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1.
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.  相似文献   

2.
The concentrations of DMS were simultaneously measured in both water and air at the sea surface on board a vessel during a trans-Pacific cruise around 40° N in August 1988. Those in the surface seawater varied widely with a mean of 162 ng S/1 and a standard deviation of 134 ng S/1 (n=37), but the variation was not a mere fluctuation and the high concentration (376 ng S/1) was found in the area between 145° W and 170° W. The atmospheric DMS concentration varied more widely with a mean value of 177 ng S/m3 and a standard deviation of 203 ng S/m3 (n=23). The diurnal variation of DMS was not significant in the air near the sea surface. However, the concentrations in the surface water was fairly well correlated with those in the surface air. The correlation coefficient (r 2=0.86) was larger than that between the atmospheric concentration and outflux of DMS (r 2=0.64). These findings mean that the turnover time of DMS in the atmosphere is not extremely short. Based on the linear relation between the atmospheric and seawater DMS, the turnover time of the atmospheric DMS has been calculated to be 0.9 days with an uncertainty of around 50%. The oxidation rate agrees fairly well with that expected from the OH radical concentration in the marine atmosphere.  相似文献   

3.
A method has been developed for determining trace quantities of dimethyl sulfoxide (DMSO) in aqueous solutions using isotope dilution gas chromatography/mass spectrometry. The method consisted of first reducing DMSO to dimethyl sulfide (DMS), followed by purge and trap preconcentration of DMS. The concentration of DMSO was determined from the signal ratio obtained for the parent ions of DMS and d6-DMS, and the known aqueous concentration of d6-DMSO. The precision of this method was determined to be ± 2.9 %, based on replicate DMSO determinations of a test solution prepared by adding isotopically unenriched (h6-DMSO) to distilled water. The detection limit was 0.010 nmoles/L for the sampling conditions used in this study. This method was applied to the determination of DMSO concentrations in both rain and sea water. The concentration of DMSO in rain was found to be in the range of 2–4 nmoles/L for samples collected at an inland location (Phila, PA) and 8–11 nmoles/L for samples collected at a coastal location (Lewes, DE). Determination of DMSO in sea water required special sample preparation steps to eliminate positive interferences. A depth profile of DMS, DMSO, and dimethyl sulfoniopropionate (DMSP) concentrations is reported for sea water collected off the coast of Ocean City, Md, in August, 1990  相似文献   

4.
Potential impact of climate change on marine dimethyl sulfide emissions   总被引：1，自引：0，他引：1  
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.  相似文献   

5.
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.  相似文献   

6.
Dimethylsulfide (DMS) measurements in the seawater of the subtropical and the temperate western Indian Ocean were conducted for the first time from 3 December to 20 December 1997. In total, 443 surface seawater DMS determinations were performed between 24°–49° S and 50° E–77° E with a frequency of 1 sample every 10 km. An important spatial variability was observed in seawater DMS concentrations with values ranging from 0.9 to 35.8 nM. DMS maxima coincided in most cases with thermal fronts and were in reasonable agreement with mean pigment figures obtained from satellite observations. The deduced DMS fluxes are consistent with long-term observations of atmospheric DMS and rainwater concentrations of nss- SO4= and MSA measured at Amsterdam island (37° S, 77° E); then account for the differences observed in atmospheric DMS concentrations between Amsterdam island and Cape Grim, Indian Ocean monitoring stations.  相似文献   

7.
Dimethylsulphide (DMS) has been implicated in climate change as a possible negative feedback to global warming, and several Models have been developed that simulate the production of DMS in the marine environment. The focus of this study is to improve the nitrogen based Gabric Model, using field data collected during the Southern Hemisphere First Marine Aerosol Characterisation Experiment (ACE-1) in the Southern Ocean in 1995. Two Model Runs (Series A and B) were carried out with six simulations of varying biotic and abiotic inputs applied over the voyage transect (41-48°S), reflecting Model default values or field values from the experiment. The abiotic inputs were time-step, dissolved dimethylsulphoniopropionate (DMSP) and DMS, and the biotic nitrogen inputs were from phytoplankton, bacteria, zooflagellates, large protozoa, micro and mesozooplankton. The focus of the abiotic assessment was nutrient (nitrate) uptake and dissolved DMSP and DMS output. Model output of the biotic compartments was assessed for congruence with predicted ecological patterns of succession.

Despite a limited data set the study provides a good insight into the utility of the Model, which functioned as a heuristic rather than predictive tool. In simulation 1 (Series A) where the only field value was nitrate, all latitudes from 41-48°S concurred with the ecological succession predicted by the Model authors and the successional pattern predicted by other researchers, with a double phytoplankton peak indicating remineralisation of nitrogen via the microbial loop. In many simulations the Model produced lower values of dissolved DMS than were measured, and production of DMS in the Model appears constrained. However, in simulation 5 (Series A) DMS model outputs were closest to the mean dissolved DMS levels reported on RV Discoverer. In this simulation, field values were used for phytoplankton, nitrate, dissolved DMSP and DMS, with bacterial abundance and micro and mesozooplankton increased over their Gabric default values. Also, the phytoplankton double peak occurred earlier, as did the peaks in bacteria, zooflagellates, and large protozoa. Simulations that deviated more significantly from the predicted successional patterns were characterised by single peaks in phytoplankton growth and delayed bacterial growth. Series C simulations at latitude 43°S, in an attempt to reduce phytoplankton predation by bacteria, increased DMS output reasonably successfully. However, significant recalibration of the Model is recommended in conjunction with field studies to gather vital background biological data - particularly in the areas of nutrient limitation, phytoplankton speciation, and the cellular content of the DMS precursor compound, DMSP.  相似文献   

8.
Abstract

Dimethylsulfoxide (DMSO) is an ubiquitous, albeit poorly understood, component of the marine sulfur cycle. Conventionally, the accepted formation pathways are the photochemical and microbial oxidation of dimethylsulfide (DMS). The principal loss mechanism is thought to be via microbial transformation, either consumption or reduction to DMS. The interactions between DMSO and DMS are likely to be important in controlling sea surface concentrations of DMS, and thus DMSO could influence the role played by DMS in global climate regulation. This review examines current knowledge of the distribution of DMSO in aquatic environments and the possible link between DMSO, DMS and global climate control. Mechanisms for the formation and loss of DMSO are also considered in addition to some of the factors influencing these processes. The review also considers that DMSO may be biosynthesized by phytoplankton, representing a non‐DMS source for DMSO, and that DMSO can undergo photochemical oxidation, a potential loss mechanism for DMSO in the marine environment.  相似文献   

9.
We present a technique for the measurement of dimethyl sulfide (DMS) from airborne and ground-based platforms, using whole air sampling followed by gas chromatography with mass spectrometer and flame ionization detection. DMS measurements that were obtained during the 1999 NASA Pacific Exploratory Mission-Tropics B showed excellent agreement with independent in-flight DMS measurements, over a wide range of concentrations. The intercomparison supports two key results from this study, first that DMS can be accurately quantified based on ethane and propane per-carbon-response-factors (PCRFs), and second that DMS is stable in water-doped electropolished stainless steel canisters for at least several weeks. In addition, our sampling frequency and duration are flexible and allow detail in the vertical structure of DMS to be well captured. Sampling times as fast as 8 s were achieved and these data are suitable for DMS flux calculations using the mixed-layer gradient technique. Correlations between DMS and other marine tracers can also be readily investigated by this whole air sampling technique, because DMS is analyzed together with more than 50 simultaneously sampled hydrocarbons, halocarbons, and alkyl nitrates. The detection limit of the DMS measurements is 1 part per trillion by volume (pptv), and we conservatively estimate the accuracy to be ±20% or 3 pptv, whichever is larger. The measurement precision (1 ) is 2–4% at high mixing ratios (> 25 pptv), and 1 pptv or 15%, whichever is larger, at low mixing ratios (<10 pptv).  相似文献   

10.
The major components of the marine boundary layer biogeochemical sulfur cycle were measured simultaneously onshore and off the coast of Washington State, U.S.A. during May 1987. Seawater dimethylsulfide (DMS) concentrations on the continental shelf were strongly influenced by coastal upwelling. Concentration further offshore were typical of summer values (2.2 nmol/L) at this latitude. Although seawater DMS concentrations were high on the biologically productive continental shelf (2–12 nmol/L), this region had no measurable effect on atmospheric DMS concentrations. Atmospheric DMS concentrations (0.1–12 nmol/m3), however, were extremely dependent upon wind speed and boundary layer height. Although there appeared to be an appreciable input of non-sea-salt sulfate to the marine boundary layer from the free troposphere, the local flux of DMS from the ocean to the atmosphere was sufficient to balance the remainder of the sulfur budget.  相似文献   

11.
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%.  相似文献   

12.
Dimethylsulphide (DMS) is an important sulphur‐containing trace gas produced by enzymatic cleavage of its precursor compound, dimethylsulphoniopropionate (DMSP), which is released by marine phytoplankton in the upper ocean. After ventilation to the atmosphere, DMS is oxidised to form sulphate aerosols which in the unpolluted marine atmosphere are a major source of cloud condensation nuclei (CCN). Because the micro‐physical properties of clouds relevant to climate change are sensitive to CCN concentration in air, it has been postulated that marine sulphur emissions may play a rôle in climate regulation. The Subantarctic Southern Ocean (41–53°S) is relatively free of anthropogenic sulphur emissions, thus sulphate aerosols will be mainly derived from the biogenic source of DMS, making it an ideal region in which to evaluate the DMS‐climate regulation hypothesis. We have extended a previous modelling analysis of the DMS cycle in this region by employing a coupled general circulation model (CGCM) which has been run in transient mode to provide a more realistic climate scenario. The CGCM output provided meteorological data under the IPCC/IS92a radiative forcing scenario. A DMS production model has been forced with the CGCM climate data to simulate the trend in the sea‐to‐air DMS flux for the period 1960 to 2080, corresponding to equivalent CO2 tripling relative to pre‐industrial levels. The results confirm a minor but non‐negligible increase in DMS flux in this region, in the range +1% to +6% predicted over the period simulated. Uncertainty analysis of the DMS model predictions have confirmed the positive sign for the change in DMS flux, that is a negative DMS feedback on warming.  相似文献   

13.
A one-month experiment was performed at Amsterdam Island in January 1998, to investigate the factors controlling the short-term variations of atmospheric dimethylsulfide (DMS) and its oxidation products in the mid-latitudes remote marine atmosphere. High mixing ratios of DMS, sulfur dioxide (SO2) and dimethylsulfoxide (DMSO) have been observed during this experiment, with mean concentrations of 395 parts per trillion by volume (pptv) (standard deviation, = 285, n = 500), 114 pptv ( = 125, n = 12) and 3 pptv ( = 1.2, n = 167), respectively. Wind speed and direction were identified as the major factors controlling atmospheric DMS levels. Changes in air temperature/air masses origin were found to strongly influence the dimethylsulfoxide (DMSO)/DMS and SO2/DMS molar ratios, in line with recent laboratory data. Methanesulfonic acid (MSA) and non-sea-salt sulfate (nss-SO4 2–) mean concentrations in aerosols during this experiment were 12.2± 6.5 pptv (1, n=47) and 59 ± 33 pptv (1, n=47), respectively. Evidence of vertical entrainment was reported following frontal passages, with injection of moisture-poor, ozone-rich air. High MSA/ nss-SO4 2– molar ratios (mean 0.44) were calculated during these events. Finally following frontal passages, few spots in condensation nuclei (CN) concentration were also observed.  相似文献   

14.
The atmospheric sulfur cycle of the remote Arctic marine boundary layer is studied using trajectories and measurements of sulfur compounds from the International Arctic Ocean Expedition 1991, along with a pseudo-Lagrangian approach and an analytical model. The dimethyl sulfide [DMS(g)] turnover time was  h. Only  % of DMS(g) followed reaction paths to sulfur dioxide [SO2(g)], sub-micrometre aerosol non-seasalt sulfate (nss-SO42−) or methane sulfonate (MSA). During the first 3 d of transport over the pack ice, fog deposition and drizzle resulted in short turnover times;  h for SO2(g),  h for MSA and  h for nss-SO42−. Therefore, DMS(g) will, owing to its origin along or south of the ice edge and longer turnover time, survive the original sub-micrometre sulfur aerosol mass and gradually replace it with new biogenic sulfur aerosol mass. The advection of DMS(g) along with heat and moisture will influence the clouds and fogs over the Arctic pack ice through the formation of cloud condensation nuclei (CCN). If the pack ice cover were to decrease owing to a climate change, the total Arctic Ocean DMS production would change, and potentially there could be an ice–DMS–cloud–albedo climate feedback effect, but it would be accompanied by changes in the fog aerosol sink.  相似文献   

15.
Measurements of atmospheric dimethylsulfide (DMS) and its oxidation products, sulfur dioxide (SO2), methanesulfonic acid (MSA) and non-sea-salt sulfate (nss-SO4 2-) were monitored during the period June 9–26, 1989 at a coastal site in Brittany. As indicated by the radon (Rn-222) activities and the high concentrations of NOx the air masses, for most of the experiment, were continental in origin. The observed concentrations range from 1.9 to 65 nmol/m3 for DMS (n=157), 0.6 to 94.2 nmol/m3 for SO2 (n=50), 0.6 to 11.6 nmol/m3 for MSA (n=44) and 42 to 350 nmol/m3 for nss-SO4 2- (n=44). Aitken nuclei reached values as high as 4.5 × 105 particles/m3. When continental conditions predominated, the measured SO2 concentrations were lower than those expected from a consideration of the observed DMS concentrations and the existence of SO2 background of the continental air masses. Similarly, compared to the MSA/DMS ratio in the marine atmosphere, higher concentrations of MSA were observed than those expected from the measured levels of DMS. The presence of enhanced levels of MSA was also endorsed by the observation that the measured mean MSA/nss-SO4 2- ratio of 6±3% was similar to the mean value of 6.9% observed in the marine atmosphere. These above observations are in line with recent laboratory findings by Barnes et al. (1988), which show an increase of the MSA/DMS yield with a simultaneous decrease of the SO2/DMS yield in the presence of NOx.  相似文献   

16.
Dimethylsulfide (DMS) in surface seawater and the air, methanesulfonic acid (MSA) and non-sea-salt sulfate (nss-SO4 2–) in aerosol, and radon-222 (Rn-222) were measured in the northern North Pacific, including the Bering Sea, during summer (13 July – 6 September 1997). The mean atmospheric DMS concentrations in the eastern region (21.0 ± 5.8 nmole/m3 (mean ± S.D.), n=30) and Bering Sea (19.9 ± 9.8 nmole/m3, n=10) were higher than that in the western region (11.1 ± 6.4 nmole/m3, n=31) (p<0.05), although these regions did not significantly differ in the mean DMS concentration in surface seawater. Mean sea-to-air DMS flux in the eastern region (21.0 ± 10.4 mole/m2/day, n=19) was larger than those in the western region (11.3 ± 16.9 mole /m2/day, n=22) and Bering Sea (11.2 ± 7.8 mole/m2/day, n=7) (p<0.05). This suggests that the longitudinal difference in atmospheric DMS was produced by that in DMS flux owing to wind speed, while the possible causes of the higher DMS concentrations in the Bering Sea include (1) later DMS oxidation rates, (2) lower heights of the marine boundary layer, and (3) more inactive convection. The mean MSA concentrations in the eastern region (1.18 ± 0.84 nmole/m3, n=35) and Bering Sea (1.17 ± 0.87 nmole/m3, n=13) were higher than that in the western region (0.49 ± 0.25 nmole/m3, n=28) (p < 0.05). Thus the distribution of MSA was similar to that of DMS, while the nss-SO4 2– concentrations were higher near the continent. This suggests that nss-SO4 2– concentrations were regionally influenced by anthropogenic sulfur input, because the distribution of nss-SO4 2– was similar to that of Rn-222 used as a tracer of continental air masses.  相似文献   

17.
This study reports comparisonsbetween model simulations, based on current sulfurmechanisms, with the DMS, SO2 and DMSOobservational data reported by Bandy et al.(1996) in their 1994 Christmas Island field study. For both DMS and SO2, the model results werefound to be in excellent agreement with theobservations when the observations were filtered so asto establish a common meteorological environment. Thisfiltered DMS and SO2 data encompassedapproximately half of the total sampled days. Basedon these composite profiles, it was shown thatoxidation of DMS via OH was the dominant pathway withno more than 5 to 15% proceeding through Cl atoms andless than 3% through NO3. This analysis wasbased on an estimated DMS sea-to-air flux of 3.4 ×109 molecs cm-2 s-1. The dominant sourceof BL SO2 was oxidation of DMS, the overallconversion efficiency being evaluated at 0.65 ± 0.15. The major loss of SO2 was deposition to theocean's surface and scavenging by aerosol. Theresulting combined first order k value was estimated at 1.6 × 10-5 s-1. In contrast to the DMSand SO2 simulations, the model under-predictedthe observed DMSO levels by nearly a factor of 50. Although DMSO instrument measurement problems can notbe totally ruled out, the possibility of DMSO sourcesother than gas phase oxidation of DMS must beseriously considered and should be explored in futurestudies.  相似文献   

18.
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 NOx (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.  相似文献   

19.
本文利用一维光化学模式，以二甲硫醚（ＤｉｍｅｔｈｙｌＳｕｌｆｉｄｅ，简称ＤＭＳ）为源模拟了西太平洋对流层的硫化物循环。ＤＭＳ海－气通量由“ｓｔａｇｎａｎｔ－ｆｉｌｍ”模式进行计算。尽管海洋大气中ＯＣＳ浓度比ＤＭＳ大一个量级，但它对ＳＯ２的贡献很小，ＤＭＳ仍是海洋大气中ＳＯ２的主要源。在大气垂直湍流输送过程中，ＤＭＳ白天与ＯＨ反应，夜间与ＮＯ３反应被氧化成ＳＯ２，ＳＯ２大部分通过非均相转化形成Ｈ２ＳＯ４。模拟结果与ＰＥＭ－ＷＥＳＴ－Ａ观测资料对比，取得了较好的一致性。  相似文献   

20.
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%.  相似文献   

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