Laboratory studies of some environmental variables controlling sulfur emissions from plants

Several trace sulfur gases that can have a significant influence on atmospheric chemistry are emitted from biological systems. In order to begin to address biological questions on the mechnisms of production of such gases, laboratory-scale experiments have been developed that reproduce such emissions under controlled conditions. Using a flux chamber technique, flats containing soil, or soil plus plants were sampled for the net fluxes of sulfur gases. The major sulfur gas emitted from all the plants tested (corn, alfalfa, and wheat) was dimethyl sulfide (DMS). Alfalfa and wheat also emitted lesser amounts of methanethiol, variable amounls of hydrogen sulfide, and in some experiments wheat emitted carbon disulfide. The use of a plant incubator allowed a systematic study of the effects of variables such as temperature, photon flux, and carbon dioxide levels, on these emissions. Fluxes of all the emitted sulfur gases increased exponentially with increasing air temperature, and increased with increasing photon flux up to a saturation level of \~300 E/m^–2 sec^-1. Three to four-fold changes in DMS flux were observed during light to dark or dark to light transitions. By varying the CO₂ content of the chamber flush gas, it was shown that the observed sulfur fluxes from corn and alfalfa were not related to the CO₂ concentration. Growing these crop plants through holes in a Teflon soil-covering film allowed a separate determination of soil and foliage emissions and substantiation of the light dependent uptake of COS by growing vegetation observed in previous field studies.     

On the wet removal of gaseous and particulate sulfur and nitrogen species from the atmosphere

The role of trace gases and aerosol particles in the control of sulfur and nitrogen levels in atmospheric precipitation is estimated on the basis of the enrichment factor in the precipitation of these elements relative to particulate matter in the air. By using air and precipitation chemistry data obtained at a Hungarian background air pollution station (K-puszta) it is found that the fraction of ammonium, nitrate and sulfate in precipitation, due to the removal of particulate matter is at least 59, 27 and 31%, respectively. The relationship between wet depositions and air concentrations of different species is determined statistically by applying daily data set. The regression equations obtained make the estimation of the sub-cloud scavenging ratios possible and they give some information on the magnitude of in-cloud scavenging processes. The results show that the in-cloud scavenging is a determining factor for precipitation sulfate, while it is relatively unimportant in the case of ammonium. The sub-cloud scavening of NO₂ and SO₂ is not too significant. However, for HNO₃, and NH₃ it is an effective process. The sub-cloud scavenging ratio of sulfur and nitrogen-containing particles varies around 0.25×10⁶.     

Wet removal of highly soluble gases

Partition, not kinetics, ultimately determines the concentration of highly soluble gases in cloud droplets. Partition equations are formulated and applied to idealized air-mass thunderclouds and precipitating stratus. Contribution to aqueous concentrations from sub-cloud scavenging of highly soluble gases is estimated at between 10 and 20% under relatively unpolluted conditions. Data indicate that evaporation can produce enhancements in concentration of as much as a factor of 3. The calculations give large-scale mean coefficients of wet removal of highly soluble gases of about 2.8×10^-6 s^-1 (4-day residence time) for air-mass thunderclouds and precipitating stratus. Removal is so effective that the mean scale heights of these gases should be decreased to 2 km or less. The criterion of high solubility in this paper is that K ^H (Henry's Law coefficient) > 10⁵ mol l^-1 atm^-1. Gases that are effectively highly soluble include HCl, HNO₃, H₂SO₄, H₂O₂, NH₃ in acid droplets, SO₂ in oxidizing droplets (and probably some light amines and sulfonic acids), but not SO₂ in the absence of oxidants, nor HCHO. A variation of removal coefficient and scale height with solubility is presented. A comparison of atmospheric NH₃ concentrations deduced from rain NH₄ ⁺ and measured directly gives reasonable agreement.     

Effects of high CO2 levels on surface temperature and atmospheric oxidation state of the early Earth

One-dimensional radiative-convective and photochemical models are used to examine the effects of enhanced CO₂ concentrations on the surface temperature of the early Earth and the composition of the prebiotic atmosphere. Carbon dioxide concentrations of the order of 100–1000 times the present level are required to compensate for an expected solar luminosity decrease of 25–30%, if CO₂ and H₂O were the only greenhouse gases present. The primitive stratosphere was cold and dry, with a maximum H₂O volume mixing ratio of 10^–6. The atmospheric oxidation state was controlled by the balance between volcanic emission of reduced gases, photo-stimulated oxidation of dissolved Fe⁺² in the oceans, escape of hydrogen to space, and rainout of H₂O₂ and H₂CO. At high CO₂ levels, production of hydrogen owing to rainout of H₂O₂ would have kept the H₂ mixing ratio above 2×10^–4 and the ground-level O₂ mixing ratio below 10^–11, even if no other sources of hydrogen were present. Increased solar UV fluxes could have led to small changes in the ground-level mixing ratios of both O₂ and H₂.     

Free tropospheric reservoir of natural sulfate

¹⁰Be is used as a spike of the natural background atmospheric aerosol to calculate the global flux of sulfur (F_S) into the free troposphere. The sulfate and¹⁰Be concentrations determined in polar snow are compared. On the basis of an annual¹⁰Be production rate of 1.21 10⁶ at.cm^-2, a very low figure of 2.9 Tg S a^-1 is calculated for F_S, which suggests that most of the sulfur emitted at ground level remains in the boundary layer. The role of OCS in the upper tropospheric sulfur budget is reviewed. It is also shown that cataclysmic volcanic eruptions may disturb considerably for 1–2 years this vast background tropospheric sulfur reservoir.     

Measurements of H2S and SO2 over the Atlantic Ocean

Concentrations of sulfur gases H₂S and SO₂ have been measured in the marine atmosphere over the Atlantic Ocean at various sites. Mean values of 40 ng H₂S m^-3 STP and 209 ng SO₂ m^-3 STP are the results of the measurements. A diurnal variation of H₂S concentration was detected on the west coast of Ireland with nighttime concentrations of up to 200 ng H₂S m^-3 STP and values below detection limit (15 ng H₂S m^-3 STP) during daytime.     

云水酸化数值模式计算

假定形成在硫酸、硫酸盐和硝酸盐核上的云滴,溶解酸、碱性气体在很短时间达到气—液平衡,进行了云水酸度的数值模式计算。计算结果表明,云水酸化不仅与云空气中酸、碱性气体和气溶胶粒子组分的初始浓度有关,而且还与云含水量有关。     

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.     

Atmospheric chemistry of carbon disulphide

The oxidation of carbon disulphide has been studied under conditions which are likely to pertain in the atmosphere. The quantum yield for direct photo-oxidation of CS₂ in air at 1 atm pressure, using near UV radiation was 0.012, with OCS as a major product. The rate coefficient (k ₁) for the reaction of OH with CS₂, was determined from measurements of OCS formation in the near UV photolysis of HONO?CS₂?O₂?N₂ mixtures. k ₁ was dependent on oxygen concentration rising from ≤4×10^-14 cm³ molecule^-1 s^-1 at O₂≤15 Torr to (2.0±1.0)×10^-12 cm³ molecule^-1 s^-1 at 1 atm air and 300 K. Equimolar amounts of carbonyl sulphide and sulphur dioxide were the major reaction products. The concentration of carbon disulphide in the ambient atmosphere was measured and the concentration to be expected in the background atmosphere was estimated. Rate and concentration data were used to show that carbon disulphide oxidation represents a major source for atmospheric carbonyl sulphide. It can also serve as an alternate source for atmospheric sulphur dioxide in addition to that produced from hydrogen sulphide and dimethyl sulphide. A consideration of atmospheric concentrations and rate data for these trace sulphur gases suggests that the natural sulphur budget is much smaller than the yearly amounts of sulphur dioxide emitted from anthropogenic sources.     

Determination of Atmospheric Sulfur Compounds Near a Volcanic Area in Greece

Volcanoes have been identified as an important natural source of sulfur compounds such as H₂S, CS₂, SO₂ and COS. The emission of volcanic sulfur compounds lead to the formation of sulfate aerosol and contribute to the acidity of precipitation. Two weekly measuring campaigns have been performed in the non-erupting volcanic area of Sousaki, Korinthou, to determine the concentration levels of the above-mentioned compounds in the region, while meteorological parameters were also recorded. The samplings have been performed during in a 24 h basis, covering two seasons of the year, a week in August 1998 and a week in January 1999. Reduced sulfur compounds were determined by a simple method of gas chromatography. Quality assurance procedure showed a very good precision and accuracy of the method utilized for the sulfur compounds determination. In accordance with literature, H₂S was the dominant sulfur compound at the volcano area, while COS, and CS₂ didn't present significantly high values. Nevertheless, the concentration levels of the above pollutants are varying depending on the volcano magnitude and status (active, extinct).     

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.     

A global three-dimensional model of the tropospheric sulfur cycle

The tropospheric part of the atmospheric sulfur cycle has been simulated in a global three-dimensional model. The model treats the emission, transport, chemistry, and removal processes for three sulfur components; DMS (dimethyl sulfide), SO₂ and SO₄ ^2– (sulfate). These processes are resolved using an Eulerian transport model, the MOGUNTIA model, with a horizontal resolution of 10° longitude by 10° latitude and with 10 layers in the vertical between the surface and 100 hPa. Advection takes place by climatological monthly mean winds. Transport processes occurring on smaller space and time scales are parameterized as eddy diffusion except for transport in deep convective clouds which is treated separately. The simulations are broadly consistent with observations of concentrations in air and precipitation in and over polluted regions in Europe and North America. Oxidation of DMS by OH radicals together with a global emission of 16 Tg DMS-S yr^–1 from the oceans result in DMS concentrations consistent with observations in the marine boundary layer. The average turn-over times were estimated to be 3, 1.2–1.8, and 3.2–6.1 days for DMS, SO₂, and SO₄ ^2– respectively.     

Synergistic Effects of Nitrogen Amendments and Ethylene on Atmospheric Methane Uptake under a Temperate Old-growth Forest

An increase in atmospheric nitrogen (N) deposition can promote soil acidification, which may increase the release of ethylene (C2H4) under forest floors. Unfortunately, knowledge of whether increasing N deposition and C2H4 releases have synergistic effects on soil methane (CH4) uptake is limited and certainly deserves to be examined. We conducted some field measurements and laboratory experiments to examine this issue. The addition of (NH4)2SO4 or NH4Cl at a rate of 45 kg N ha-1 yr-1 reduced the soil CH4 uptake under a temperate old-growth forest in northeast China, and there were synergistic effects of N amendments in the presence of C2H4 concentrations equal to atmospheric CH4 concentration on the soil CH4 uptake, particularly in the NH4Cl-treated plots. Effective concentrations of added C2H4 on the soil CH4 uptake were smaller in NH+4 -treated plots than in KNO3-treated plots. The concentration of ca 0.3 μl C2H4 L-1 in the headspace gases reduced by 20% soil atmospheric CH4 uptake in the NH4Cl-treated plots, and this concentration was easily produced in temperate forest topsoils under short-term anoxic conditions. Together with short-term stimulating effects of N amendments and soil acidification on C2H4 production from forest soils, our observations suggest that knowledge of synergistic effects of NH+4 , rather than NO3- , amendments and C2H4 on the in situ soil CH4 uptake is critical for understanding the role of atmospheric N deposition and cycling of C2H4 under forest floors in reducing global atmospheric CH4 uptake by forests. Synergistic functions of NH4+ -N deposition and C2H4 release due to soil acidification in reducing atmospheric CH4 uptake by forests are discussed.     

Numerical study of the oxidation process of dimethylsulfide in the marine atmosphere

A box model, involving simple heterogeneous reaction processes associated with the production of non-sea-salt sulfate (nss-SO ₄ ^2– ) particles, is used to investigate the oxidation processes of dimethylsulfide (DMS or CH₃SCH₃) in the marine atmosphere. The model is applied to chemical reactions in the atmospheric surface mixing layer, at intervals of 15 degrees latitude between 60° N and 60° S. Given that the addition reaction of the hydroxyl radical (OH) to the sulfur atom in the DMS molecule is faster at lower temperature than at higher temperature and that it is the predominant pathway for the production of methanesulfonic acid (MSA or CH₃SO₃H), the results can well explain both the increasing tendency of the molar ratio of MSA to nss-SO ₄ ^2– toward higher latitudes and the uniform distribution with latitude of sulfur dioxide (SO₂). The predicted production rate of MSA increases with increasing latitude due to the elevated rate constant of the addition reaction at lower temperature. Since latitudinal distributions of OH concentration and DMS reaction rate with OH are opposite, a uniform production rate of SO₂ is realized over the globe. The primary sink of DMS in unpolluted air is caused by the reaction with OH. Reaction of DMS with the nitrate radical (NO₃) also reduces DMS concentration but it is less important compared with that of OH. Concentrations of SO₂, MSA, and nss-SO ₄ ^2– are almost independent of NO _x concentration and radiation field. If dimethylsulfoxide (DMSO or CH₃S(O)CH₃) is produced by the addition reaction and further converted to sulfuric acid (H₂SO₄) in an aqueous solution of cloud droplets, the oxidation process of DMSO might be important for the production of aerosol particles containing nss-SO ₄ ^2– at high latitudes.     

On the scavenging of SO2 by cloud and raindrops: II. An experimental study of SO2 absorption and desorption for water drops in air

For the purpose of testing our previously described theory of SO₂ scavenging a laboratory investigation was carried out in the UCLA 33 m long rainshaft. Drops with radii between 250 and 2500 m were allowed to come to terminal velocity, after which they passed through a chamber of variable length filled with various SO₂ concentrations in air. After falling through a gas separating chamber consisting of a fluorocarbon gas the drops were collected and analyzed for their total S content in order to determine the rate of SO ₂ absorption.The SO₂ concentration in air studied ranged between 1 and 60% (v). Such relatively large concentrations were necessary due to the short times the drops were exposed to SO₂ in the present setup. The present experimental results were therefore not used to simulate atmospheric conditions but rather to test our previously derived theory which is applicable to any laboratory or atmospheric condition. Comparison of our studies with the results from our theory applied to our laboratory conditions led to predicted values for the S concentration in the drops which agreed well with those observed if the drops had radii smaller than 500 m. In order to obtain agreement between predicted and observed S concentrations in larger drops, an empirically derived eddy diffusivity for SO₂ in water had to be included in the theory to take into account the effect of turbulent mixing inside such large drops.In a subsequent set of experiments, drops initially saturated with S (IV) were allowed to fall through S-free air to determine the rate of SO ₂ desorption. The results of these studies also agreed well with the results of our theoretical model, thus justifying the reversibility assumption made in our theoretical models.In a final set of experiments, the effects of oxidation on SO₂ absorption was studied by means of drops containing various amounts of H₂O₂. For comparable exposure times to SO₂, the S concentration in drops with H₂O₂ was found to be up to 10 times higher than the concentration in drops in which no oxidation occurred.     

Observation of hydrogen peroxide concentrations in a Japanese red pine forest

In order to study the concentrations of hydrogen peroxide (H₂O₂) and the factors controlling its concentrations, we monitored concentrations of H₂O₂ and other gases such as sulfur dioxide, ozone, and NO _x as well as meteorological factors such as air temperature, relative humidity, and wind direction/speed during eight measurement periods from 2000 to 2002 in a Japanese red pine forest in Japan. The H₂O₂ concentrations ranged from below 0.01 to 1.64 ppb, and analysis of the diurnal variation in H₂O₂ concentration showed high concentrations around noon, and low concentrations in the morning and late afternoon. The H₂O₂ concentrations were high in early summer, when O₃ concentration, temperature, and solar radiation were high, and were low in fall, when O₃ concentration, temperature, and solar radiation were low. We propose that O₃ concentration affects the production of H₂O₂ in the monitored region during the period under study, but that high H₂O₂ concentrations were sometimes caused by the transport of polluted air from urban regions. H₂O₂ concentrations decreased remarkably when SO₂ concentrations increased by transported volcanic emission on Miyake Island. In the absence of the effects of SO₂, H₂O₂ concentrations increased with increasing O₃ concentration and temperature.     

南京地区大气冰核浓度的测量及分析

2011年5～8月期间使用5L混合型云室以及静力扩散云室对南京不同成核机制的大气冰核进行了观测,进而分析了近地层冰核浓度特征。结果表明:活化温度为－20°C时,5L混合型云室观测的总冰核浓度为20.11个/L,静力扩散云室模拟高水汽(计算的云室内水面过饱和度为5%)和低水汽(计算的云室内冰面过饱和度为5%)条件下冰核浓度分别为0.93个/L以及0.29个/L。晴好条件下冰核浓度具有明显的日变化特征,白天冰核浓度高于夜间;在下午时段冰核浓度达到全天最高值,这说明大气冰核可能与大气湍流强度、人类活动以及工业污染有关。降水对冰核的清除作用明显,台风系统过程中冰核浓度明显增加。南京地区冰核浓度随温度降低和湿度增加而增加。后向轨迹模式分析表明东北海洋气团冰核浓度最高,不同气团中冰核浓度的差异随着活化温度的降低而减小。个例分析秸秆燃烧生成的PM₁(大气中直径小于或者等于1 μm的颗粒物)与冰核关系发现燃烧产物对冰核有一定的贡献。     

Emissions, Concentrations, & Temperature: A Time Series Analysis

We use recent advances in time series econometrics to estimate the relation among emissions of CO₂ and CH₄, the concentration of these gases, and global surface temperature. These models are estimated and specified to answer two questions; (1) does human activity affect global surface temperature and; (2) does global surface temperature affect the atmospheric concentration of carbon dioxide and/or methane. Regression results provide direct evidence for a statistically meaningful relation between radiative forcing and global surface temperature. A simple model based on these results indicates that greenhouse gases and anthropogenic sulfur emissions are largely responsible for the change in temperature over the last 130 years. The regression results also indicate that increases in surface temperature since 1870 have changed the flow of carbon dioxide to and from the atmosphere in a way that increases its atmospheric concentration. Finally, the regression results for methane hint that higher temperatures may increase its atmospheric concentration, but this effect is not estimated precisely.     

Biogenic hydrogen sulphide emissions and non-sea sulfate aerosols over the Indian Sundarban mangrove forest

Temporal variations in atmospheric hydrogen sulphide concentrations and its biosphere-atmosphere exchanges were studied in the World’s largest mangrove ecosystem, Sundarbans, India. The results were used to understand the possible contribution of H₂S fluxes in the formation of atmospheric aerosol of different size classes (e.g. accumulation, nucleation and coarse mode). The mixing ratio of hydrogen sulphide (H₂S) over the Sundarban mangrove atmosphere was found maximum during the post-monsoon season (October to January) with a mean value of 0.59?±?0.02 ppb and the minimum during pre-monsoon (February to May) with a mean value of 0.26?±?0.01 ppb. This forest acted as a perennial source of H₂S and the sediment-air emission flux ranged between 1213?±?276 μg S m^?2 d^?1(December) and 457?±?114 μg S m^?2 d^?1 (August) with an annual mean of 768?±?240 μg S m^?2d^?1. The total annual emissions of H₂S from the Indian Sundarban were estimated to be 1.2?±?0.6 Tg S. The accumulation mode of aerosols was found to be more enriched with non-sea salt sulfate with an average loading of 5.74 μg m^?3 followed by the coarse mode (5.18 μg m^?3) and nucleation mode (1.18 μg m^?3). However, the relative contribution of Non-sea salt sulfate aerosol to total sulfate aerosol was highest in the nucleation mode (83%) followed by the accumulation (73%) and coarse mode (58%). Significant positive relations between H₂S flux and different modes of NSS indicated the likely link between H₂S, a dominant precursor for the non-sea salt sulfate, and non-sea sulfate aerosol particles. An increase in H₂S emissions from the mangrove could result in an increase in enhanced NSS in aerosol and associated cloud albedo, and a decrease in the amount of incoming solar radiation reaching the Sundarban mangrove forest.     

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.