The Absorption of Atmospheric Sulfur Dioxide by Water Solutions

Results of a laboratory study indicate that the rate of solution of atmospheric sulfur dioxide in distilled water, over the range of atmospheric concentrations of 0.81?8.73 mg SO₂/M³, is a function of the concentration of SO2 in the atmosphere, with saturation being reached more rapidly at the higher concentrations. This would indicate that rain water, with constantly renewed surfaces, can be very effective in the removal of atmospheric SO₂. The pH of the exposed water samples reached values of 4.0 or less, comparable to values observed in fog and cloud water near large industrial areas. Overall solubility of sulfur dioxide in distilled water did not follow the law of partial pressure. At the atmospheric concentrations used it was found that over 98.5% of the sulfite in solution was in the form of the bisulfite ion with, the remainder present as unionized sulfurous acid. Computations using the concentration of unionized sulfurous acid in the solution showed that the solubility of this portion of dissolved sulfite did follow the law of partial pressure.     

Photo-Oxidation of Sulfur Dioxide

SO₂/O₂ mixtures were photolyzed at 3130 Å and in the range 2500–4000 Å at room temperature. The only product of photolysis was SO₃. Attempts to estimate ф(S0₃) using mass spectrometry, l.R. spectroscopy and pressure change measurements were unsuccessful, because it was not possible to obtain reproducible quantitative estimates of SO₃. ф(SO₂) values were determined by monitoring the 3130 Å absorption for its concentration measurements. ф(SO₂) was independent of SO₂ (11.6 to 50.4 torr) and O₂ (50.0 to 390.6 torr) pressures. At 3130 Å, ф(SO₂) varied between 1.5 × 10^?2 and 2.2 X 10^?2. Over the integrated range 2500–4000 Å ф(SO₂) values of 2.1 X 10^?3 to 2.9 X 10^?3 were obtained. The differences in ф(SO₂) values are explained in terms of wavelength dependence of the rate constants for the two primary reactions: ¹SO₂ + SO₂ → 2SO₂(1) and ¹SO₂ + SO₂ → ³SO₂ + SO₂(2); (k₂/k₁) _{3130 Å} ≈ 10(k₂/k₁)_{2500–4000 Å}.     

Nashville Sulfur Dioxide Emission Inventory and the Relationship of Emission to Measured Sulfur Dioxide

A detailed inventory of sulfur dioxide emissions was prepared as part of the Nashville Community Air Pollution Study conducted by the Public Health Service during 1958–59. The primary purpose of the inventory was to provide data for a study of the relationship between the emission of sulfur dioxide and measured ambient levels. The development of the inventory, data collection methods, and calculations are described. Ambient levels of sulfur dioxide were related to average emissions of sulfur dioxide in such a way (correlation coefficient = 0.81) that mean seasonal concentrations of atmospheric sulfur dioxide in square-mile areas could be predicted with fairly good confidence from a knowledge of sulfur dioxide emissions. For these long-period {average) predictions meteorological variables can be disregarded. On a square-mile basis, on the average, one ton of sulfur dioxide emitted per day produced a mean atmospheric sulfur dioxide concentration of 0.022 ppm, and 10 tons of sulfur dioxide per day produced a concentration of 0.067 ppm.     

Sulfur Dioxide and Material Damage

Whereas most estimates of material damage are based on industrial surveys, the estimates produced in this study were derived from material damage experiments and ambient air quality data. Air quality data on SO₂ were obtained from 200 or more monitoring sites primarily located in heavily populated or polluted areas. Material threshold damage function data were then compared with SO₂ levels, and an estimate of losses, as reflected in increased maintenance and replacement costs, was determined. Estimates of the total stock of various materials in use were derived from census and industry data and allocated geographically according to population. A substantial decrease in the ambient SO₂ levels, particularly in larger urban areas, has occurred during the past five years. From 1968 to 1972, the estimated amount of material damage from SO₂ in the U. S. decreased from $900 million/yr to less than $100 million. During this period, the estimated percentage of man made materials exposed to SO₂ levels exceeding the proposed secondary annual average standard (60 μg/m³) and primary annual average standard (80 μg/m³) in the U. S. fell respectively, from 20% to less than 5% and from more than 10% to less than 1%. Most of the present loss is attributed to corrosion damage of metallic surfaces that are normally exposed to the ambient environment.     

Simultaneous Sulfur Dioxide and Nitrogen Dioxide Removal by Calcium Hydroxide and Calcium Silicate Solids

ABSTRACT

At conditions typical of a bag filter exposed to a coal-fired flue gas that has been adiabatically cooled with water, calcium hydroxide and calcium silicate solids were exposed to a dilute, humidified gas stream of nitrogen dioxide (NO₂) and sulfur dioxide (SO₂) in a packed-bed reactor. A prior study found that NO₂ reacted readily with surface water of alkaline and non-alkaline solids to produce nitrate, nitrite, and nitric oxide (NO). With SO₂ present in the gas stream, NO₂ also reacted with S(IV), a product of SO₂ removal, on the exterior of an alkaline solid. The oxidation of S(IV) to S(VI) by oxygen reduced the availability of S(IV) and lowered removal of NO₂. Subsequent acidification of the sorbent by the removal of NO₂ and SO₂ facilitated the production of NO. However, the conversion of nitrous acid to sulfur-nitrogen compounds reduced NO production and enhanced SO₂ removal. A reactor model based on empirical and semi-empirical rate expressions predicted rates of SO₂ removal, NO₂ removal, and NO production by calcium silicate solids. Rate expressions from the reactor model were inserted into a second program, which predicted the removal of SO₂ and NO_x by a continuous process, such as the collection of alkaline solids in a baghouse. The continuous process model, depending upon inlet conditions, predicted 30-40% removal for NO and 50-90% removal for SO₂. These x 2 results are relevant to dry scrubbing technology for combined SO₂ and NO_x removal that first oxidizes NO to NO₂ by the addition of methanol into the flue duct.     

Modification of Sulfur Dioxide Injury to Tobacco and Tomato by Varying Nitrogen and Sulfur Nutrition

The body of information presented in this paper is directed to plant scientists who are concerned with factors which modify the susceptibility of plants to air pollutants.

Tobacco and tomato plants grown in sand-solution culture with varying levels of nitrogen or sulfur were exposed to injurious levels of sulfur dioxide. Plants of both species which were deficient in either nutrient exhibited decreased susceptibility to the gas compared with plants grown at optimal levels of each nutrient. Foliage of these plants was also found to have increased stomatal resistance as measured by a porometer and decreased total sulfur accumulations. Plants grown at optimum levels of each nutrient showed increased susceptibility over that of the deficient plants. Stomatal resistance was lower and sulfur accumulation was greater than in the deficient plants. At the supra-optimal nitrogen and sulfur levels, there were differences in susceptibility. Over-abundant nitrogen appeared to decrease susceptibility whereas over-supplies of sulfur increased it.

The response of plants with deficient or optimal supplies of either nutrient might be explained by the effects of nutrition on stomatal activity and hence on ability to absorb SO₂S from the atmosphere, mineral deficiency being known to increase stomatal resistance, and mineral sufficiency, to decrease stomatal resistance by virtue of increased efficiency of water use. The difference in response between plants overfertilized with respect to nitrogen or sulfur is explained by the fact that sulfur is both nutrient and phytotoxicant at the same time. Having already been oyersupplied with sulfur by absorption from the nutrient substrate, the high-sulfur plants were unable to withstand additional sulfur accumulation from the atmosphere and hence were more severely injured.

Increased carbohydrate accumulation in the nitrogen- and sulfur-deficient plants might play an additional role in protection from SO2-injury.     

Flash Photolysis of Sulfur Dioxide

The body of information presented in this paper is directed to photochemists and air pollution scientists interested in species which result from the interaction of SO₂ and light. When SO₂ at low pressures is subjected to an intense photolysis flash, the characteristic, very structured SO₂absorption spectrum disappears immediately after the flash and is replaced by a continuous absorption. The continuous absorption gradually decays and the normal SO₂ absorption spectrum returns. The initial absorbance of the continuous absorption is proportional to the square of the SO₂ pressure and the square of the flash irradiance. From these facts we propose the formation of a metastable dimer of SO₂ formed by the collision of two excited molecules. Some properties of this dimer are: natural lifetime = 2 sec; energy above separated monomers = 4 kcal; lifetime at atmospheric pressure = 1 sec (quenching coefficients with several foreign gases = 10^-20 cm³/sec molecule); absorption of ultraviolet light results in photode-composition of the dimer into monomeric SO₂. The long lifetime of this species and its low quenching cross section may make it an important intermediate in photochemical reactions of SO₂. The relatively low excitation energy of the metastable species indicates it may also be an intermediate in thermally excited reactions and perhaps an important component of smoke stack effluent.     

硫化碱脱除二氧化硫工业烟气的可行性分析

分析了国内外烟气脱硫的研究现状,论述了用硫化碱脱除二氧化硫化工业烟气在理论上和实验上的可能性。     

Alternative Strategies for Control of Sulfur Dioxide Emissions

Achievement of air quality goals now more than ever requires careful consideration of alternative control strategies in view of national concerns with energy and the economy. Three strategies which might be used by coal-fired steam electric plants to achieve ambient air quality standards for sulfur dioxide have been compared, and the analysis shows that the desired objective can be achieved using the intermittent control strategy with substantially less impact on the environment, less consumption of energy, and at a much lower economic cost than using either stack gas scrubbing or low-sulfur coal.     

Multi-Instrument Performance Evaluation of Conductivity-Type Sulfur Dioxide Analyzers

Three different recording analyzers for sulfur dioxide were operated in parallel under field conditions. Manual sampling for sulfur dioxide using the West-Gaeke procedure supplemented the instrumental evaluation tests. Two of the analyzers were of the continuous-flow type. These were found to give markedly higher readings for SO₂ in the atmosphere (in some cases as much as threefold) than did the other recorder which was sequential-batch or the West-Gaeke manual method.     

Improvement of Ambient Sulfur Dioxide Concentrations by Conversion from Low to High Stacks

A study of the “before” and “after” ground-level S0₂ concentrations near the Muskingum River Plant of the American Electric Power System shows that the conversion from low to high stacks has accomplished marked reductions in ambient concentrations. These reductions are in reasonable agreement with theoretical calculations and are most apparent within 5 km of the source. EPA Standards are now being met in this area despite the presence of the 1440 MW power plant burning 5% sulfur fuel with no treatment of the stack gas.     

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.     

Responses of Hybrid Poplar Trees to Sulfur Dioxide Fumigation

This paper verifies the presence of significant interclonal variation in the tolerance of hybrid poplar (Populus deltoides Bartr. cv. Angulata × P. trichocarpa Torr. and Gray) to sulfur dioxide fumigation. Rooted stem cuttings of four hybrid poplar clones were exposed to 5 ppm sulfur dioxide for 0, 3, 6, 9, or 12 hours in controlled environment chambers. Multivariate analyses were made from the shoot growth measurements recorded for 4 weeks before and after fumigation and on the data of foliar injury induced by sulfur dioxide. The following factors were statistically significant in determining growth response and foliar injury: (1) genotype; (2) duration of treatment; and (3) interaction between genotype and hours of fumigation. All partial correlations between foliar injury and subsequent shoot growth were positive and significant. Sufficient genetic variation appears to exist in this Populus hybrid to encourage selection of clones tolerant to short-term exposures of high levels of sulfur dioxide.     

Performance Characteristics of Instrumental Methods for Monitoring Sulfur Dioxide

The performance characteristics of commercially available continuous sulfur dioxide monitors were determined. Conductimetric, colorimetric, and coulometric analyzers were investigated. The study was conducted to develop information on such instrument characteristics as stability, sensitivity, response time, collection efficiency, and response to interfering substances. The methodology and apparatus used to determine each operational parameter are described. The instrument performance data developed in this study should be useful to those involved in selection of instrumental methods for monitoring atmospheric sulfur dioxide.     

Performance Characteristics of Instrumental Methods for Monitoring Sulfur Dioxide

The performance characteristics of commercially available sulfur dioxide monitors were determined. Con-ductimetric, colorimetric, and coulometric analyzers were investigated. During this phase of the study, characteristics that were more closely related to field operation were studied. These included comparability of data among the instruments over a period of time, weekly calibration drift, maintenance requirements (including operating cost), unattended operation performance, and the effect of rotameter changes on calibration. The methodology and apparatus used to determine each operational parameter are described. The results of this study should be useful in the selection of instruments for monitoring sulfur dioxide.     

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.     

Particulate and Sulfur Dioxide Concentration Measurements in Patras,Greece

Abstract

The purpose of this study was to obtain a better assessment of the Patras, Greece, air quality, in terms of the primary pollutants total suspended particulates (TSPs) and sulfur dioxide (SO₂), because limited and short-duration measurements have been conducted in the past. Installation and operation of a mobile air monitoring station at two different locations in the Patras downtown area and one location in the outskirts of the city was undertaken and covered the periods July 1, 1994-January 30, 1995; March 18-August 23, 1995; and April 19-July 27, 1996, respectively. For both pollutants measured at each location, the monthly average concentrations and typical weekly variation of daily averages, as well as the diurnal variations and frequency concentration distributions in each month of the monitoring periods, were calculated and are presented in bar diagrams. The annual and winter period medians and the annual 98th percentile were also calculated and are compared with the limit and guide values provided by the European Economic Community Council Directive 80/779/EEC. In addition, comparison of SO₂ values is made with the limit values adopted by the more recent Directive 1999/30/EC. It was found that the TSP and SO₂ levels at all locations were very low and were lower than the levels found in Thessaloniki and Athens, Greece. An attempt to explain what had been measured is also undertaken. The data presented are considered essential for future reference and comparison purposes.     

Appraisal and Modification Of West-Gaeke Method For Sulfur Dioxide Determination

The West-Gaeke method has been shown to be feasible for detecting changes in SO₂ concentration greater than 10%. Reliable results can be obtained if one makes up stock solutions of the pararosaniline dye from the same powder batch at the same time. Gum arabic stabilizes the SOvtetrachloromercurate complex at concentrations of SO₂ > 8 μg/ml.