Constraints on 2-Way Transport across the Arctic Tropopause Based on O3, Stratospheric Tracer (SF6) Ages, and Water Vapor Isotope (D, T) Tracers

Based upon airborne trace gas and isotope observations in the winter months 1991/1992 to1994/1995, transport pathways across the mid-latitude and Arctic tropopause areinvestigated. A powerful set of contrasting transport tracers are examined, such asdeuterated water vapor (HDO) which is shown to trace the passage of water vapor from thetroposphere into the lowermost stratosphere (LS), or the `SF₆ age' defined as theresidence time of an air parcel within the stratosphere since its entry at thetropopause. Cross-tropopause transport in both directions was found near mid-latitudecyclones (at baroclinic flanks of troughs in the polar front), in which about 80% of thestratosphere-to-troposphere flux proceeded along potential temperature ()surfaces of 300 ± 10 K. As these isentropes are the lowest which reach into the LS(in winter), a mixing zone just above the Arctic tropopause (at least 1.5 km thick) isformed. Here, upwelling tropospheric air is mixed with downwelling LS air which isaffected by air from higher altitudes, the surf-zone and the polar vortex. The observedelevated D/H isotope ratio of water vapor within the mixing zone can be explained byinjection of subtropical water vapor that is transported to the tropopause by the warmconveyor belt associated with mid-latitude cyclones. Downward vertical transport ofArctic LS air, which may be influenced by ouflowing chemically disturbed polar vortexair, into the Arctic troposphere was found to be small.     

The biogeochemical sulfur cycle in the marine boundary layer over the Northeast Pacific Ocean

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.     

Seasonal variations of atmospheric sulfur dioxide and dimethylsulfide concentrations at Amsterdam Island in the southern Indian Ocean

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%.     

Oxidation of sulfur dioxide by ozone in highly dispersed water droplets

The oxidation of S(IV) by ozone in aqueous solution has been studied in highly dispersed droplets in a laboratory could chamber at 20°C. Urban air was used. Ozone concentrations ranged from 15 to 120 ppb, orders of magnitude lower than most previous works. Rate constants were derived from differential product determination, rather than from rates of decay of bulk reactants. Comparison of the results obtained here with those from previous work indicates that the reaction rate is indeed first order with respect to ozone. The second-order reaction rate constants found in this work lay between, or close to, other recent results, and could be represented by:k=1.23×10⁴ [H⁺]^–0.51 M^–1 s^–1.     

Vertical distribution of dimethylsulfide,sulfur dioxide,aerosol ions,and radon over the Northeast Pacific Ocean

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.     

The effect of gas-phase chemistry on aqueous-phase sulfur dioxide oxidation rates

The rates and mechanisms of both gas and liquid phase reactions for the oxidation of sulfur dioxide play an important role in the production of atmospheric acids and aerosol particles. Rhodeet al. (1981) concluded that sulfate production rates were highly non-linear functions of sulfur dioxide emission rates. Their modelling study used an HO _x termination mechanism for the HO—SO₂ reaction in the gas-phase. Stockwell and Calvert (1983) determined that one of the products of the overall reaction of HO with sulfur dioxide was an HO₂ radical. The National Research Council (1983) using a version of the Rhodeet al. (1981) model modified to include HO₂ production from the HO—SO₂ reaction concluded that sulfate production becomes much more linear with respect to reductions in sulfur dioxide emissions. However, the cause of this increased linearity was not explained by the National Research Council report. It is demonstrated that the increased linearity is due to the coupling of gas-phases and aqueous phase chemistry. The gas-phase sulfur dioxide oxidation mechanism has a very significant effect on hydrogen perodide production rates.     

Sulfur dioxide in the North American Arctic

Determinations of atmospheric sulfur dioxide were made across the North American Aretic using gas chromatography with a detection limit of 25 parts per trillion by volume and a precision of 25% or better. The vertical distribution of sulfur dioxide in the Arctic atmosphere in April, 1986 was highly variable, with concentrations ranging from the detection limit to 15 parts-per-billion by volume (ppbv). While SO₂ exceeded 10 ppbv in an exceptional haze layer in the Alaskan Arctic, sulfur dioxide was sometimes in the 1 – 5 ppbv range when the haze was absent. This was particularly true for the Canadian Arctic in the vicinity of Alert. In the lower stratosphere over Ellesmere Island, sulfur dioxide was 0.85 ppbv.     

青藏高原及其邻近区域穿越对流层顶质量通量的时空演变特征

利用1958~2001年ECMWF资料, 根据Wei公式估算了青藏高原及其邻近区域穿越对流层顶的质量通量 (CTF), 分析了CTF的时空分布特征。分析结果表明: (1) CTF分布呈现纬向型, 在副热带西风急流北侧即对流层顶断裂带中存在东西向的TST (对流层向平流层输送)[CD*2]STT (平流层向对流层输送)[CD*2]TST的波列结构 (水平输送项决定), 而南侧分布决定于垂直输送项。 (2) 在80°E~105°E范围内, 冬春季节, 青藏高原南部及其以南区域为TST, 北部为STT; 夏秋季节, 整个区域几乎由TST所控制。西风急流南侧的CTF主要决定于垂直项, 而北侧主要决定于水平项, 再往北, 垂直项与水平项贡献相当。 (3) 青藏高原与孟加拉湾区域平均CTF在所有季节均为TST, 即有从对流层到平流层净的向上输送, 2月强度最大, 7月为另一个极大值; 两个极大值有不同的产生机制, 后者决定于垂直项, 而前者由水平项决定。 (4) 青藏高原 (及孟加拉湾) 区域年平均CTF在1958~2001年之间的变化趋势在1982年左右出现一个转折: 1982年之前, CTF为递减过程; 而之后CTF为相对较强的增长。上述结果表明: 尽管冬季高原上空为下沉气流, 但高原上空的水平输送项有很强的向上贡献, 这与丛春华等 (2003) 得出的STT不一致。但需要指出的是, 根据Wei公式计算的CTF, 〖JP2〗尤其在急流附近, 对资料中存在的误差十分敏感 (Gettleman等, 2000), 因此青藏高原主体上空在冬季是STT还是TST, 有待于进一步的分析研究。     

Field study of dimethylsulfide oxibation in the boundary layer: Variations of dimethylsulfide,methanesulfonic acid,sulfur dioxide,non-sea-salt sulfate and aitken nuclei at a coastal site

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.     

Observation of a summer tropopause fold by ozonesonde at Changchun,China: Comparison with reanalysis and model simulation

Tropopause folds are one of the key mechanisms of stratosphere-troposphere exchange (STE) in extratropical regions, transporting ozone-rich stratospheric air into the middle and lower troposphere. Although there have been many studies of tropopause folds that have occurred over Europe and North America, a very limited amount of work has been carried out over northeastern Asia. Ozonesondes produced by the Institute of Atmospheric Physics were launched in Changchun (43.9°N, 125.2°E), Northeast China, in June 2013, and observed an ozone-enriched layer with thickness of 3 km and an ozone peak of 180 ppbv at 6 km in the troposphere. The circulation field from the European Centre for Medium-Range Weather Forecasts Interim Reanalysis (ERA-Interim) dataset shows that this ozone peak was caused by a tropopause fold associated with a jet stream at the eastern flank of the East Asian trough. By analyzing the ozone data from the ozone monitoring instrument and Weather Research and Forecasting model with Chemistry (WRF-Chem) simulations, it was found that a high ozone concentration tongue originating from the lower stratosphere at high latitude (near central Siberia) intruded into the middle troposphere over Changchun between 5 and 8 km on 12 June 2013. The high-resolution WRF-Chem simulation was capable of describing events such as the tropopause fold that occurred on the cyclonic shear side of the jet stream. In addition, the TRAJ3D trajectory model was used to trace the origin of measured secondary ozone peaks in the middle troposphere back, for example, to stratospheric intrusion through the tropopause fold.     

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.     

Airborne measurements of dimethylsulfide,sulfur dioxide,and aerosol ions over the Southern Ocean South of Australia

Vertical distributions of dimethylsulfide (DMS), sulfur dioxide (SO₂), aerosol methane-sulfonate (MSA), non-sea-salt sulfate (nss-SO₄ ^2-), and other aerosol ions were measured in maritime air west of Tasmania (Australia) during December 1986. A few cloudwater and rainwater samples were also collected and analyzed for major anions and cations. DMS concentrations in the mixed layer (ML) were typically between 15–60 ppt (parts per trillion, 10^–12; 24 ppt=1 nmol m^–3 (20°C, 1013 hPa)) and decreased in the free troposphere (FT) to about <1–2.4 ppt at 3 km. One profile study showed elevated DMS concentrations at cloud level consistent with turbulent transport (cloud pumping) of air below convective cloud cells. In another case, a diel variation of DMS was observed in the ML. Our data suggest that meteorological rather than photochemical processes were responsible for this behavior. Based on model calculations we estimate a DMS lifetime in the ML of 0.9 days and a DMS sea-to-air flux of 2–3 mol m^–2 d^–1. These estimates pertain to early austral summer conditions and southern mid-ocean latitudes. Typical MSA concentrations were 11 ppt in the ML and 4.7–6.8 ppt in the FT. Sulfur-dioxide values were almost constant in the ML and the lower FT within a range of 4–22 ppt between individual flight days. A strong increase of the SO₂ concentration in the middle FT (5.3 km) was observed. We estimate the residence time of SO₂ in the ML to be about 1 day. Aqueous-phase oxidation in clouds is probably the major removal process for SO₂. The corresponding removal rate is estimated to be a factor of 3 larger than the rate of homogeneous oxidation of SO₂ by OH. Model calculations suggest that roughly two-thirds of DMS in the ML are converted to SO₂ and one-third to MSA. On the other hand, MSA/nss-SO₄ ^2- mole ratios were significantly higher compared to values previously reported for other ocean areas suggesting a relatively higher production of MSA from DMS oxidation over the Southern Ocean. Nss-SO₄ ^2- profiles were mostly parallel to those of MSA, except when air was advected partially from continental areas (Africa, Australia). In contrast to SO₂, nss-SO₄ ^2- values decreased significantly in the middle FT. NH₄ ⁺/nss-SO₄ ^2- mole ratios indicate that most non-sea-salt sulfate particles in the ML were neutralized by ammonium.     

A comparison between natural and anthropogenic emissions of the reduced sulfur compounds H2S, COS, and CS2 in a tropical industrialized region

Extensive ambient concentration and flux measurements have been performed in the heavily polluted region of Cubatão/Brazil. Substantial contribution of anthropogenic sources to the local reduced sulfur burden has been observed. As a result of this atmospheric sulfur burden average gas exchange between vegetated soils and the atmosphere shows net deposition. Based mainly on own field measurements a local budget for H₂S, COS, and CS₂ has been made up in order to calculate anthropogenic emissions. All major sources and sinks in the chosen atmospheric reservoir (24×20×1 km) have been taken into account. Due to the small reservoir size fluxes across its boundaries are dominant sources and sinks. The differences between outflux and influx therefore account for the unknown anthropogenic emissions which have been determined to be 80±10 (H₂S), 66±15 (COS), and 29±6 Mmol year^-1 (CS₂). Other sources and sinks like natural emissions, chemical conversion, and dry deposition turned out to be of minor importance on a local scale. In fact, inside the investigated reservoir natural emissions were below 0.5% of anthropogenic emissions. Anthropogenic emissions of H₂S, COS, and CS₂ quantified in this work have been compared with global emission estimates for these compounds made by other authors. We conclude that global anthropogenic emissions of reduced sulfur compounds especially of COS and CS₂ are currently under-estimated.     

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.     

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 in rain clouds: Gas-liquid scavenging efficiencies and wet deposition rates in the presence of formaldehyde

The interaction of formaldehyde with SO₂ dissolved in the aqueous phase of clouds leads to the formation of hydroxymethane sulfonate. The impact of this process upon the gas-liquid equilibrium distribution of SO₂ in rain clouds and the ensuing wet SO₂ precipitation rate is explored. Model vertical SO₂ distributions are derived from observational data for three atmospheric regions: continental polluted, continental remote, and marine. The wet deposition rate for SO₂ in the polluted atmosphere increases by about a factor of two in the presence of formaldehyde compared with its absence. The effect is much stronger in the remote atmosphere leading to a potentially significant enhancement of wet SO₂ deposition. In the marine atmosphere, wet deposition of SO₂ may contribute as much as 35% to the total removal rate for SO₂ by all processes including dry deposition and chemical conversion to sulfate.     

Kinetics of ammonia and ammonium ion inhibition of the atmospheric oxidation of aqueous sulfur dioxide by oxygen

This is the first study, which shows both NH₃ and NH₄⁺ to inhibit the autoxidation of aqueous SO₂ in the pH range 7.0–8.5. The rate of the autoxidation, R _aut , in both buffered and unbuffered media at a fixed pH is in conformity with the rate law:

A Three-Dimensional Global Model Study of Carbonyl Sulfide in the Troposphere and the Lower Stratosphere

Global distributions of carbonyl sulfide and carbon disulfide have been calculated with a three-dimensional global model of the atmospheric general circulation (ECHAM). The model calculates a global sink strength for carbonyl sulfide of 0.3 Tg S yr^-1, with vegetation uptake being the largest sink. With this sink strength, the sources have to be close to the lower limit of the present estimate in the literature. The calculated mixing ratios are higher in the Southern Hemisphere than in the Northern Hemisphere. This interhemispheric gradient is the opposite of what is observed demonstrating that the present knowledge of the distribution of sinks and sources is not fully adequate. The model calculations support the idea that the open oceans could act as a net sink of carbonyl sulfide. The calculated stratospheric photolysis of carbonyl sulfide constitutes about 4% of the total sink of carbonyl sulfide. A stratospheric production of sulfate from carbonyl sulfide of 0.013 Tg S yr^-1 is obtained, which is 3 to 12 times less than what is needed to maintain the stratospheric sulfate aerosol layer. Although these results are associated with uncertainties, due to the low upper boundary and coarse vertical resolution of the model, they support recent findings of a low stratospheric production of sulfate from carbonyl sulfide. Instead, sulfur dioxide transported from the troposphere is calculated to be the most important precursor for the stratospheric sulfate aerosol layer.     

The characterization and distribution of aerosol and gaseous species in the winter monsoon over the western pacific ocean

In order to obtain a better understanding of the behavior of aerosols and SO₂ in the longrange transport through a marine boundary layer, a simple box-model is applied to the evaluation of the residence times of the species from the concentrations of gases and aerosols measured simulataneously on two islands in the West Pacific Ocean in the north-west monsoon. For Aitken and large particles, the residence time is varied from 3.7 to 7.4 days depending on the particle size, and their flux to the sea is equal to or slightly smaller than that of the free atmosphere. The residence time of giant particles is about one day and their flux to the sea is three times larger than that of the free atmosphere. The residence time of SO₂ is 15 hr, and the relative SO₂ mass flows of the deposition to the sea, of the diffusion to the free atmosphere and of the transformation to SO₄ ^2- are approximately 4, 1 and 1, respectively.     

The carbon isotopic ratio of atmospheric carbon dioxide at Tsukuba,Japan

To find out the secular and seasonal trends of the ¹³C value and CO₂ concentration in the surface air and the determination of the ¹³C in the atmospheric CO₂ collected at Tsukuba Science City was carried out during the period from July 1981 to October 1983. The monthly average of the ¹³C value of CO₂ in the surface air collected at 1400 LMT ranged from -7.52 to \s-8.45 with an average of -7.96±0.25 and the CO₂ concentration in the air varied from 334.5 l 1^-1 to 359 l 1^-1 with an average of 347.2±6.3 l 1^-1. The ¹³C value is high in summer and low in winter and is negatively correlated with the CO₂ concentration. In general, the relationship between the ¹³C and the CO₂ concentration is explainable by a simple mixing model of two different constant carbon isotopic species but the relationship does not always follow the model. The correlation between the ¹³C value and the CO₂ concentration is low during the plant growth season and high at other times. The observed negative deviation of the ¹³C value from the simple mixing model in the plant growth season is partly due to the isotopic fractionation process which takes place in the land biota.