.51 W m(-2). The system has a demonstrated capacity to mitigate surges in sulfide load, and appears to use much less radiant power than comparable systems. The efficacy with which this energy was used for sulfide removal was 1.47 g day(-1) W-1. The biofilm was dominated by GSB, and evidence gathered indicated that other types of phototrophs were not present. (C) 2004 Wiley Periodicals, Inc.

Performance of a substratum-irradiated photosynthetic biofilm reactor for the removal of sulfide from wastewater

The performance of a sulfide-removal system based on biofilms dominated by green sulfur bacteria (GSB) has been investigated. The system was supplied with radiant energy in the band 720-780 nm, and fed with a synthetic wastewater. The areal net sulfide removal rate and the efficacy of the incident radiant energy for sulfide removal have been characterized over ranges of bulk sulfide concentration (1.6-11.5 mg L-1) and incident irradiance (0.21-1.51 W m(-2)). The areal net sulfide removal rate increased monotonically with both increasing incident irradiance and increasing bulk sulfide concentration. The efficacy of the radiant energy for sulfide removal (the amount of sulfide removed per unit radiant energy supplied) also increased monotonically with rising bulk sulfide concentration, but exhibited a maximum value with respect to incident irradiance. The maximum observed values of this net removal rate and this efficacy were, respectively, 2.08 g m(-2) d(-1) and 2.04 g W-1 d(-1). In-band changes in the spectral composition of the radiant energy affected this efficacy only slightly. The products of sulfide removal were sulfate and elemental-S. The elemental-S was scarcely released into the liquid, however, and reasons for this, such as sulfur reduction and polysulfide formation, are considered. Between 1.45 and 3.85 photons were needed for the net removal of one electron from S-species. Intact samples of the biofilm were characterized by microscopy, and their thicknesses lay between 39 +/- 9 and 429 +/- 57 mum. The use of the experimentally determined rates and efficacies for the design of a pilot-scale system is illustrated. (C) 2004 Wiley Periodicals, Inc.

Effects of acetate and propionate on the performance of a photosynthetic biofilm reactor for sulfide removal

The effects of acetate and propionate on the performance of a recently proposed and characterized photosynthetic biological sulfide removal system have been investigated with a view to predicting this concept's suitability for removing sulfide from wastewater undergoing or having undergone anaerobic treatment. The concept relies on substratum-irradiated biofilms dominated by green sulfur bacteria (GSB), which are supplied with radiant energy in the band 720 - 780 nm. A model reactor was fed for 7 months with a synthetic wastewater free of volatile fatty acids (VFAs), after which time intermittent dosing of the wastewater with acetate or propionate was begun. Such dosing suppressed the areal net sulfide removal rate by similar to50%, and caused the principal net product of sulfide removal to switch from sulfate to elemental-S. Similarly suppressed values of this rate were observed when the wastewater was dosed continuously with acetate, and this rate was not significantly affected by changes in the concentration of ammonia-N in the feed. The main net product of sulfide removal was again elemental-S, which was scarcely released into the liquid, however. Sulfate reduction and sulfur reduction were observed when the light supply was interrupted and were inferred to be occurring within the irradiated biofilm. A preexisting conceptual model of the biofilm was augmented with both of these reductive processes, and this augmented model was shown to account for most of the observed effects of VFA dosing. The implications of these findings for the practicality of the technology are considered. (C) 2004 Wiley Periodicals, Inc.

(Table 2) Hydrogen sulphide and methane content, and loss on ignition in sediments obtained in the Gotland Deep, Baltic Sea

The distribution of methane and hydrogen sulfide concentrations in sediments of various basins of the Baltic Sea was investigated during 4 cruises in 1995 and 1996. Significant differences in the concentrations of both compounds were recorded between the basins and also between different areas within the Gotland Deep. High-methane sediments with distinctly increasing concentrations from the surface to deeper layers were distinguished from low-methane sediments without a clear gradient. Methane concentrations exhibited a fair correlation with the sediment accumulation rate, determined by measuring the total thickness of the post-Ancylus Holocene sequence on echosounding profiles in the Gotland Deep. Only weak correlations were observed with the content of organic matter in the surface layers of the sediments. Hydrogen sulfide concentrations in the sediments showed a positive correlation with methane concentrations, but, in contrast to methane concentrations, were strongly influenced by the transition from oxic to anoxic conditions in the water column between 1995 and 1996. Sediments in the deepest part of the Gotland Basin (>237 m water depth), covering an area of approximately 35 km**2, were characterized by especially high accumulation rates (>70 cm/ka) and high methane and hydrogen sulfide contents. Concentrations of these compounds decreased rapidly towards the slope of the basin.

(Table T1) Dissolved sulfide concentration and d34S of dissolved sulfate and sulfide in pore waters of ODP Leg 204

We report dissolved sulfide sulfur concentrations and the sulfur isotopic composition of dissolved sulfate and sulfide in pore waters from sediments collected during Ocean Drilling Program Leg 204. Porewater sulfate is depleted rapidly as the depth to the sulfate/methane interface (SMI) occurs between 4.5 and 11 meters below seafloor at flank and basin locations. Dissolved sulfide concentration reaches values as high as 11.3 mM in Hole 1251E. Otherwise, peak sulfide concentrations lie between 3.2 and 6.1 mM and occur immediately above the SMI. The sulfur isotopic composition of interstitial sulfate generally becomes enriched in 34S with increasing sediment depth. Peak d34S-SO4 values occur just above the SMI and reach up to 53.1 per mil Vienna Canyon Diablo Troilite (VCDT) in Hole 1247B. d34S-Sigma HS values generally parallel the trend of d34S-SO4 values but are more depleted in 34S relative to sulfate, with values from -12.7 per mil to 19.3 per mil VCDT. Curvilinear sulfate profiles and carbon isotopic composition of total dissolved carbon dioxide at flank and basin sites strongly suggest that sulfate depletion is controlled by oxidation of sedimentary organic matter, despite the presence of methane gas hydrates in underlying sediments. Preliminary data from sulfur species are consistent with this interpretation for Leg 204 sediments at sites not located on or near the crest of Hydrate Ridge.