Sulfur Gas Emissions Research Articles

A simple magma-mixing model for sulphur behaviour in calc-alkaline volcanic rocks: mineralogical evidence from Mount Pinatubo 1991 eruption

The increasing recognition of anhydrite as a primary magmatic mineral in volcanic products, including the important 1991 Pinatubo eruption, places new emphasis on the cycling of sulphur from deep sources including the upper mantle. We present a simple model for the supersaturation of sulphur during mingling and mixing in calc-alkaline magmas due to the quenching and oxidation of the mafic end member, which may have important consequences for predicting the annual flux of igneous sulphur. This model predicts the coexistence of anhydrite and sulphur dioxide gas, and explains the discrepancy between erupted magma volumes and sulphur gas emissions. Although sulphur may exist as a number of species in volcanic emissions, one of its most important phases in volcanic rocks is primary anhydrite (CaS0 4 ). A number of important historic eruptions of calc-alkaline volcanoes have now been found to involve anhydrite-bearing magmas. These include Mount Lamington in Papua New Guinea (Arculus et al. 1983), Nevado del Ruiz in Colombia (Fournelle 1990), and El Chichon in Mexico ( Rose et al. 1984 ). The Ruiz eruption involved documented magma mixing, and both the Nevado del Ruiz and El Chichon eruptions were associated with very high sulphur emissions (both approximately 3.3 x 10 6 tonnes; Krueger 1983 ; Williams et al. 1990 ). We have observed magma-mixing textures in detailed studies of two neighbouring calc-alkaline volcanoes in northern Chile, at Lascar ( Matthews 1992 ) and Tumisa ( Gardeweg 1988 ). Anhydrite has been found associated with these textures in pumice from Lascar Volcano. Both anhydrite and similar disequilibrium textures indicative of magma

Emissions of biogenic sulfur gases from Alaskan tundra

Fluxes of the biogenic sulfur gases carbonyl sulfide (COS), dimethyl sulfide (DMS), methyl mercaptan (MeSH), and carbon disulfide (CS2) were determined for several freshwater and coastal marine tundra habitats using a dynamic enclosure method and gas chromatography. In the freshwater tundra sites, highest emissions, with a mean of 6.0 nmol m−2 h−1 (1.5–10) occurred in the water‐saturated wet meadow areas inhabited by grasses, sedges and Sphagnum mosses. In the drier upland tundra sites, highest fluxes occurred in areas inhabited by mixed vegetation and labrador tea at 3.0 nmol m−2 h−1 (0–8.3) and lowest fluxes were from lichen‐dominated areas at 0.9 nmol m−2 h−1. Sulfur emissions from a lake surface were also low at 0.8 nmol m−2 h−1. Of the compounds measured, DMS was the dominant gas emitted from all of these sites. Sulfur emissions from the marine sites were up to 20‐fold greater than fluxes in the freshwater habitats and were also dominated by DMS. Emissions of DMS were highest from intertidal soils inhabited by Carex subspathacea (150–250 nmol m−2 h−1). This Carex sp. was grazed thoroughly by geese and DMS fluxes doubled when goose feces were left within the flux chamber. Emissions were much lower from other types of vegetation which were more spatially dominant. Sulfur emissions from tundra were among the lowest reported in the literature. When emission data were extrapolated to include all tundra globally, the global flux of biogenic sulfur from this biome is 2–3 × 108 g yr−1. This represents less than 0.001% of the estimated annual global flux (∼50 Tg) of biogenic sulfur and <0.01% of the estimated terrestrial flux. The low emissions are attributed to the low availability of sulfate, certain hydrological characteristics of tundra, and the tendency for tundra to accumulate organic matter.

Global inventory of sulfur emissions with 1°×1° resolution

A global inventory of gaseous sulfur emissions with 1°×1° resolution is described. Emissions from fuel combustion and industrial activities are estimated for countries where no detailed inventories are available by using economic data for individual sulfur‐emitting activities, sulfur emission factors, and information on sulfur recovery. Fuel sulfur contents are specified as a function of fuel type and country of origin and are conserved during international trading. This procedure for estimating emissions reproduces well existing inventories for countries in Europe and North America, suggesting that it can be applied with some confidence to other countries. Emissions from biomass burning, volcanoes, and oceans are derived from existing data bases and are distributed with fine spatial resolution. Emissions from terrestrial vegetation are computed as a function of leaf area index, temperature, and solar radiation. The global emission of sulfur gases in 1980 is estimated to be 102 Tg S yr−1, apportioned among fuel combustion and industrial activities (76%), marine biosphere (12%), volcanoes (9%), biomass burning (2%), and terrestrial biosphere (1%). Detailed breakdowns of anthropogenic and natural sources are given for individual countries and regions. Anthropogenic sources account for 84% of total sulfur emissions in the northern hemisphere and for 50% in the southern hemisphere. Biomass burning dominates emissions in central Africa during the dry season but is of minor importance elsewhere. Smelters dominate anthropogenic emissions in the Arctic and in the southern hemisphere. Volcanoes are significant contributors to the sulfur budget in Central America, the East Indies, and some subarctic regions.

Sulfur emissions to the atmosphere from natural sourees

Emissions of sulfur gases from both natural and anthropogenic sources strongly influence the chemistry of the atmosphere. To assess the relative importance of these sources we have combined the measurements of sulfur gases and fluxes during the past decade to create a global emission inventory. The inventory, which is divided into 12 latitude belts, takes into account the seasonal dependence of sulfur emissions from biogenic sources. The total emissions of sulfur gases from natural sources are approximately 0.79 Tmol S/a. These emissions are 16% of the total sulfur emissions in the Northern Hemisphere and 58% in the Southern Hemisphere. The inventory clearly shows the impact of anthropogenic sulfur emissions in the region between 35° and 50°N.

Global Emissions of Nitrogen and Sulfur Oxides in Fossil Fuel Combustion 1970–1986

Statistical models previously introduced by the authors for estimating emission rates from rates of fuel combustion have been utilized to obtain emissions of nitrogen and sulfur gases in fossil fuel combustion for every country in the world for every year from 1970 to 1986. Changes in the global emission rates of these gases are presented together with the trends over individual continents. Global emissions of NOx increased by nearly a third in this period, i.e., from 18 Mt N/year in 1970 to 24 Mt N/year in 1986. Emissions of SOx increased by approximately 18 percent, from 57 Mt S/year in 1970 to 67 Mt S/year in 1986. The geographical distribution of NOx and SOx emissions for 1986 are presented on a latitude-longitude grid suitable for use in three-dimensional simulations of atmospheric chemistry in general circulation models.

Emission of Biogenic Sulfur Gases from Agricultural Land

Emission of Biogenic Sulfur Gases from Agricultural Land

The disposal of flue gas desulphurisation waste: sulphur gas emissions and their control

Flue gas desulphurisation (FGD) equipment to be fitted to UK coal-fired power stations will produce more than 0.8 Mtonnes of calcium sulphate, as gypsum. Most gypsum should be of commercial quality, but any low grade material disposed as waste has the potential to generate a range of sulphur gases, including H2S, COS, CS2, DMS and DMDS. Literature data from the USA indicates that well-oxidised waste with a high proportion of calcium sulphate (the main UK product of FGD) has relatively low emissions of sulphur gases, which are comparable to background levels from inland soils. However, sulphur gas fluxes are greatly enhanced where reducing conditions become established within the waste, hence disposal strategies should be formulated to prevent the sub-surface consumption of oxygen.

Identification and quantification of sulfur gases emitted from soils, leaf litter and live plant parts

Sulfur gas emission potentials can be quantified by incubating soil, leaf litter or plant parts in polypropylene centrifuge bottles, followed by analysis of accumulated head space gases with a gas chromatograph having a sulfur-specific flame photometric detector. Biological sulfur gas emissions can make a small contribution to atmospheric sulfur and to sulfuric acid rain. Sulfur gas emissions by plants are potentially significant as defenses against root rot fungi, nematodes and insects. Sulfur gas emissions which inhibit nutrification may function to conserve NH 4 in the upper soil profile.

The atmospheric sulfur cycle over the Amazon Basin: 2. Wet season

We determined the fluxes and concentrations of atmospheric sulfur species at ground level and from aircraft over the Amazon Basin during the 1987 wet season, providing a comprehensive description of the sulfur cycle over a remote tropical region. The vertical profile of dimethylsulfide (DMS) during the wet season was found to be very similar to that measured during the dry season, suggesting little seasonal variation in DMS fluxes. The concentrations of hydrogen sulfide (H2S) were almost an order of magnitude higher than those of DMS, which makes H2S the most important biogenic source species in the atmospheric sulfur cycle over the Amazon Basin. Using the gradient‐flux approach, we estimated the flux of DMS at the top of the tree canopy. The canopy was a source of DMS during the day, and a weak sink during the night. Measurements of sulfur gas emissions from soils, using the chamber method, showed very small fluxes, consistent with the hypothesis that the forest canopy is the major source of sulfur gases. The observed soil and canopy emission fluxes are similar to those measured in temperate regions. The concentrations of SO2 and sulfate aerosol in the wet season atmosphere were similar to dry season values. The sulfate concentration in rainwater, on the other hand, was lower by about a factor of 5 during the wet season. Due to the higher precipitation rate, however, the wet deposition flux of sulfate was not significantly different between the seasons. The measured fluxes and concentrations of DMS, H2S, and SO2 were consistent with a model describing transport and chemistry of these sulfur species in the boundary layer. The concentrations of aerosol and the sulfate deposition rate, on the other hand, could only be explained by import of significant amounts of marine and anthropogenic sulfate aerosol into the Amazon Basin.

Sulphur gas emissions in the boreal forest: The West Whitecourt case study VIII: Pine tree mineral nutrition

Nutrient analyses of foliage from a naturally occurring hybrid of Pinus contorta Loud. and P. banksiana Lamb. (lodgepole pine × jack pine), were used to determine if chronic exposure to S gas emissions had affected the nutrient status of the trees. This study was part of a larger case study investigating the effects of 17 yr of exposure to S gas emissions from a S-recovery gas plant on a forest ecosystem in west central Alberta, Canada. Significant inverse, linear relationships were found between foliar sulphate-S levels and distance from the S source in all three age classes of pine foliage tested. Sulphate-S levels increased with increasing age of foliage at sites near the source while they decreased with increasing age of foliage at sites not frequently exposed to the S gas emissions. Soil pH was reduced in the top 5 cm of soil at sites near the source and elevated contents of total S in the soil were also found at those sites. Manganese concentrations in foliage from the sites near the source were significantly higher than in foliage from sites away from the source. The level of Mn also increased with increasing age of tissues. The elevated level of sulphate-S in foliage and lower soil pH at sites near the source indicated significant amounts of S from the source had been deposited at those sites. The lower soil pH most likely contributed to the increased availability of Mn that was found in the foliage.

The variability of biogenic sulfur flux from a temperate salt marsh on short time and space scales

Three emission chambers were deployed simultaneously to measure rates of emission of dimethyl sulfide, methane thiol and carbonyl sulfide within or across vegetation zones in a New Hampshire salt marsh. Short term (a few hours) variation in fluxes of all S gases from replicate sites were small within a monospecific stand of either Spartina alterniflora or S. patens. The quantity of emergent biomass and the type of vegetation present were the primary factors regulating the rate of emission. Dimethyl sulfide fluxes from the S. alterniflora soils ranged from 800 to 18,000 nmol m −2 h −1 compared to emissions of 25–120 nmol m −2 h −1 from S. patens. This difference was probably due to the presence of the dimethyl-sulfide precursor dimethylsulfoniopropionate which is an osmoregulator in S. alterniflora but not in S. patens. Methane thiol emissions from S. alterniflora were 20–280 nmol m −2 h −1 and they displayed a similar diel trend as dimethyl sulfide, although at much lower rates, suggesting that methane thiol is produced primarily by leaves. Methane thiol emissions from S. patens were 20–70 nmol m −2 h −1. Net uptake of carbonyl sulfide of 25–40 nmol m −2 h −1 occurred in stands of S. alterniflora while net efflux of 10–36 nmol m −2 h −1 of carbonyl sulfide occurred in stands of S. patens. In general, ranges of emissions of sulfur gases were similar to most other published values.

Foliar sulphur species in pine: A new indicator of a forest ecosystem under air pollution stress

An eleven-year foliar sulphur (S) monitoring program was carried out from 1976 to 1986 near a sulphur recovery-gas plant in west-central Alberta, Canada, as part of a case study designed to determine the effects of chronic, low concentration sulphur gas emissions on the forest ecosystem surrounding the gas plant. Measurements of both foliar total sulphur (S T) and foliar inorganic sulphur (SO 4-S) concentration in lodgepole × jack pine trees at the end of each of the 11 growing seasons were taken to provide an indication of S loading of the forest from industrial sulphur emissions. To measure the state of the forest ecosystem, foliar S T was separated into foliar accumulated sulphur (inorganic sulphur or SO 4-S) and foliar assimilated sulphur (organic sulphur or S 0) and the ratio of SO 4-S/S 0 taken. Foliar S 0 was calculated as the difference between foliar S T and foliar SO 4-S. The median SO 4-S/S 0 ratio, with all three years of needles considered, varied from 0·29 at a reference location ( A V) to 0·88 at the location with the highest stress ( A I). The corresponding mean values ranged from 0·3 at the reference location to 2·2 at the location of highest stress. The mean seasonal photosynthetic rate of current year's foliage of the pine trees and soil pH were reduced at a stressed location ( A I) compared to the reference location ( A V), between 1976 and 1981. Over this same time period the mean foliar SO 4-S/S 0 ratio increased from 0· ± 0·1 to 1·0 ± 0·3 at the stressed location ( A I) and remained nearly the same at the reference location ( A V) at 0·3 ± 0·1. This research suggests that the foliar SO 4-S/S 0 ratio is a useful indicator of the state of forest ecosystems under S air pollution stress. It is concluded that foliar S separated into various fractions has potential as an early warning environmental management tool.

Measurement of biogenic sulfur emissions from soils and vegetation using dynamic enclosure methods: Total sulfur gas emissions via MFC/FD/FPD determinations

Metal foil collection/flash desorption/flame photometric detection (MFC/FD/FPD) was one of the analytical methods used to measure emissions of gaseous, sulfur-containing compounds from several terrestrial natural sources during a cooperative field program in the summer of 1985. Nonspeciated, total sulfur gas emissions were determined by using the MFC/FD/FPD technique in combination with a Nafion Perma-Pure drying device to sample air from three designs of dynamic enclosure chambers. These enclosures were placed over various soil orders and vegetation in the vicinity of field sites in Iowa and Ohio previously examined during the 1977–80 SURE study of biogenic sulfur fluxes. Because of the sensitivity and detection characteristics of the MFC/FD/FPD technique, it was possible to obtain measurements on enclosure air samples that were collected for relatively short time periods,. e.g., 1 to 5 min. The magnitudes of these time-resolved, total sulfur gas emissions are correlated exponentially with internal enclosure air temperatures. Potential errors and uncertainties associated with this application of the MFC/FD/FPD methodology are assessed.

Widespread occurrence of bacterial thiol methyltransferases and the biogenic emission of methylated sulfur gases.

A majority of heterotrophic bacteria isolated from soil, water, sediment, vegetation, and marine algae cultures methylated sulfide, producing methanethiol. This was demonstrated with intact cells by measuring the emission of methanethiol with a sulfur-selective chemiluminescence detector, and in cell extracts by detection of sulfide-dependent thiol methyltransferase activity. Extracts of two Pseudomonas isolates were fractionated by gel-filtration and ion-exchange chromatography, and with sulfide as the substrate a single peak of thiol methyltransferase activity was seen in each case. Extracts of several bacterial strains also contained thiol methyltransferase activity with organic thiols as substrates. Thus, S-adenosylmethionine-dependent thiol methyltransferase activities are widespread in bacteria and may contribute to biogenic emissions of methylated sulfur gases and to the production of methyl thioethers.

Sulphur gas emissions in the boreal forest: The West Whitecourt case study

Sulphur gas emissions in the boreal forest: The West Whitecourt case study

Sulphur gas emissions in the boreal forest: The West Whitecourt case study

The water relations physiology of Pinus contorta × Pinus banksiana and several other important boreal species was studied intensively during 1975–1976 in the vicinity of the West Whitecourt Sulphur Recovery Gas Plant near Whitecourt, Alberta, Canada as part of the West Whitecourt Case Study. Xylem pressure potentials of pine varied from −0.3 MPa to −1.6 MPa and were not noticeably different from pine in areas not receiving S gas emissions such as the Richardson Fire Tower near Fort McMurray, Alberta. Leaf diffusive resistance varied from 2 scm−1 to 60+ s cm−1. The xylem pressure potentials of Picea mariana, Arctostaphylos uva-ursi, and Ledum groenlandicum, were not measurably different from values reported in the literature. Based upon xylem pressure potentials, and leaf diffusive resistances, the water relations of all the species studied in the vicinity of the West Whitecourt Gas Plant did not seem to be measurably affected by S gas emissions. It is concluded that the effects of S gas emission upon photosynthesis are not due to moisture stress.

Sulphur gas emissions in the boreal forest: The west whitecourt case study IV: Air quality and the meteorological environment

A program of atmospheric measurements was carried out in support of the West Whitecourt case study in the summers of 1975 and 1976. Measurements in and around an isolated stand of mature lodgepole × Jack pine trees included temperature, moisture, and wind measurements at a climatological station outside the stand and at several levels on a 30 m radio mast tower within the stand. Sulphur dioxide concentrations were also measured on the tower. A number of short-term, intensive measurements were made to document the meteorological and SO2 environments in more detail, with special attention given to the transport of S gas from the source to the sink. The major source of SO2 at the intensive experimental site was very likely the flare stacks at the gas processing plant. Sulphur dioxide events at the study site were typically daytime, low concentration bursts of a few minutes in duration which occurred with westerly winds under fair weather conditions. Air impinging on the stand tended to flow around the edges of the stand, over the canopy, and into the trunk space. This aerodynamic effect, together with the uptake of SO2 by the vegetation, caused a minimum in SO2 concentration in the crown of the forest.

Annual cycle of gaseous sulfur emissions from a New England Spartina alterniflora marsh

A flow-through chamber was used to measure the net gaseous sulfur fluxes (emission minus uptake) to the atmosphere from an area of Spartina alterniflora in a New England salt marsh. The fluxes of hydrogen sulfide, dimethyl sulfide, carbonyl sulfide, carbon disulfide and dimethyl disulfide were measured monthly over a year to obtain the annual emission estimates. Peak releases of the various sulfur gases did not occur simultaneously but were measured from July through to October depending on the individual sulfur species. The total annual emission was estimated to be 5.8 g S m −2 y −1, with dimethyl sulfide (49% of the total) and hydrogen sulfide (35% of the total) the major components emitted. The emissions of the other sulfur gases were nearly 10-fold lower.

Emissions of biogenic sulfur gases from a danish estuary

The diurnal variations in sulfur emission were studied at seven sites in a Danish estuary, Norsminde Fjord. The sites comprised grass vegetation, intertidal mud flats, accretions of green algae, an exposed shore and a river outlet. Direct measurements of emission rates from soil and water were done by a dynamic flux chamber technique in connection with gas Chromatographie detection and separation of the cryogenically trapped sulfur gases. Sulfur gas concentrations in air and sea water were measured together with emission rates at 0.5–1 h intervals over 25–40 h periods. DMS was the most important sulfur gas released from grass and algae, while mostly H 2S was released from intertidal mud flats. OCS, CH 3SH and CS 2 were released from most sites at lower rates. Emission of DMS followed the daylight variations, often with a delay towards maximum emission rates in the evening. H 2S was mostly emitted at night or in short outbursts during low tides. Total sulfur emission rates were 1–10μmol Sm −2 d −1. Extreme rates of 335μmol DMSm −2 d −1 were measured over decomposing green algae ( Ulva lactuca). H 2S emission fractions were < 10 −6 to 2.10 −4. H 2S was detected, along with DMS, CH 3SH, OCS and CS 2, in the oxic seawater of the estuary at diurnal mean concentrations of 0.1–6.5nmol S/ol −1 . This may indicate a more widespread occurrence of H 2S in shallow, near-shore waters at nanomolar levels.

Sulphur gas emissions in the Boreal Forest: The West Whitecourt case study V. Stable sulphur isotopes

Sulphur (S) gas emissions from the West Whitecourt Gas Plant were shown to have δ34S value near +22%. while the δ34S value for pre-industrial soil and ground water was found to be near 0‰ This isotopic ‘leverage’ provided a means of assessing the fate of S-gas emissions and the movement of S-compounds among the four main compartments of the forest ecosystem: air, vegetation, soil, and water. Several high volume sampling techniques were used to relate the δ34S values of atmospheric S-compounds to wind direction at the intensive experimental site 1.5 km cast of the gas plant. These techniques included field testing of a wind directionally controlled high volume sampling array. Winds from the direction of the gas plant carried particulates and SO2 which were considerably more enriched in δ34S than for other wind directions. The stable S isotopic compositions of lodgepole × jack pine needles at sampling locations around the S-gas emission source were consistent with the wind rose summary for the area. Height dependences were found for the δ34S values of atmospheric particulates and for pine foliage. Needles in the upper canopy frequently had δ34S values 5 to 10‰ higher than S-gas emission from the gas plant, thereby suggesting an isotopically selective metabolic process. δ34S values of total S-compounds in surface waters increased with increasing organic S content, approaching a limit near +22‰, suggesting that both parameters were mutually influenced by the input of S-gas emissions to the forest ecosystem. Limited soil profile δ34S data indicated that S of industrial origin penetrated the soil to at least 1 m depth in exposed, dry areas lacking biological cover while in a light forest cover, penetration to 60 cm had not yet occurred. Stable S isotopes were found to be a practical environmental tracer of industrial S in the forest ecosystem in Alberta.