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1.
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.  相似文献   

2.
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   

3.
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   

4.
Daily measurements of atmospheric sulfur dioxide (SO2) concentrations were performed from March 1989 to January 1991 at Amsterdam Island (37°50 S–77°30 E), a remote site located in the southern Indian Ocean. Long-range transport of continental air masses was studied using Radon (222Rn) as continental tracer. Average monthly SO2 concentrations range from less than 0.2 to 3.9 nmol m-3 (annual average = 0.7 nmol m-3) and present a seasonal cycle with a minimum in winter and a maximum in summer, similar to that described for atmospheric DMS concentrations measured during the same period. Clear diel correlation between atmospheric DMS and SO2 concentrations is also observed during summer. A photochemical box model using measured atmospheric DMS concentrations as input data reproduces the seasonal variations in the measured atmospheric SO2 concentrations within ±30%. Comparing between computed and measured SO2 concentrations allowed us to estimate a yield of SO2 from DMS oxidation of about 70%.  相似文献   

5.
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.  相似文献   

6.
Measurements of NOx (NO +NO2) and the sum of reactive nitrogenconstituents, NOy, were made near the surface atAlert (82.5°N), Canada during March and April1998. In early March when solar insolation was absentor very low, NOx mixing ratios were frequentlynear zero. After polar sunrise when the sun was abovethe horizon for much or all of the day a diurnalvariation in NOx and NOy was observed withamplitudes as large as 30–40 pptv. The source ofactive nitrogen is attributed to release from the snowsurface by a process that is apparently sensitized bysunlight. If the source from the snowpack is a largescale feature of the Arctic then the diurnal trendsalso require a competing process for removal to thesurface. From the diurnal change in the NO/NO2ratio, mid-April mixing ratios for the sum of peroxyand halogen oxide radicals of 10 pptv werederived for periods when ozone mixing ratios were inthe normal range of 30–50 ppbv. Mid-day ozoneproduction and loss rates with the active nitrogensource were estimated to be 1–2 ppbv/day and in nearbalance. NOy mixing ratios which averaged only295±66 pptv do not support a large accumulation inthe high Arctic surface layer in the winter and springof 1998. The small abundance of NOy relative tothe elevated mixing ratios of other long-livedanthropogenic constituents requires that reactivenitrogen be removed to the surface during transport toor during residence within the high Arctic.  相似文献   

7.
In 1978–1980 nine aircraft flights to an altitude of up to 15 km were made over western Europe. Sulfur dioxide was measured with a sensitive chemiluminescence method consisting of separate sampling and analysis stages and application of a wet chemical filter procedure (detection limit: 8 pptv SO2).The measurements performed in the upper troposphere and lower stratosphere lead to some unexpected results: (a) the meteorological conditions at the tropopause level have an important influence on the observed SO2 mixing ratio; (b) between the 500 mb and the actual tropopause level the SO2 mixing ratio is found to be <100 pptv, and weak vertical gradients of SO2 suggest only a small flux of tropospheric SO2 into the stratosphere; (c) increasing SO2 mixing ratios within the first kilometers of the stratosphere give strong support to a stratospheric source of SO2.In the light of improved one-dimensional models considering the vertical distribution of stratospheric sulfur compounds (Crutzen, 1981; Turco et al. 1981) it can be shown that the oxidation of organic sulfur compounds (e.g., OCS, CS2) seems to be a stratospheric source of SO2. Furthermore, the flux calculations based on the SO2 mixing ratios measured at the tropopause level indicate that the contribution of tropospheric (man-made) SO2 to the stratospheric aerosol layer is of only minor importance.  相似文献   

8.
Measurements of formaldehyde (HCHO) were made at the Cape Verde Atmospheric Observatory between November 2006 and June 2007 using the Long-Path Differential Optical Absorption Spectroscopy (LP-DOAS) technique. Observations show that typical HCHO mixing ratios ranged between 350 and 550 pptv (with typical 2-σ uncertainties of ~110 pptv), with several events of high HCHO, the maximum being 1,885?±?149 pptv. The observations indicate a lack of strong seasonal or diurnal variations, within the uncertainty of the measurements. A box model is employed to test whether the observations can be explained using known hydrocarbon photochemistry; the model replicates well the typical diurnal profile and monthly mean values. The model results indicate that on average 20% of HO2 production and 10% of OH destruction can be attributed to the mean HCHO levels, suggesting that even at these low average mixing ratios HCHO plays an important role in determining the HOx (HO2+OH) balance of the remote marine boundary layer.  相似文献   

9.
Daily measurements of atmospheric concentrations of dimethylsulfide (DMS) were carried out for two years in a marine site at remote area: the Amsterdam Island (37°50S–77°31E) located in the southern Indian Ocean. DMS concentrations were also measured in seawater. A seasonal variation is observed for both DMS in the atmosphere and in the sea-surface. The monthly averages of DMS concentrations in the surface coastal seawater and in the atmosphere ranged, respectively, from 0.3 to 2.0 nmol l-1 and from 1.4 to 11.3 nmol m-3 (34 to 274 pptv), with the highest values in summer. The monthly variation of sea-to-air flux of DMS from the southern Indian Ocean ranges from 0.7 to 4.4 mol m-2 d-1. A factor of 2.3 is observed between summer and winter with mean DMS fluxes of 3.0 and 1.3 mol m-2 d-1, respectively.  相似文献   

10.
Dimethylsulfide (DMS), sulfur dioxide (SO2), methanesulfonate (MSA), nonsea-salt sulfate (nss-SO4 2–), sodium (Na+), ammonium (NH4 +), and nitrate (NO3 –) were determined in samples collected by aircraft over the open ocean in postfrontal maritime air masses off the northwest coast of the United States (3–12 May 1985). Measurements of radon daughter concentrations and isentropic trajectory calculations suggested that these air masses had been over the Pacific for 4–8 days since leaving the Asian continent. The DMS and MSA profiles showed very similar structures, with typical concentrations of 0.3–1.2 and 0.25–0.31 nmol m–3 (STP) respectively in the mixed layer, decreasing to 0.01–0.12 and 0.03–0.13 nmol m–3 (STP) at 3.6 km. These low atmospheric DMS concentrations are consistent with low levels of DMS measured in the surface waters of the northeastern Pacific during the study period.The atmospheric SO2 concentrations always increased with altitude from <0.16–0.25 to 0.44–1.31 nmol m–3 (STP). The nonsea-salt sulfate (ns-SO4 2–) concentrations decreased with altitude in the boundary layer and increased again in the free troposphere. These data suggest that, at least under the conditions prevailing during our flights, the production of SO2 and nss-SO4 2– from DMS oxidation was significant only within the boundary layer and that transport from Asia dominated the sulfur cycle in the free troposphere. The existence of a sea-salt inversion layer was reflected in the profiles of those aerosol components, e.g., Na+ and NO3 –, which were predominantly present as coarse particles. Our results show that long-range transport at mid-tropospheric levels plays an important role in determining the chemical composition of the atmosphere even in apparently remote northern hemispheric regions.  相似文献   

11.
Emissions of marine biogenic sulfur to the atmosphere of northern Europe   总被引：1，自引：0，他引：1  
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.  相似文献   

12.
Springtime measurements of NOx, ozone, PAN,J(NO2), and other compounds were made near Ny-Ålesund,Svalbard (78°54N, 11°53E), in 1994 and Poker Flat,Alaska (65°08N, 147°29W), in 1995. At Svalbard medianmixing ratios for PAN and NOx of 237 and 23.7 pptv,respectively, were observed. The median mixing ratios at Poker Flat for PANand NOx were 79.5 and 85.9 pptv, respectively. These data areused to estimate thermal PAN decomposition using several differentapproaches. At Svalbard PAN decomposition was very small, while at PokerFlat up to 30 pptv/h PAN decomposed. At both sites the NOx/PANratio increased with temperature between –10 and 20°C implyingthat PAN decomposition is an important NOx source. In-situozone production was calculated from the measured NO, NO2,O3, J(NO2), and temperature data, using thesteady state assumption Median ozone production was 605 pptv/h at PokerFlat, and one order of magnitude smaller at Svalbard during the daytime.Only at Poker Flat could a direct influence on the diurnal ozone cycle beobserved from in-situ production. These results imply that PAN decompositionis a major source of NOx in the high latitude troposphere, andthat this contributes to the observed spring maximum in surface ozone.  相似文献   

13.
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   

14.
Aircraft observations of oxides of nitrogen (NO y ), measured with a ferrous sulfate converter, over the sea surrounding the Japanese islands (30–43° N, 131–141° E) were carried out in the winter of 1983 and 1984 at altitudes mostly between 3 and 8 km. NO y defined here is the sum of NO, NO2, and other unstable oxides of nitrogen that are converted to NO by ferrous sulfate. The main observations were:
  1. Over the Pacific Ocean between the latitudes of 30–35° N, the observed NO y mixing ratio between 3 and 8 km was a fairly constant 200 pptv. The NO mixing ratio increased with altitude from 15 pptv at 3 km to 35 pptv at 7 km.
  2. Over the Sea of Japan, tropospheric NO y mesured between 1 and 6 km started increasing with latitude North of 35° N and reached about 1000 pptv at 40° N.
  3. NO y was measured in an air mass transported from the stratosphere near a tropopause fold region. When the ozone mixing ratio was between 80 and 140 ppbv, the NO y mixing ratio was about 200 pptv.
  相似文献   

15.
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.  相似文献   

16.
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   

17.
Atmospheric concentrations of ca. 250 C6–C15 hydrocarb on and C4–C12 oxygenated volatile organic compounds (VOC) including alkanes, benzene and alkyl benzenes, monoterpenes and aldehydes were measured in August 1994 during the POPCORN campaign (POPCORN = Photo-Oxidant formation by Plant emitted Compounds and OH Radicals in North-Eastern Germany). About 80 substances together contributed 90% of the atmospheric carbon in this range of molecular weight. During this field campaign VOC-emissions from several crop and tree species and the ambient concentrations of CO, C2–C7 non-methane hydrocarbons (NMHC), C1 and C2 aldehydes, nitrogen oxides, ozone and hydroxyl-radicals (OH) were also measured. These data were used to interpret the VOC measurements presented here. The on-line GC–MS used for the VOC measurements combines adsorptive sampling with thermal desorption and GC–MS analysis in an automated system. Internal standards were used to quantify the measurements. Ozone was destroyed prior to the sample preconcentration through the gas phase reaction with NO. Aromatic compounds like benzene, toluene and xylenes were the most abundant compound class among the measured substances, -pinene and 3-carene, most probably originating from pineforests ca. 1 km away from the measuring site, were the most abundant monoterpenes. The highest mixing ratios of most compounds were measured in nights with strong inversion situations. The toluene mixing ratios then reached 630 pptv; -pinene mixing ratios went up to 430 pptv. The median of all toluene and -pinene measurements during the campaign was 125 pptv or 22 pptv, respectively. These values are on the lower end of ambient measurements reported for continental sites. In most samples also n-pentanal, n-hexananl, n-nonanal and n-undecanal were present. Median mixing ratios were 9, 16, 14 and 8 pptv, respectively. Emission studies indicate that these highly reactive compounds are most probably emitted from maize. It is shown by a simple first order approach that the potential for ozone formation during the POPCORN campaign was roughly equal for anthropogenic and biogenic VOC. From measured concentrations of ozone, OH-radicals, methane, CO, C2–C15 nonmethane hydrocarbons (NMHC) and C5–C11 aldehydes a photochemical production of ozone in the order of 3.5 ppb/h can be estimated. Apart from formaldehyde and acetaldehyde, which are at least partly products of VOC oxidation, the substance group with the largest contribution to the VOC turnover are the monoterpenes. They contribute ca. 30%. However, the mechanism of terpene oxidation is very complex and presently only partly understood. Thus the actual contribution of monoterpenes to ozone formation is very uncertain. Other measured compound classes such as light alkenes, alkanes, aromatics, and C5–C11 aldehydes contribute each between 10% and 15% to ozone formation. The measuring site was not influenced directly from strong biogenic or anthropogenic sources, and the results obtained during the POPCORN campaign can be regarded as a typical picture of a remote rural central European environment.  相似文献   

18.
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   

19.
An atmospheric monitoring station is operated at Cape Matatula, American Samoa, by the Geophysical Monitoring for Climatic Change program under the National Oceanic and Atmospheric Administration. A nearly continuous record of condensation nucleus (CN) concentration and multiwavelength aerosol scattering extinction coefficient (sp) is available from mid-1977 to the present. This report presents the 1977–1983 data. The long-term mean of CN concentration is 274 cm-3 the long-term mean of sp (550 nm) is 1.54×10-5, and no significant long-term, annual, or diurnal trend is apparent in either data record.  相似文献   

20.
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   

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