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A static enclosure method was applied to determine the exchange of dimethyl sulfide (DMS) and carbonyl sulfide (OCS) between the surface of Sphagnum peatlands and the atmosphere. Measurements were performed concurrently with dynamic (flow through) enclosure measurements with sulfur-free air used as sweep gas. This latter technique has been used to acquire the majority of available data on the exchange of S gases between the atmosphere and the continental surfaces and has been criticized because it is thought to overestimate the true flux of gases by disrupting natural S gas gradients. DMS emission rates determined by both methods were not statistically different between 4 and greater than 400 nmol/sq m/h, indicating that previous data on emissions of at least DMS are probably valid. However, the increase in DMS in static enclosures was not linear, indicating the potential for a negative feedback of enlosure DMS concentrations on efflux. The dynamic enclosure method measured positive OCS flux rates (emission) at all sites, while data using static enclosures indicated that OCS was consumed from the atmosphere at these same sites at rates of 3.7 to 55 nmol/sq m/h. Measurements using both enclosure techniques at a site devoid of vegetation showed that peat was a source of both DMS and OCS. However, the rate of OCS efflux from decomposing peat was more than counterbalanced by OCS consumption by vegetation, including Sphagnum mosses, and net OCS uptake occurred at all sites. We propose that all wetlands are net sinks for OCS.

Rates of emissions of the biogenic sulfur (S) gases carbonyl sulfide (COS), methyl mercaptan (MSH), dimethyl sulfide (DMS), and carbon disulfide (CS2) were measured in a variety of marine and freshwater wetland habitats in the Florida Everglades during a short duration period in October using dynamic chambers, cryotrapping techniques, and gas chromatography. The most rapid emissions of over 500 nmol/sq m/h occurred in red mangrove-dominated sites that were adjacent to open seawater and contained numerous crab burrows. Poorly drained red mangrove sites exhibited lower fluxes of about 60 nmol/sq m/h, which were similar to fluxes from the black mangrove areas which dominated the marine-influenced wetland sites in the Everglades. DMS was the dominant organo-S gas emitted especially in the freshwater areas. Spectral data from a scene from the Landsat TM were used to map habitats in the Everglades. Six vegetation categories were delineated using geographical information system software and S gas emissions were extrapolated for the entire Everglades National Park. The black mangrove-dominated areas accounted for the largest portion of S gas emissions to the area. The large area extent of the saw grass communities accounted for about 24 percent of the total S emissions.

Results of sulfur emission measurements made in freshwater and marine wetlands in Alaskan tundra during the Arctic Boundary Layer Expedition 2A (ABLE 3A) in July 1988 are presented. The data indicate that this type of tundra emits very small amounts of gaseous sulfur and, when extrapolated globally, accounts for a very small percentage of the global flux of biogenic sulfur to the atmosphere. Sulfur emissions from marine sites are up to 20-fold greater than fluxes from freshwater habitats and are dominated by dimethyl sulfide (DMS). Highest emissions, with a mean of 6.0 nmol/sq m/h, occurred in water-saturated wet meadow areas. In drier upland tundra sites, highest fluxes occurred in areas inhabited by mixed vegetation and labrador tea at 3.0 nmol/sq m/h and lowest fluxes were from lichen-dominated areas at 0.9 nmol/sq m/h. DMS was the dominant gas emitted from all these sites. Emissions of DMS were highest from intertidal soils inhabited by Carex subspathacea.

Rates of emissions of the biogenic sulfur (S) gases carbonyl sulfide (COS), methyl mercaptan (MSH), dimethyl sulfide (DMS), and carbon disulfide (CS2) were measured in a variety of marine and freshwater wetland habitats in the Florida Everglades during a short duration period in October using dynamic chambers, cryotrapping techniques, and gas chromatography. The most rapid emissions of greater than 500 nmol/m(sup -2)h(sup -1) occurred in red mangrove-dominated sites that were adjacent to open seawater and contained numerous crab burrows. Poorly drained red mangrove sites exhibited lower fluxes of approximately 60 nmol/m(sup -2)h(sup -1) which were similar to fluxes from the black mangrove areas which dominated the marine-influenced wetland sites in the Everglades. DMS was the dominant organo-S gas emitted especially in the freshwater areas. Spectral data from a scene from the Landsat thematic mapper were used to map habitats in the Everglades. Six vegetation categories were delineated using geographical information system software and S gas emission were extrapolated for the entire Everglades National Park. The black mangrove-dominated areas accounted for the largest portion of S gas emissions to the area. The large area extent of the saw grass communities (42 percent) accounted for approximately 24 percent of the total S emissions.

Sulfur gases are important components of the global cycle of S. They contribute to the acidity of precipitation and they influence global radiation balance and climate. The role of terrestrial sources of biogenic S and their effect on atmospheric chemistry remain as major unanswered questions in our understanding of the natural S cycle. The role of northern wetlands as sources and sinks of gaseous S by measuring rates of S gas exchange as a function of season, hydrologic conditions, and gradients in tropic status was investigated. Experiments were conducted in wetlands in New Hampshire, particularly a poor fen, and in Mire 239, a poor fen at the Experimental Lakes Area (ELA) in Ontario. Emissions were determined using Teflon enclosures, gas cryotrapping methods and gas chromatography (GC) with flame photometric detection. Dynamic (sweep flow) and static enclosures were employed which yielded similar results. Dissolved S gases and methane were determined by gas stripping followed by GC.

A summary of the results of a multi-year project which studied the release of biogenic sulfur gases from wetland habitats is reported. This project also included an initial study of factors that control terminal decomposition in temperate salt marsh sediments. This preliminary research was used as a biogeochemical foundation for the interpretation of data collected during other aspects of the work. As time progressed the research moved greatly into freshwaters since it became clear that these habitats had a greater influence on regional and global processes and these habitats were grossly understudied with respect to their role as producers and consumers of atmospheric S compounds. More detailed information is provided as appendices.

Peatlands, as fens and bods, make up a large percentage of northern latitude terrestrial environments. They are organic rich and support an active community of anaerobic bacteria, such as methanogenic and sulfate-reducing bacteria. The end products of these microbial activities, methane and hydrogen sulfide, are important components in the global biogeochemical cycles of carbon and sulfur. Since these two bacterial groups compete for nutritional substrates, increases in sulfate deposition due to acid rain potentially can disrupt the balance between these processes leading to a decrease in methane production and emission. This is significant because methane is a potent greenhouse gas that effects the global heat balance. A section of Mire 239 in the Experimental Lakes Area, in Northwestern Ontario, was artificially acidified and rates of sulfate reduction and methane production were measured with depth. Preliminary results suggested that methane production was not affected immediately after acidification. However, concentrations of dissolved methane decreased and dissolved sulfide increased greatly after acidification and both took several days to recover. The exact mechanism for the decrease in methane was not determined. Analyses are under way which will be used to determine rates of sulfate reduction. These results will be available by Spring and will be discussed.

The mechanisms by which certain animals and plants affect redox processes in sediments was examined by studying three environments: (1) subtidal sediments dominated by the deposit-feeding polychaete Heteromastus filiformis; (2) a saltmarsh inhabited by the tall form of Spartina alterniflora; and (3) tropical carbonate sediments inhabited by three species of seagrasses. S-35-sulfide production rates were compared to pool sizes of dissolved sulfide and dissolved iron. In all of the sediments studied, rates of sulfide reduction were enhanced by macroorganisms while the rate of turnover of dissolved sulfide increased. The polychaete enhanced microbial activity and redox cycling primarily by subducting particles of organic matter and oxidized iron during sediment reworking. The Spartina species enhanced anaerobic activity by transporting primarily dissolved organic matter and oxidants. Although the final result of both animal and plant activities was the enhancement of sub-surface cycling of sulfur and iron, decreased dissolved sulfide and increased dissolved iron concentrations, the mechanisms which produced these results differed dramatically.

Summer sulfate reduction and sulfide and iron chemistry were monitored in marsh soils along a gradient from a creekside Spartina alterniflora region to an inland area dominated by S. patens. Sulfate reduction rates measured using S-35 increased from 0.4 in June to as much as 4.5 micro-mole/ml(sup -1)d(sup -1) in July in S. alterniflora soils with most rapid rates occurring in the upper few cm. Rates in S. patens soils were approximately equal to 5-8 fold slower with the most rapid rates occurring generally in soils deeper than 10 cm. The recovery percentage of reduced S-35 sulfur varied with depths at both locations; dissolved and acid-volatile sulfides dominating S. alterniflora regions while chromium-reducible solid phases were abundant in S. patens soils. Dissolved sulfide in S. alterniflora soils increased throughout the summer to approximately equal to 2.8 mM while sulfide in S. patens soils was abundant only in soils deeper than 15 cm. Dissolved sulfide covaried inversely with iron. Diel studies demonstrated that sulfide and iron varied approximately equal to two-fold in response to a semi-diurnal tide. Dissolved sulfide turnover was most rapid during periods of active plant growth.

Short and long-term impacts of increased S deposition on fluxes of volatile S compounds (VSC's) from Sphagnum peatlands were investigated in an artificially acidified (sulfuric and nitric acids) poor fen (Mire 239) at the Experimental Lakes Area (ELA), Ontario, Canada. Additional experiments were conducted in a poor fen (Sallie's Fen) in Barrington, NH, USA. At Mire 239, emissions of VSC's were monitored, before and after acidification, at control (unacidified) and experimental sections within two major physiographic zones of the mire (oligotrophic and minerotrophic). The experimental segments of the mire received S amendments since 1983, in amounts equivalent to the annual S deposition in the highest polluted areas of Canada and U.S. Dimethyl sulfide (DMS) was the predominant VSC released from the mire and varied largely with time and space (i.e., from 2.5 to 127 nmol/m(sup -2)h(sup -1)). Sulfur addition did not affect DMS emissions in a period of hours to a few days, although it stimulated production of DMS and MSH in the anoxic surficial regions of the peat. DMS emissions in the experimental oligotrophic segment of the mire was approximately 3-fold greater than in the control oligotrophic segment, and approximately 10-fold greater than in the minerotrophic zones. These differences could be due to a combination of differences in types of vegetation, nutritional status, and S input. At Sallie's Fen, DMS fluxes were approximately 8 times higher from a Sphagnum site than from a bare peat site. Fluxes of VSC's were not significantly affected by sulfate amendments at both sites, while DMS and MSH concentrations increases greatly with time in the top 10 cm of the peat column. Our data indicated that although Sphagnum is not the direct source of DMS released from Sphagnum peatlands, it might play a role in regulating DMS emissions to the atmosphere.

A static enclosure method was applied to determine the exchange of dimethyl sulfide (DMS) and OCS between the surface of Sphagnum peatlands and the atmosphere. Measurements were performed concurrently with dynamic enclosure measurements with S-free air used as sweep gas. DMS emission rates determined by both methods were comparable between 5 and 500 nmol/m(sup -2)h(sup -1). The dynamic method provided positive OCS flux rates (emission) for measurements performed at sites containing Sphagnum. Conversely, data from the static method indicated that OCS was consumed from the atmosphere. Measurements using both techniques at a site devoid of vegetation showed that peat is a source of both DMS and OCS. Results suggested that OCS is produced in surface peat but it is taken up from the atmosphere by Sphagnum mosses. However, the net effect of both processes is that OCS uptake exceeds emission. The dynamic enclosure technique is adequate to measure rates of emissions of S gases which are produced in peatlands but not consumed, as long as attention is paid to the rate of sweep flow.

This project was directed toward the quantification of fluxes of gaseous biogenic sulfur compounds from freshwater wetlands. These compounds (primarily hydrogen sulfide (H2S), dimethyl sulfide (DMS), and carbonyl sulfide (OCS)) have been implicated in the regulation of planetary albedo by the formation of microscopic atmospheric aerosols when they oxidize, and the further role of these aerosols as cloud condensation nuclei (CCN). The role of continental sources and sinks for these compounds is poorly understood. The present study was undertaken to quantify the source and sink strength of high latitude wetlands, and to delineate factors that regulate this flux.

Atmosphere-peatland exchange of reduced sulfur gases was determined seasonally in fen in NH, and in an artificially-acidified fen at the Experimental Lakes Area (ELA) in Canada. Dimethyl sulfide (DMS) dominated gas fluxes at rates as high as 400 nmol/m(sup -2)hr(sup -1). DMS fluxes measured using enclosures were much higher than those calculated using a stagnant-film model, suggesting that Sphagnum regulated efflux. Temperature controlled diel and seasonal variability in DMS emissions. Use of differing enclosure techniques indicated that vegetated peatlands consume atmospheric carbonyl sulfide. Sulfate amendments caused DMS and methane thiol concentrations in near-surface pore waters to increase rapidly, but fluxes of these gases to the atmosphere were not affected. However, emission data from sites experiencing large differences in rates of sulfate deposition from the atmosphere suggested that chronic elevated sulfate inputs enhance DMS emissions from northern wetlands.

Acetate is important in anaerobic metabolism of non-vegetated sediments but its role in salt marsh soils was not investigated thoroughly. Acetate concentrations, oxidation (C-14) and SO4(2-) reduction (S-35) were measured in S. alterniflora soils in NH and MA. Pore water from cores contained greater than 0.1 mM acetate and in some instances greater than 1.0 mM. Non-destructive samples contained less than 0.01 mM. Acetate was associated with roots and concentrations were highest during vegetative growth and varied with changes in plant physiology. Acetate turnover was very low whether whole core or slurry incubations were used. Radiotracers injected directly into soils yielded rates of SO4(2-) reduction and acetate oxidation not significantly different from core incubation techniques. Regardless of incubation method, acetate oxidation did not account for a significant percentage of SO4(2-) reduction. These results differ markedly from data for non-vegetated coastal sediments where acetate levels are low, oxidation rate constants are high and acetate oxidation rates greatly exceed rates of SO4(2-) reduction. The discrepancy between rates of acetate oxidation and SO4(2-) reduction in marsh soils may be due either to the utilization of substrates other than acetate by SO4(2-) reducers or artifacts associated with measurements of organic utilization by rhizosphere bacteria.

The role of terrestrial sources of biogenic S and their effect on atmospheric chemistry remain as major unanswered questions in our understanding of the natural S cycle. The role of northern wetlands as sources and sinks of gaseous S was investigated by measuring rates of S gas exchange as a function of season, hydrologic conditions, and gradients in trophic status. Experiments were conducted in wetlands in New Hampshire (NH), and in Mire 239, a poor fen at the Experimental Lakes Area (ELA) in Ontario. Emissions were determined using Teflon enclosures, gas cryotrapping methods, and GC with flame photometric detection. Emissions of DMS dominated fluxes. In NH, DMS fluxes were greater than 1.6 micromol/m(sup -2)d(sup -1) in early summer, 1989 when temperatures were warm and the water table was approximately 5 cm below the surface. These rates are several-fold faster than average oceanic rates of DMS emission. A rapid drop in the water table resulted in a 6-fold decrease in DMS emissions in late July. In 1990, a new beaver dam kept water levels above the surface and S emissions were much lower than during 1989. The elimination of the beaver and a drop in the water table in August produced a rapid increase in S gas emissions. Emissions of DMS were highest in the most oligotrophic areas. Mire 239 (ELA) was irrigated with sulfuric and nitric acids to simulate acid rain. S emissions were determined before and after an acidification event in control and experimental areas in both minerotrophic and oligotrophic regions. Emissions of DMS were higher in the acidified areas compared to unacidified controls. Emissions were also much higher in the oligotrophic regions compared to the minerotrophic ones. Despite the wide differences in S gas fluxes (20-fold), it was difficult to determine whether acidification or variations in trophic status was not responsible for differences in S gas emissions. DMS emitted into the atmosphere was not derived from the water table but originated in peat in the unsaturated zone.

Sulfate reduction rates, dissolved iron and sulfide concentrations, and titration alkalinity were measured in salt marsh soils along a transect that included areas inhabited by both the tall and short forms of Spartina alterniflora and by Spartina patens. Pore waters were collected with in situ 'sippers' to acquire temporal data from the same location without disturbing plant roots. During 1984, data collected at weekly intervals showed rapid temporal changes in belowground biogeochemical processes that coincided with changes in S. alterniflora physiology. Rates of SO4(-2) reduction increased fivefold (to greater than 2.5 micromol ml(sup -1)d(sup -1)) when plants began elongating aboveground yet decreased fourfold upon plant flowering. This rapid increase in rates of SO4(-2) reduction must have been fueled by dissolved organic matter released from roots only during active growth. Once plants flowered, the supply of oxidants to the soil decreased and sulfide and alkalinity concentrations increased despite decreases in SO4(-2) reduction and increases in SO4(-2):Cl(-) ratios. Sulfide concentrations were highest in soils inhabited by tallest plants. During 1985, S. alterniflora became infested with fly larvae (Chaetopsis apicalis John) and aboveground growth ceased in late June. This cessation was accompanied by decreased rates of SO4(-2) reduction similar to those noted during the previous year when flowering occurred. After the fly infestation, the pore-water chemical profiles of these soils resembled profiles of soils inhabited by the short form of S. alterniflora. The SO4(-2) reduction rates in S. patens soils are the first reported. Rates were similar to those in S. alterniflora except that they did not increase greatly when S. patens was elongating. Tidal and rainfall events produced desiccation-saturation cycles that altered redox conditions in the S. patens soils, resulting in rapid changes in the dissolution and precipitation of iron and in the magnitude and spatial distribution of SO4(-2) reduction.

Data on the emissions of sulfur gases from marine and freshwater wetlands are summarized with respect to wetland vegetation type and possible formation mechanisms. The current data base is largest for salt marshes inhabited by Spartina alterniflora. Both dimethyl sulfide (DMS) and hydrogen sulfide (H2S) dominate emissions from salt marshes, with lesser quantities of methyl mercaptan (MeSH), carbonyl sulfide (COS), carbon disulfide (CS2) and dimethyl disulfide (DMDS) being emitted. High emission rates of DMS are associated with vegetation that produces the DMS precursor dimethylsulfonionpropionate (DMSP). Although large quantities of H2S are produced in marshes, only a small percentage escapes to the atmosphere. High latitude marshes emit less sulfur gases than temperate ones, but DMS still dominates. Mangrove-inhabited wetlands also emit less sulfur than temperate S. alterniflora marshes. Few data are available on sulfur gas emissions from freshwater wetlands. In most instances, sulfur emissions from temperate freshwater sites are low. However, some temperate and subtropical freshwater sites are similar in magnitude to those from marine wetlands which do not contain vegetation that produces DMSP. Emissions are low in Alaskan tundra but may be considerably higher in some bogs and fens.

Sulfur gases are important components of the global cycle of S. They contribute to the acidity of precipitation and they influence global radiation balance and climate. The role of terrestrial sources of biogenic S and their effect on atmospheric chemistry remain as major unanswered questions in our understanding of the natural S cycle. The role of northern wetlands as sources and sinks of gaseous S was investigated by measuring rates of S gas exchange as a function of season, hydrologic conditions, and gradients in trophic status. The effects of inorganic S input on the production and emission of gaseous S were also investigated. Experiments were conducted in wetlands in New Hampshire, particularly a poor fen, fens within the Experimental Lakes Area (ELA) in Ontario, Canada and in freshwater and marine tundra. Emissions were determined using Teflon enclosures, gas cryotrapping methods, and gas chromatography (GC) with flame photometric detection. Dynamic (sweep flow) and static enclosures were employed. Dissolved gases were determined by gas stripping followed by GC.

Coastal wetland areas occupy a small percentage of the terrestrial environment yet are extremely productive regions which support rapid rates of belowground bacterial activity. Wetlands appear to be significant as biogenic sources of gaseous sulfur, carbon, and nitrogen. These gases are important as tracers of man's activities, and they influence atmospheric chemistry. The interactions among wetland biogeochemical processes regulate the anaerobic production of reduced gases and influence the fate of these volatiles. Therefore, spatial and temporal variations in hydrology, salinity, temperature and specification, and growth of vegetation affect the type and magnitude of gas emissions thus hindering predictive estimates of gas flux. Our research is divided into two major components, the first is the biogeochemical characterization of a selected tidal wetland area in terms of factors likely to regulate sulfide flux; the second is a direct measurement of gaseous sulfur flux as related to changes in these biogeochemical conditions. Presently, we are near completion of phase one.

The major environmental factors controlling fluxes of dimethyl sulfide (DMS) in a Sphagnum-dominated peatland were investigated in a poor fen in New Hampshire. DMS emissions from the surface of the peatland varied greatly over 24 hours and seasonally. Maximum DMS emissions occurred in summer with minima in the late fall. Temperature was the major environmental factor controlling these variabilities. There was also some evidence that the changes in water table height might have contributed to the seasonable variability in DMS emission. The influence of the water table was greater during periods of elevated temperature. DMS and MSH were the most abundant dissolved volatile sulfur compound (VSC) in the surface of the water table. Concentrations of dissolved VSC's varied with time and space throughout the fen. Dissolved MDS, MSH, and OCS in the surface of the water table were supersaturated with respect to their concentrations in the atmosphere suggesting that the peat surface was a source of VSC's in the peatland. VCS in peatlands seemed to be produced primarily by microbial processes in the anoxic surface layers of the peat rich in organic matter and inorganic sulfide. Sphagnum mosses were not a direct source of VSC's. However, they increased transport of DMS from the peat surface to the atmosphere.