Sensitivity of Native Desert Vegetation To SO2 and to SO2 and NO2 Combined

Interest in air pollution injury to native vegetation has been generated with the construction and planned construction of large coal-fired power plants near the coal reserves in the southwest desert areas of the United States. Since information on the effects of SO₂ on these native species was not available in the literature, fumigation studies were conducted with portable chambers placed over native species in the field with SO₂ and SO₂ + NO₂. Pollutant concentrations were measured and controlled with instruments located in a mobile laboratory. Each fumigation was of two hours duration and the concentration ranged from 0.5 to 11 ppm SO₂ and from 0.1 to 5 ppm NO₂. Concentrations of SO₂ above 2 ppm were required to cause injury to all but a few of the 87 species studied. Many of the native desert species proved to be highly resistant to injury from these gases.     

Effects of SO2 and/or NO2 on Native Plants of the Mojave Desert and Eastern Mojave-Colorado Desert

Ten species of plants, five perennials and five annuals, native to the Mojave desert were grown in pots and fumigated in open top plastic greenhouses, 25 hours/week, with SO₂ and/or NO₂. Three levels of SO₂: 2.0, 0.67, and 0.22 parts per million (ppm); three levels of NO₂: 1.0, 0.33, and 0.11 ppm; three treatments with 2.0 ppm SO₂ + 1.0 ppm NO₂, 0.67 ppm SO₂ + 0.33 ppm NO₂ and 0.22 ppm SO₂ + 0.11 ppm NO₂ plus untreated control plants were used in the fumigations. The perennials were fumigated for 16 weeks in 1977 and 32 weeks in 1978. Three species of annuals were grown and fumigated for 17 weeks, a fourth for 16 weeks, and a fifth for 12 weeks. A second crop of the first three annuals were grown; one for 12 weeks, a second for 8, and a third for 9 weeks.

Individual species differed widely in their particular responses to the fumigants. The fumigations of perennials with 2.0 ppm of SO₂ or NO₂ at 1.0 ppm caused extensive leaf injury, and reduced growth or dry weight of Larrea divaricate Cav., Chilopsls linearis Cav., and Ambrosia dumosa (Gray) Payne. The combined fumigants had additive effects. No suggestion of synergism was noted. These fumigants at lower concentrations stimulated lateral growth of Encelia farinosa Gray ex Torr. and Erodium cicutarium (L.) L’Her., dry weight of Atriplex canescens (Pursh) Nutt. and Plantago insularis Eastw. and increased flowering of Balleya pleniradiata Harv. and Gray, thus indicating beneficial effects.

Annual species were more severely affected by 2.0 ppm SO₂ than the perennials and extensive injury or death of plants occurred in all annuals. At the 0.67 ppm level severe leaf injury occurred. NO₂ at 1.0 ppm was less injurious than SO₂ and addition of NO₂ to SO₂ suggested an antagonistic effect. Plant survival and flowering was increased by adding NO₂ to plants being treated with SO₂

Comparison of perennial species showed Larrea sensitive, Chilopsis, Encella and Ambrosia intermediate, and Atriplex resistant. The annual species showed Erodium cicutarium and Plantago Insularis to be extremely sensitive, Phacelia crenulata Torr very sensitive and Baileya pleniradiata sensitive. Chaenactis carphoclinia Gray grew poorly and no valid rating was possible.     

Variable Responses of Soybeans to Mixtures of Ozone and Sulfur Dioxide

Foliar injury and shoot fresh weight responses of soybeans (Glycine max L.) ‘Lee 68’ and ‘Dare’ exposed to mixtures of ozone (O₃) and sulfur dioxide (SO₂) were greater than additive (synergistic), less than additive (antagonistic), or additive. The result depended on the concentrations of O₃ and SO₂, the exposure duration, and the amount of injury caused by each gas singly. Synergism usually occurred when injury from O₃ or SO₂ singly was slight to moderate. Antagonism usually occurred when injury from either gas singly was severe. In many cases of antagonism, the injury and fresh weight effects of the mixture were less than those from SO₂ alone, suggesting that O₃ can sometimes protect soybeans from SO₂.     

Stainless Steel Anti-Smog Mufflers—Cut Air Pollution

An automatic process gas chromatograph has been developed for use on the recovery furnace stack of a Kraft pulp mill. The instrument analyzes for widely varying concentrations of H₂S, SO₂, CH₃SH and higher order sulfur compounds. It is insensitive to the fixed gases and water vapor, and performs its analysis in approximately ten minutes. The instrument features a microcoulometric detector giving it sensitivity to H₂S as low as 0.1 ppm, and SO₂ and CH₃SH as low as 0.5 ppm. The major limit to even higher sensitivity at this stage of development lies with two problems: the background noise level in the detector and the sulfur compound absorption in the Porapak Q chromatograph column. At the reported sensitivity, a 40-ml gas sample was used. The instrument also contains a data analysis system supplementary to the usual strip chart recorder. This system is made up of a digital voltmeter, a digital translator, and a teletype and hence allows the transfer of the output data to a digital computer for processing. The processed data are usually presented in the form of ppm quantities of the component gases in the stack gas. The instrument has worked successfully on small furnace effluent for periods of 25 hr but has not been tried on recovery furnace stacks. It has also run on prepared samples for periods of up to seven days with no maintenance or attendance necessary.     

Use of Plants for Air Pollution Monitoring

Leaf injury data from acute and chronic exposure studies of Dare soybean were regressed against the logarithms of exposure time and O₃ and SO₂ concentrations to develop a new two-pollutant leaf injury model (which explains 88% of the variance) and to calculate the parameters of best fit for this new model and a previously developed one-pollutant model. Using the calculated parameters, the percentage of leaf surface Injured over a growing season by O₃, SO₂, or both simultaneously was estimated for an ambient air sampling site located 2 miles from a coal burning power plant. For this site, the one- and two-pollutant models predicted that SO₂ effects would be negligible If SO₂ concentrations never exceeded the National Ambient Air Quality Standard (NAAQS) of 0.50 ppm, averaged over 3 h. However, calculations suggest that O₃ may injure up to 24% of Dare soybean leaf surface over a growing season even though the O₃ NAAQS of 0.12 ppm, averaged over 1 h, is never exceeded. Because the 3 h SO₂ standard is exceeded at very few places, the O₃ model is usually sufficient to estimate Dare soybean leaf Injury. Leaf injury is estimated by taking the logarithm of the summation of each daytime hour’s exponentiated O₃ concentration (c) measured at an ambient air sampling site over a growing season. This is expressed as: z = -0.0828 + 0.4876 in (Σco₃ ^2.618), where z is the Gaussian transform of percent leaf injury. The methods developed in this paper, using Dare soybean data as an example, may apply to other plants.     

Hybrid-Type Electrostatic Precipitator

Three experiments were designed to determine the effects of SO₂ concentration on two Southeastern oat varieties—Caroiee and Coker 227. The plants were grown under uniform conditions prior to and after the experimental growth period. During the 7 to 14 day experimental growth period the plants were subjected to four growth temperatures (18/14, 22/18, 26/22 and 30/26° C day/night temperatures) and exposed 2 or 4 times to specific concentrations of SO₂ (from 0 to 4 ppm) for 1.5 or 3.0 hr periods. In the first two experiments, the exposure temperatures were varied (18° to 30° C). In the third design, the exposure temperatures remained constant and two exposure relative humidities (55 and 80%) were used. Injury and growth reductions were more severe in Coker 227 than in Caroiee. Root dry weight (RDW) was affected more than top dry weight (TDW). Plants were more sensitive at the higher growth temperatures. Exposure temperatures had little to variable effects. Plants were more sensitive at 80% than at 55% relative humidity. Biomass was reduced at 0.4 ppm SO₂ after four 3 hr exposures and at 0.75 ppm after two 1.5 hr exposures, but growth was also increased as often. These concentrations approached the accepted threshold for adverse effects to sensitive vegetation. Foliar injury was highly correlated with growth reductions.     

Control of Claus Plant Sulfur Compound Emissions

The body of information of this paper is directed to those individuals charged with selecting a process to control atmospheric sulfur emissions from Claus plants serving refineries, gas processing installations, and chemical plants. The TGT process developed by the French Petroleum Institute (IFP) is an extension of the Claus reaction itself in the liquid phase. Mixed H₂S and SO₂ in tail gas from Claus units is fed to a packed tower in which a solution of proprietary catalyst in a high BP polyglycol circulates countercurrent to the gas flow. The mixed gases react with the catalyst to form a complex, which in turn reacts with more gases to produce elemental sulfur. Reaction temperature keeps the sulfur above its melting point. Product accumulates in the boot of the tower and is drawn off continuously through a seal leg.

The IFP TGT process is simple in design and units have simple construction, characterized by use of low carbon steel and the use of very few pieces of equipment. Of all processes used today to take effluent sulfur values down to 1000 ppm SO₂ after incineration, the IFP TGT process requires the least capital investment and the lowest operating costs. Twenty-six full scale plants are operating or under design or construction: nine each in the U.S. and Japan, five in the U.S.S.R. and Poland, two in western Europe and one in Canada. Capacities of the Claus plants served range from 45 to 800 Lt/d sulfur.     

An Air Quality Data Analysis System for Interrelating Effects,Standards, and Needed Source Reductions: Part 3. Vegetation Injury

Acute leaf injury data are analyzed for 19 plant species exposed to ozone or sulfur dioxide. The data can be depicted by a new leaf injury mathematical model with two characteristics: (1) a constant percentage of leaf surface is injured by an air pollutant concentration that is inversely proportional to exposure duration raised to an exponent; (2) for a given exposure duration, the percent leaf injury as a function of pollutant concentration tends to fit a lognormal frequency distribution. Leaf injury as a function of laboratory exposure duration is modeled and compared with ambient air pollutant concentration measurements for various averaging times to determine which exposure durations are probably most important for setting ambient air quality standards to prevent or reduce visible leaf injury. The 8 hour average appears to be most important for most of the plants investigated for most sites, 1 hr concentrations are important for most plants at a few sites, and 3 hr S0₂ concentrations are important for some plants, especially those exposed to isolated point sources of the pollutant. The 1, 3, and 8 hr threshold injury concentrations are listed for each of the 19 plant species studied. To prevent or reduce acute leaf injury, fixed, nonoverlapping ambient air quality measurements and standards are recommended for averaging times of 1, 3, and 8hr.     

Discharge Electrodes and Electrostatic Precipitators

Controlled fumigation experiments were conducted to determine the dose-response relationships for four species of urban trees exposed to sulfur dioxide. The species chosen were ginkgo, Norway maple, pin oak, and Chinese elm.

Results indicated that resistance to SO₂ increased among the species in the following order: Chinese elm, Norway maple, ginkgo, pin oak. Elm showed almost 100% leaf necrosis at exposures over 2 ppm for 6 hr, and severe chlorosis and necrosis at 0.25 ppm for 30 days. Fifty per cent leaf necrosis occurred on Norway maple at 3 ppm for 6 hr, and on ginkgo at 4 ppm for 6 hr, and both species developed moderate marginal chlorosis at 0.50 ppm for 30 days. Injury on pin oak was minor, even at 8 ppm for 8 hr, but at 0.50 ppm for 30 days, a slight overall chlorosis developed on the leaves.

The relative susceptibilities of the four species were the same in the long-term as in the short-term exposures. The shapes of the dose-response surfaces indicated that duration of exposure and concentration of the pollutant were of equal importance in producing injury on Chinese elm and probably on pin oak, but on Norway maple and ginkgo, concentration of SO₂ was of greater importance than the duration of exposure.     

Long-Term Operation of a Biofilter for Simultaneous Removal of H2S and NH3

Abstract

Simultaneous removal of NH₃ and H₂S was investigated using two types of biofilters—one packed with wood chips and the other with granular activated carbon (GAC). Experimental tests and measurements included analyses of removal efficiency (RE), metabolic products, and results of long-term operation (around 240 days). The REs for NH₃ and H₂S were 92 and 99.9%, respectively, before deactivation. After deactivation, the RE for NH₃ and H₂S were decreased to 30–50% and 75%, respectively. The activity of nitrifying bacteria was inhibited by high concentrations of H₂S (over 200 ppm) but recovered gradually after H₂S addition was ceased. However, the Thiobacillus thioparus as sulfur oxidizing bacteria did not show inhibition at the NH₃ concentration under 150-ppm conditions. The deactivation of the biofilter was caused by metabolic products [elemental sulfur and (NH₄)₂SO₄] ac-cumulating on the packing materials during the extended operation. The removal capacities for NH₃ and H₂S were 6.0–8.0 and 45–75 mg N, S/L/hr, respectively.     

Inhalation Route Effects on Exposure to 2.0 Parts Per Million Sulfur Dioxide in Normal Subjects

A number of Investigations have attributed the control of the nasal to oral/nasal ventilation transition to nasal resistance. To investigate possible changes In nasal resistance due to sulfur dioxide (SO₂) exposure, 14 subjects (7 men and 7 women), healthy nonsmokers, between the ages of 20 and 46 years, were exposed for 30 minutes to filtered air while free breathing and to 2.0 ppm SO₂ with either free breathing, forced oral or forced nasal breathing with continuous exercise at a workload 300 kg>m/min below the workload which Initiated cross-over from nasal to oral/nasal breathing in a preliminary incremental workload test. An Incremental work test under the ambient conditions was performed immediately following the 30-minute exercise to ascertain any change in the cross-over ventilation. Pre- and post-measures of pulmonary functions were obtained to ascertain any changes In these parameters due to the exposure. There was a significant difference in the workload at which cross-over occurred following forced oral breathing in 2.0 ppm sulfur dioxide. The nasal ventilation prior to cross-over and the nasal component of ventilation were significantly smaller for this exposure condition, indicating a possible change in nasal dynamics following the 30 minutes of forced oral breathing in 2.0 ppm SO₂. Lack of concomitant changes in pulmonary function tests including airway resistance suggests that breathing 2.0 ppm SO₂ does not affect normal subjects whether administration is by free, forced oral or forced nasal breathing.     

Shock Wave Cleaning of Air Filters

The trends in and relationships between ambient air concentrations of sulfur dioxide and sulfate aerosols at 48 urban sites and 27 nonurban sites throughout the U.S. between 1963 and 1972 have been analyzed. The substantial decreases in ambient SO₂ concentrations measured at urban sites in the eastern and midwestern U.S. are consistent with the corresponding reductions in local SO₂ emissions, but these decreases have been accompanied by only modest decreases in ambient sulfate concentrations. Large differences in the amounts of SO₂ emitted within individual air quality control regions are associated with much smaller differences in the corresponding ambient sulfate concentrations. Substantial changes in the patterns of SO₂ emissions between air quality regions result in essentially no differences between ambient sulfate concentrations in those air quality regions. Comparisons of several air quality regions in the eastern and western U.S. with similar SO₂ emission levels and patterns of emissions clearly demonstrates the higher ambient sulfate concentration levels in eastern air quality control regions. Relationships between SO₂, sulfates, and vanadium concentrations at eastern nonurban U.S. sites cannot be explained by local emission sources. These various observed results can be best explained by long distance sulfur oxide transport with chemical conversion of SO₂ to sulfates occurring over ranges of hundreds of kilometers. This conclusion has been suggested earlier and the present analysis strongly supports previous discussions. An impact of long range transport of sulfates is to emphasize the need for Consistent strategies for reduction of sulfur oxides throughout large geographical regions. Additions of large capacities involving elevated sources in mid-continental or western regions could result in significant increases in sulfate concentrations well downwind of such sources. Some of the types of research activities required to quantitate crucial experimental parameters are discussed.     

The Survival of Airborne Serratia marcescens in Urban Concentrations of Sulfur Dioxide

Aerosols of Serratia marcescens ATCC 274 were suspended in a 709L rotating drum at 20 ± 1 °C and high to mid-range relative humidities. At specified times after bacterial aerosolization, sulfur dioxide was added to concentrations of 2.5, or 5 mg/m³. Viable cell decay rate constants, in control aerosols without added sulfur dioxide, increased rapidly from near 100% to 60% RH in the first hour (termed: young aerosol) of suspension, and from a minimum rate constant at 80% in the succeeding four hours (termed: old aerosol).Upon addition of sulfur dioxide to a cloud of S. marcescens, generally, viable cell decay rate constants increased further. One exception was at 80% relative humidity where maximum resistance to SO₂ accelerated death was observed for old aerosols. Cells in young aerosols were particularly sensitive to SO₂ addition at mid-range humidities, while in older aerosols the cells were insensitive to up to 5 mg SO₂/m³ introduced at high RH; but were up to 10 times more sensitive than cells in young aerosols to a given increase (from 2.5 to 5 mg/m³) in SO₂ concentration at mid-range humidities.     

Toxicologic Appraisal of Particulate Matter,Oxides of Sulfur,and Sulfuric Acid

An examination of the available toxicological literature indicates that sulfur dioxide itself would be properly classified as a mild respiratory irritant, the main portion of which is absorbed in the upper respiratory tract. The reported industrial experience of symptoms of mild chronic respiratory irritation from exposures at or above 5 ppm is compatible with what would have been predicted on the basis of available toxicological data. The basic physiological response to inhalation of pure SO₂ appears to be a mild degree of bronchoconstriction reflected in a measurable increase in flow resistance. Although the response is highly variable, most individuals tested have responded to 5 ppm and levels of 5 to 10 ppm have upon occasion produced severe bronchospasm in sensitive individuals. This serves to point up the fact that experience with the industrial Threshold Limit Value (5 ppm) is not applicable as a guide for the general population. Although the majority of individuals tested have shown no detectable response to levels of 1 ppm, there are again sensitive individuals who have responded. It is not known whether these individuals would have responded to concentrations lower than this. The response of these more sensitive individuals to 1 ppm would be classified as detectable response, not as severe bronchospasm. An examination of the available toxicological literature also indicates that sulfuric acid and irritant sulfates, to the extent that the latter have been examined, are more potent irritants than sulfur dioxide. This has been demonstrated in studies using morality and lung pathology as criteria as well as in studies using alterations in pulmonary function in experimental animals and human subjects. The irritant potency of these substances is affected by particle size and by relative humidity, which factors are probably interrelated. It is unfortunate that these substances have not been as yet studied in as great detail as has the less irritant sulfur dioxide. There is evidence which cannot be ignored, even though it is based entirely on animal experiments of one investigator, indicating that the presence of particulate material capable of oxidizing sulfur dioxide to sulfuric acid caused a three to fourfold potentiation of the irritant response. The aerosols causing this potentiation were soluble salts of ferrous iron, manganese and vanadium all of which would become droplets upon inhalation. Insoluble aerosols such as carbon, iron oxide fume, triphenylphosphate or fly ash did not cause a potentiation of the irritant action of SO₂ even when used at higher concentrations. The concentrations of SO₂ used in these various experiments were in some cases as low as 0.16 ppm. The catalytic aerosols were used at concentrations of 0.7 to 1 mg/m³ which is above any reported levels of these metals in urban air. If the SO₂ present as an air pollutant remained unaltered until removed by dilution, there would be no evidence in the toxicological literature suggesting that it would be likely to have any effects on man at prevailing levels. Studies of atmospheric chemistry have shown that SO₂ does not remain unaltered in the atmosphere, especially under onditions of high humidity and in the presence of particulate material, but is converted to H₂SO₄. Such a conversion increases its irritant potency. On this basis the toxicological literature combined with the literature of atmospheric chemistry suggest that sulfur dioxide levels be controlled in terms of the potential formation of irritant particles. This means that control measures as far as feasible should be aimed at both SO₂ and particulate material and not against either alone.     

Interactions of Sulfur Dioxide with Insoluble Suspended Particulate Matter

A laboratory study was conducted of the heterogeneous catalysis of sulfur dioxide at ppm concentrations in air by insoluble particles of CaCO₂, V₂O₅, Fe₂0₃, flyash from a coal-burning power plant, MnCO₂, activated carbon, and suspended particulate matter from urban air. The investigalion was performed by utilizing a new technique for aerosol stabilization which consists of depositing the aerosol on Teflon beads in a fluidized bed. The Teflon beads with deposited aerosol particles were then packed into a flow reactor. Progress of the chemical reaction of SO₂ with deposited particles was continuously monitored by determining the SO₂ concentrations in the reactor effluent with a microcoulometer.

In this investigation, CaCOg, V₂O₅, and flyash were essentially inert to SO₂ at room temperature. Fe₂O₃, activated carbon, MnO₂, and suspended particulate matter from urban air sorbed SO₂ from air streams with up to 14.4 ppm SO₂ in air. Evidence is presented which suggests that a substantial part of the sorbed SO₂ was physically adsorbed.

Bioassay procedures which utilize pulmonary flow resistance changes in guinea pigs to monitor response to inhaled SO₂-aerosol mixtures in air have indicated the weak or non-potentiating capacity of insoluble aerosols as contrasted to soluble aerosols. Potentiating response of an aerosol appears to be strongly associated with reaction of SO₂ in a water droplet containing aerosol ions and not with physically adsorbed SO₂ on an insoluble aerosol.     

A simulation of sulfur wet deposition and its dependence on the inflow of sulfur species to storms

Numerical precipitation scavenging models are used to investigate the relationship between the inflow concentrations of sulfur species to precipitation systems and the resulting sulfur wet deposition. Simulations have been made for summer and winter seasons using concentration ranges of SO₂, aerosol SO₄²⁻, H₂O₂ and O₃ appropriate for the eastern U.S. summer simulations use one-dimensional timedependent convective cloud and scavenging models; winter simulations use two-dimensional steady-state warm-frontal models. Sulfur scavenging mechanisms include nucleation scavenging of aerosol, aqueous reactions of H₂O₂, O₃ and HCHO with S(IV), and nonreactive S(IV) scavenging. Over the wide range of conditions that have been examined, the relation between sulfur inflow and sulfur wet deposition varies from nearly linear to strongly nonlinear. The degree of nonlinearity is most affected by aerosol SO₄²⁻ levels and relative levels of SO₂ vs H₂O₂. Higher aerosol SO₄²⁻ levels (as found in summer) produce a more linear relation. The greatest nonlinearity occurs when SO₂ exceeds H₂O₂. Winter simulations show more nonlinearity than summer simulations.     

Gaseous Sulfur Pollutants from Urban and Natural Sources

Major aspects of the circulation through the atmospheric environment of sulfur pollutants have been estimated, including source magnitudes, residual atmospheric concentrations, and scavenging processes. The compounds considered include SO₂ and H₂S, as well as sulfates. One-third of the sulfur reaching the atmosphere comes from pollutant sources, mainly as SO₂. Within the atmosphere there is a net transfer of sulfur from land to ocean areas. Pollutant sources annually amount to 73 × 10⁶ tons as sulfur while natural sources amount to 142 × 10⁶ tons, mainly as H₂S and sulfate sea spray. More than two thirds of the natural and pollutant sulfur emissions occur in the northern hemisphere. When only pollutant emissions are considered, 93 per cent occur in the northern hemisphere.     

Determination of Sulfur Oxides in the Flue Gases of the Pulping Processes

The body of information presented in this paper is directed to the operating personnel and process engineers employed in the power and recovery departments of a chemical pulping operation. The proper evaluation of the total analytical and sampling system (TASS), to be used in the determination of sulfur oxides is as important as a proper analytical and recording system (ARS). The presence of other sulfur gaseous compounds and particulates could greatly influence the results of the determination.

The analytical method employed determines sulfur dioxide and trioxide from an aliquot of the trapping solution, 3% hydrogen peroxide and 8 0% isopropyl alcohol respectively. The aliquot is titrated with barium perchlorate in the presence of Thorin indicator. The results of evaluating the method indicated negligible interference from the presence of hydrogen sulfide, mercaptans and nitrogen oxides. A blank correction of 15 parts per million (ppm) is recommended whenever 100 ppm of hydrogen sulfide or more are simultaneously present in the gas stream. Particulaies are shown to interfere either by addition or subtraction. Sulfate particulates that will add to the determination must be removed, but in doing so, care must be exerted to avoid surface-contacting conditions that promote reaction between carbonates and the sulfur oxides. The integrated method of sampling and analysis will permit determinations from a flue gas with sulfur oxides concentrations of 30 ppm and above. The relative standard deviation improves from 10% at 100 ppm SO₂ to 2.6% at 1000 ppm SO₂. In both cases, sulfides were present.     

Ambient and Source SO2 Detector Based on a Fluorescence Method

The principle of this detector is based on the measurement of the intensity of the ultraviolet fluorescence of SO₂ produced by absorption of the Zn 2138 Å or Cd 2288 Å line. The fluorescence intensity was found to be linear from 0.1 to 500 ppm of SO₂ in air with the Zn lamp and from 0.1 to 1600 ppm with the Cd lamp. The detection limit at present is about 20 ppb. There is no detectable interference from O₃, H₂S, NO₂, CO₂, CO, or H₂, although the presence of a large concentration of CS₂ (500 times as much as SO₂) NO (500 times) or C₂H₄ (4000 times) interferes with the measurement. The presence of 2% H₂0 reduces the signal by 25%, while up to 1 % CH₄ has almost no effect.     

Photochemical oxidation and dispersion of gaseous sulfur compounds from natural and anthropogenic sources around a coastal location

The photochemical oxidation and dispersion of reduced sulfur compounds (RSCs: H₂S, CH₃SH, DMS, CS₂, and DMDS) emitted from anthropogenic (A) and natural (N) sources were evaluated based on a numerical modeling approach. The anthropogenic emission concentrations of RSCs were measured from several sampling sites at the Donghae landfill (D-LF) (i.e., source type A) in South Korea during a series of field campaigns (May through December 2004). The emissions of natural RSCs in a coastal study area near the D-LF (i.e., source type N) were estimated from sea surface DMS concentrations and transfer velocity during the same study period. These emission data were then used as input to the CALPUFF dispersion model, revised with 34 chemical reactions for RSCs. A significant fraction of sulfur dioxide (SO₂) was produced photochemically during the summer (about 34% of total SO₂ concentrations) followed by fall (21%), spring (15%), and winter (5%). Photochemical production of SO₂ was dominated by H₂S (about 55% of total contributions) and DMS (24%). The largest impact of RSCs from source type A on SO₂ concentrations occurred around the D-LF during summer. The total SO₂ concentrations produced from source type N around the D-LF during the summer (a mean SO₂ concentration of 7.4 ppbv) were significantly higher than those (≤0.3 ppbv) during the other seasons. This may be because of the high RSC and SO₂ emissions and their photochemistry along with the wind convergence.