Emissions of marine biogenic sulfur to the atmosphere of northern Europe

Measurements of DMS and other reduced sulfur compounds in surface waters have been carried out from a helicopter in the seas surrounding Scandinavia. Average summer time concentrations of DMS ranged from 70 to 150 ngS L^-1. Simultaneous measurements of biological and physical parameters revealed no correlation between DMS and phytoplankton species, species assemblages, total phytoplankton biomass, chlorophyll a, temperature, and salinity. The only exception was a correlation between DMS concentration, Chrysochromulina spp. belonging to the Prymnesiophyceae, and salinity over a narrow range of salinity in the Baltic Sea.The flux of reduced sulfur to the atmosphere in July in this region is estimated to be 120–170 gS m^-2 d^-1 from the Baltic, 240–810 in the Kattegat/Skagerrak, and 120–690 in the North Sea. Annual fluxes are roughly 100 times higher than these daily fluxes. On an annual basis, biogenic sulfur emissions from the coastal seas are negligible (<1%) compared to the anthropogenic emissions in northern Europe. However, during the summer months, the biogenic sulfur emissions from the seas surrounding the Scandinavian peninsula are estimated to be as high as 20–70% of the anthropogenic emissions in Scandinavia. This makes it of interest to incorporate the biogenic emissions in calculations of long-range transport and deposition of sulfur within the region.Other volatile sulfur species, mainly methyl mercaptan, contribute about 10% of the total flux of reduced sulfur. Estimated fluxes of CS₂ to the atmosphere ranged from 1 gS m^-2 d^-1 in the Baltic Sea to 6 gS m^-2 d^-1 in the North Sea. No emissions for H₂S or COS were detected.     

The effect of nitrogen fertilization on the COS and CS2 emissions from temperature forest soils

The net fluxes of carbonyl sulfide (COS) and carbon disulfide (CS₂) to the atmosphere from nitrogen amended and unamended deciduous and coniferous forest soils were measured during the spring of 1986. We found that emissions of these gases from acidic forest soils were substantially increased after nitrogen fertilization. The total (COS+CS₂) emissions were increased by nearly a factor of three in the hardwood stand and were more than doubled in the pine stand. Furthermore, vegetation type appeared to have an influence on which was the dominant sulfur gas released from the forest soils. The added nitrogen caused a dramatic increase in COS emissions from the hardwood stand (a factor of three increase), while CS₂ emissions from this site were not affected. We observed the opposite response in the pine stand; that is, the nitrogen fertilization had no affect on COS emissions, but did stimulate CS₂ emissions (a factor of more than nine increase).     

Measurements of atmospheric dimethyl sulfide and carbon disulfide in the western Atlantic boundary layer

Shipboard measurements of atmospheric dimethyl sulfide were made during two transects along the east coast of the United States and at several stations in the Gulf of Maine. Limited measurements of carbon disulfide and hydrogen sulfide are also reported. The mean DMS mixing ratio was 29 pptv (=25, n=84, median 19 pptv) during the Atlantic transects, and 101 pptv (=67, n=77, median 79 pptv) in the Gulf of Maine. Distinct diurnal variations were found in the DMS data from the transects. The meteorology of the study area appears to control day-to-day differences in the magnitude of these diurnal variations, although rapid daytime oxidation is suggested in some cases. Diurnal variations were also evident in near-shore stations in the Gulf of Maine due to nocturnal boundary-layer inversion. Diurnal variation was not evident at other sites in the Gulf due to large scale changes in the atmospheric circulation pattern, which effectively masked any effects due to oxidation processes. Model simulations confirm that the DMS levels and diurnal variation found during the transects are not consistent with atmospheric oxidation processes alone. Atmospheric CS₂ and H₂S mixing ratios were less than 3 pptv during the transects, except for a single period of higher CS₂ mixing ratios (reaching 11 pptv) during advection of continental air. Calculations of the flux of oceanic sulfur to the eastern United States show that the contribution of natural sulfur to the North American sulfur budget is small compared to anthropogenic sources.     

Covariations in oceanic dimethyl sulfide,its oxidation products and rain acidity at Amsterdam Island in the Southern Indian Ocean

Simultaneous measurements of rain acidity and dimethyl sulfide (DMS) at the ocean surface and in the atmosphere were performed at Amsterdam Island over a 4 year period. During the last 2 years, measurements of sulfur dioxide (SO₂) in the atmosphere and of methane sulfonic acid (MSA) and non-sea-salt-sulfate (nss-SO₄ ^2-) in rainwater were also performed. Covariations are observed between the oceanic and atmospheric DMS concentrations, atmospheric SO₂ concentrations, wet deposition of MSA, nss-SO₄ ^2-, and rain acidity. A comparable summer to winter ratio of DMS and SO₂ in the atmosphere and MSA in precipitation were also observed. From the chemical composition of precipitation we estimate that DMS oxidation products contribute approximately 40% of the rain acidity. If we consider the acidity in excess, then DMS oxidation products contribute about 55%.     

DMS and SO2 Measurements in the Tropical Marine Boundary Layer

Dimethyl sulfide (DMS) and sulfur dioxide (SO₂) mixing ratios were measured in the boundary layer on Oahu, Hawaii in April and May 2000. Average DMS and SO₂ levels were 22 ± 7 (n = 488) pmol/mol and 23 ± 7 (n = 471) pmol/mol respectively. Anti-correlated DMS and SO₂ diurnal cycles, consistent with DMS + OH oxidation were observed on most days. Photochemical box model simulations suggest that the yield of SO₂ and total SO₂ sink are ∼85% and ∼2 × 10⁴ molec cm^{− 3} s^{− 1} respectively. On several days the rate of decrease in DMS and increase in SO₂ levels in the early morning were larger that predicted by the model. Dynamical and chemical causes for the anomalous early morning data are explored.     

Shipboard measurements of atmospheric dimethylsulfide and hydrogen sulfide in the Caribbean and Gulf of Mexico

Simultaneous shipboard measurements of atmospheric dimethylsulfide and hydrogen sulfide were made on three cruises in the Gulf of Mexico and the Caribbean. The cruise tracks include both oligotrophic and coastal waters and the air masses sampled include both remote marine air and air masses heavily influenced by terrestrial or coastal inputs. Using samples from two north-south Caribbean transects which are thought to represent remote subtropical Atlantic air, mean concentrations of DMS and H₂S were found to be 57 pptv (74 ng S m^-3, =29 pptv, n=48) and 8.5 pptv (11 ng S m^-3, =5.3 pptv, n=36), respectively. The ranges of measured concentrations for all samples were 0–800 pptv DMS and 0–260 pptv H₂S. Elevated concentrations were found in coastal regions and over some shallow waters. Statistical analysis reveals slight nighttime maxima in the concentrations of both DMS and H₂S in the remote marine atmosphere. The diurnal nature of the H₂S data is only apparent after correcting the measurements for interference due to carbonyl sulfide. Calculations using the measured ratio of H₂S to DMS in remote marine air suggest that the oxidation of H₂S contributes only about 11% to the excess (non-seasalt) sulfate in the marine boundary layer.     

DMS and SO2 at Baring Head, New Zealand: Implications for the Yield of SO2 from DMS

Atmospheric dimethyl sulfide (DMS) and sulfur dioxide (SO₂) concentrations were measured at Baring Head, New Zealandduring February and March 2000. Anti-correlated DMS and SO₂ diurnalcycles, consistent with the photochemical production of SO₂ from DMS, were observed in clean southerly air off the ocean. The data is used to infer a yield of SO₂ from DMS oxidation. The estimated yields are highly dependent on assumptions about the DMS oxidation rate. Fitting the measured data in a photochemical box model using model-generated OH levels and the Hynes et al. (1986) DMS + OH rate constant suggests that theSO₂ yield is 50–100%, similar to current estimates for the tropical Pacific.However, the observed amplitude of the DMS diurnal cycle suggests that the oxidation rate is higher than that used by the model, and therefore, that theSO₂ yield is lower in the range of 20–40%.     

Eddy correlation measurements of CO2, latent heat,and sensible heat fluxes over a crop surface

Eddy correlation equipment was used to measure mass and energy fluxes over a soybean crop. A rapid response CO₂ sensor, a drag anemometer, a Lyman-alpha hygrometer and a fine wire thermocouple were used to sense the fluctuating quantities.Diurnal fluxes of sensible heat, latent heat and CO₂ were calculated from these data. Energy budget closure was obtained by summing the sensible and latent heat fluxes determined by eddy correlation which balanced the sum of net radiation and soil heat flux. Peak daytime CO₂ fluxes were near 1.0 mg m^–2 (ground area) s^–1.The eddy correlation technique was also employed in this study to measure nocturnal CO₂ fluxes caused by respiration from plants, soil, and roots. These CO₂ fluxes ranged from - 0.1 to - 0.25 mg m^–2s^–1.From the data collected over mature soybeans, a relationship between CO₂ flux and photosynthetically active radiation (PAR) was developed. The crop did not appear to be light-saturated at PAR flux densities < 1800 Ei m^–2 s^–1. The light compensation point was found to be about 160 Ei m^–2 s^–1.Published as Paper No. 7402, Journal Series, Nebraska Agricultural Experiment Station. The work reported here was conducted under Nebraska Agricultural Experiment Station Project 27-003 and Regional Research Project 11–33.Post-doctoral Research Associate, Professor and Professor, respectively. Center for Agricultural Meteorology and Climatology, Institute of Agriculture and Natural Resources, University of Nebraska, Lincoln, NE 68583-0728.     

Simulations of seasonal variations of sulfur compounds in the remote marine atmosphere

A photochemical box model is used to simulate seasonal variations in concentrations of sulfur compounds at latitude 40° S. It is assumed that the hydroxyl radical (OH) addition reaction to sulfur in the dimethyl sulfide (DMS) molecule is the predominant pathway for methanesulfonic acid (MSA) production, and that the rate constant increases as the air temperature decreases. Concentration of the nitrate radical (NO₃) is a function of the DMS flux, because the reaction of DMS with NO₃ is the most important loss mechanism of NO₃. While the diurnally averaged concentration of OH in winter is a factor of about 8 smaller than in summer, due to the weak photolysis process, the diurnally averaged concentration of NO₃ in winter is a factor of about 4–5 larger than in summer, due to the decrease of DMS flux. Therefore, at middle and high latitudes in winter, atmospheric DMS is mainly oxidized by the reaction with NO₃. The calculated ratio of the MSA to SO₂ production rates is smaller in winter than in summer, and the MSA to non-sea-salt sulfate (nssSO₄ ^2-) molar ratio varies seasonally. This result agrees with data on the seasonal variation of the MSA/nssSO₄ ^2- molar ratio obtained at middle and high latitudes. The calculations indicate that during winter the reaction of DMS with NO₃ is likely to be a more important sink of NO_x (NO+NO₂) than the reaction of NO₂ with OH, and to serve as a significant pathway of the HNO₃ production. If dimethyl sulfoxide (DMSO) is produced through the OH addition reaction and is heterogeneously oxidized in aqueous solutions, half of the nssSO₄ ^2- produced in summer may be through the oxidation process of DMSO. It is necessary to further investigate the oxidation products by the reaction of DMS with OH, and the possibility of the reaction of DMS with NO₃ during winter.     

The measurement of natural sulfur emissions from soils and vegetation: Three sites in the Eastern United States revisited

Sulfur fluxes from bare soils, naturally vegetated surfaces and from several agricultural crops were measured at two mid-continent sites (Ames, Iowa and Celeryville, Ohio) and from one salt water marsh site (Cedar Island, North Carolina) during a field program conducted jointly by the NOAA Aeronomy Laboratory, Washington State University Laboratory for Atmospheric Research and University of Idaho Department of Chemistry during July and August 1985. The sites were chosen specifically because they had been characterized by previous studies (Anejaet al., 1979; Adamset al., 1980, 1981). The NOAA gas chromatographic/dynamic-enclosure measurements yielded bare soil surfaces fluxes from the mid-continent sites composed predominantly of COS, H₂S, CH₃–S–CH₃ (DMS) and CS₂, all of which were strongly correlated with air temperature. Net fluxes of approximately 5 and 15 ng S/m² min were observed in Iowa and Ohio, respectively, at appropriate weighted mean July temperatures. These fluxes are roughly a factor of 10 smaller than the earlier measurements, the greatest difference being in the measurement of the H₂S flux. The presence of growing vegetation was observed to measurably increase the flux of H₂S, significantly increase that of DMS and to decrease that of COS. Sulfur fluxes in the Cedar Island environs were observed to be both spatially and temporally much more variable and to include CH₃SH as a measurable contributor. Net fluxes, composed predominantly of DMS and H₂S, were estimated to be about 300 ngS/m²min during August; again about a factor of 10 lower than previous estimates. All measurements were corroborated to within about a factor of 2 by those of the other participating laboratories.     

Sulfur dioxide and dimethyl sulfide in the central Pacific troposphere

Boundary-layer and free-troposphere measurements of sulfur dioxide, dimethyl sulfide, and carbon disulfide were made during transits of the central and southern Pacific Ocean between Hawaii and Australia. Sulfur dioxide was generally less than 100 pptv and highly variable with no correlation with respect to geographic location or altitude. Dimethyl sulfide in the boundary layer had a concentration range of <10 to 200 pptv. Highest concentrations of DMS were in the equatorial region of the southern hemisphere although the concentrations were dependent on location and meteorological regime. In the region of the Fiji Islands several boundary layer samples had SO₂, DMS, and CS₂. In 1989, additional SO₂ measurements were made between Hawaii and the equator and to the west of Hawaii downwind of the Kilauea volcano plumes.Paper submitted to the 7th International Symposium of the Commission for Atmospheric Chemistry and Global Pollution on the Chemistry of the Global Atmosphere held in Chamrousse, France, from 5 to 11 September 1990.     

An experimental study of sulfur and NOx fluxes over grassland

Three independent sulfur sensors were used in a study of sulfur eddy fluxes to a field of wheat stubble and mixed grasses, conducted in Southern Ohio in September, 1979. Two of these sensors were modified commercial instruments; one operated with a prefilter to measure gaseous sulfur compounds and the other with a denuder system to provide submicron particulate sulfur data. The third sensor was a prototype system, used to measure total sulfur fluxes. The data obtained indicated that the deposition velocity for gaseous sulfur almost always exceeded that for particulate sulfur; average surface conductances were about 1.0 cm s^–1 for gaseous sulfur in the daytime and about 0.4 cm s^–1 for particulate sulfur. The data indicate that nighttime values were probably much lower. The total sulfur sensor provided support for these conclusions. The boundary-layer quantity ln(z ₀ /z _H )was found to be 2.75 ± 0.55, in close agreement with expectations and thus providing some assurance that the site was adequate for eddy flux studies. However, fluxes derived using a prototype NO_x sensor were widely scattered, partially as a consequence of sensor noise but also possibly because of the effects of nearby sources of natural nitrogen compounds.Formerly with Argonne National Laboratory.     

Exchange fluxes of VOSCs between rice paddy fields and the atmosphere in the oasis <Emphasis Type="Bold">of arid area</Emphasis> in Xinjiang,China

Investigations about VOSCs (volatile organic sulfur compounds) have been received increasing attention for their significant contribution to the nonvolcanic background sulfate layer in the stratosphere and the earth’s radiation balance and as a potential tool to understand the carbon budget. In this study, COS and CS₂ were always recorded throughout the entire rice cultivation season of 2014. COS fluxes appeared as emission in non-planted soil and as uptake in planted soil, the corresponding results were obtained as 2.66 and ?2.35 pmol·m^?2·s^?1, respectively. For CS₂, both planted and non-planted paddy fields acted as sources with an emission rate of 1.02 pmol·m^?2·s^?1 and 2.40 pmol·m^?2·s^?1, respectively. COS emission or uptake rates showed a distinct seasonal variation, with the highest fluxes at the jointing-booting stage. COS and CS₂ fluxes increased with increasing N fertilizer use because of improved plant and microbial growth and activity. Plots treated with both N and S reduced COS and CS₂ fluxes slightly compared with plots with only-N treatment. Light, soil moisture or temperature showed no significant correlation with COS and CS₂ fluxes, but revealed the important impacts on the magnitude and direction of gases fluxes. The results also showed that the (available) sulfur contents in soil and roots had a certain effect on VOSCs emission or uptake. Our results highlight the significance of biotic and abiotic production and consumption processes existing in the soil.     

Emission and flux of DMS from the Australian Antarctic and Subantarctic Oceans during the 1988/89 summer

DMS emissions and fluxes from the Australasian sector of the Antarctic and Subantarctic Oceans, bound by 46–68° S and 65.5–142.6° E, were determined from a limited number of samples (n=32) collected during three summer resupply voyages to Australian Antarctic continental research bases between November 1988 and January 1989 (a 92 day period). The maximum DMS emission from this sector of the Antarctic Ocean was in an area near the Antarctic Divergence (60–63° S) and the minimum DMS emission was from the Antarctic coastal and offshelf waters. The greatest emission of DMS from this sector of the Southern Ocean was from the Subantarctic waters. DMS flux from the Australasian Antarctic Ocean was 64.3×10⁶ (±115) mol d^–1 or 5.9 (±10.6)×10⁹ mol based on an emission of 10.9 (±19.5) µmol m^–2 d^–1 (n=26). The flux of DMS from the Australasian sector of the Subantarctic Ocean was probably twice the flux of DMS from the adjacent Antarctic Ocean.     

Carbonyl sulfide emissions from biomass burning in the tropics

Carbonyl sulfide emissions from biomass burning have been studied during field experiments conducted both in an African savanna area (Ivory Coast) and rice fields, central highland pine forest and savanna areas in Viet-Nam. During these experiments CO₂, CO and C₂H₂ or CH₄ have also been also monitored. COS values range from 0.6 ppbv outside the fires to 73 ppbv in the plumes. Significant correlations have been observed between concentrations of COS and CO (R ²=0.92,n=25) and COS and C₂H₂ (R ²=0.79,n=26) indicating a COS production during the smoldering combustion. COS/CO₂ emission factors (COS/CO₂) during field experiments ranged from 1.2 to 61×10^–6 (11.4×10^–6 mean value). COS emission by biomass burning was estimated to be up to 0.05 Tg S/yr in tropics and up to 0.07 Tg S/yr on a global basis, contributing thus about 10% to the global COS flux. Based on the S/C ratio measured in the dry plant biomass and the COS/CO₂ emission factor, COS can account for only about 7% of the sulfur emitted in the atmosphere by biomass burning.     

Spatial and temporal variations of methanesulfonic acid and non sea salt sulfate in Antarctic ice

A simultaneous glaciochemical study of methanesulfonic acid (MSA) and non-sea-salt sulfate (nss-SO₄ ^-) has been conducted on the Antarctic plateau (South Pole, Vostok) and in more coastal regions. The objective was to investigate marine sulfur emissions in very remote areas. Firstly, our data suggest that MSA and nss-SO₄ present in antarctic ice are mainly marine in origin and that DMS emissions have been significantly modulated by short term (eg. El Nino Southern Oscillation events) as well as long term climatic changes in the past. Secondly, our study of spatial variations of these two sulfur species seems to indicate that the atmosphere of coastal antarctic regions are mainly supplied by local DMS emissions whereas the atmosphere of the high plateau is also influenced by DMS emissions from more temperate marine latitudes. Thirdly, our study of the partitioning between MSA and nss-SO₄ suggest that the temperature could have been an important parameter controlling the final composition of the high southern latitude atmosphere over the last climatic cycle; colder temperature favoring the formation of MSA. However, our data also support a possible role played by changes in the transport pattern of marine air to the high antarctic plateau.     

Estimation of Nocturnal Area Fluxes of Carbon Cycle Gases in Saint Petersburg Suburbs

Carbon dioxide, methane, and carbon monoxide are the carbon cycle gases, the data on their emissions are needed when monitoring air pollution and developing methods for reducing anthropogenic emissions to the atmosphere and for climate forecasting. The estimates of nocturnal area fluxes for CO₂, CH₄, and CO presented for a suburb of Saint Petersburg (Peterhof) are obtained using the box model and continuous observations of concentration of these gases. The mean values of CH₄, CO₂, and CO fluxes estimated for Peterhof for 2014–2015 are 44 ± 27, 6100 ± 4000, and 90 ± 100 t/(km² year), respectively. The intensity of the CO area flux has pronounced seasonal variations characterized by the maximum of ~(160 ± 120) t/(km² year) in November—February and by the minimum of ~(30 ± 20) t/(km² year) in June-July. The analysis of the ratio of CO/CO₂ fluxes identified the main types of anthropogenic sources typical of Peterhof: motor transport, natural gas combustion, and the use of wood stoves for the heating of private low-rise buildings (in the cold season).     

Grab sampling for the determination of sulfur dioxide and dimethyl sulfide in air by isotope dilution gas chromatography/mass spectrometry

Developments allowing the direct determination of sulfur dioxide and dimethyl sulfide in grab samples by gas chromatography/mass spectrometry with isotopically labeled standards (GC/MS/ILS) are reported. Isotopomers of DMS and SO₂ are used as internal standards. Spiked air samples are dried to a dew point of <–60 °C and trapped cryogenically in loops of Teflon tubing. Sealed samples are transported to the laboratory under liquid nitrogen and later subjected to GC/MS analysis. Holding times of up to one month do not result in significant sample loss. For samples collected in a clean marine environment, concentrations of SO₂ and DMS greater than 5 and 8 pptv, respectively, are significantly different from blanks at the 95% confidence level. Average measurement precision derived from a propagation of errors are 9% for SO₂ and 42% for DMS at concentrations from 5–15 pptv.Improvements are outlined which should provide sensitivity and precision comparable to that of on-site GC/MS. The technique will allow increased flexibility for the determination of trace sulfur species in the field under conditions where deployment of a mass spectrometer is not possible.     

Potential impact of climate change on marine dimethyl sulfide emissions

Dimethyl sulfide (DMS) is a biogenic compound produced in sea-surface water and outgased to the atmosphere. Once in the atmosphere, DMS is a significant source of cloud condensation nuclei in the unpolluted marine atmosphere. It has been postulated that climate may be partly modulated by variations in DMS production through a DMS-cloud condensation nuclei-albedo feedback. We present here a modelled estimation of the response of DMS sea-water concentrations and DMS fluxes to climate change, following previous work on marine DMS modeling ( Aumont et al., 2002 ) and on the global warming impact on marine biology ( Bopp et al., 2001 ). An atmosphere–ocean general circulation model (GCM) was coupled to a marine biogeochemical scheme and used without flux correction to simulate climate response to increased greenhouse gases (a 1% increase per year in atmospheric CO₂ until it has doubled). The predicted global distribution of DMS at  1 × CO₂  compares reasonably well with observations; however, in the high latitudes, very elevated concentrations of DMS due to spring and summer blooms of Phaeocystis can not be reproduced. At  2 × CO₂  , the model estimates a small increase of global DMS flux to the atmosphere (+2%) but with large spatial heterogeneities (from −15% to +30% for the zonal mean). Mechanisms affecting DMS fluxes are changes in (1) marine biological productivity, (2) relative abundance of phytoplankton species and (3) wind intensity. The mean DMS flux perturbation we simulate represents a small negative feedback on global warming; however, the large regional changes may significantly impact regional temperature and precipitation patterns.