The Lead Dioxide Estimation Of Sulfur Dioxide Pollution

A new system of measuring sulfation is presented. Because of its simplicity, operation of large sulfation networks can be accomplished at extremely nominal costs. Because of increased sensitivity, present 1 -month sampling time intervals may be shortened to approximately 1 day. Use of this system will permit more definitive investigations of the relationship of sulfation to sulfur dioxide concentration.     

Rates of Conversion of Sulfur Dioxide to Sulfate in a Scrubbed Power Plant Plume

ABSTRACT

The rate of conversion of SO₂ to SO₄ ^2- was re-estimated from measurements made in the plume of the Cumberland power plant, located on the Cumberland River in north-central Tennessee, after installation of flue gas desulfurization (FGD) scrubbers for SO₂ removal in 1994. The ratio of SO₂ to NO_y emissions into the plume has been reduced to ~0.1, compared with a prescrubber value of ~2. To determine whether the SO₂ emissions reduction has correspondingly reduced plume-generated particulate SO₄ ^2- production, we have compared the rates of conversion before and after scrubber installation. The prescrubber estimates were developed from measurements made during the Tennessee Plume Study conducted in the late 1970s. The post-scrubber estimates are based upon two series of research flights in the summers of 1998 and 1999. During two of these flights, the Cumberland plume did not mix with adjacent power plant plumes, enabling rate constants for conversion to be estimated from samples taken in the plume at three downwind distances. Dry deposition losses and the fact the fact that SO₂ is no longer in large excess compared with SO₄ ^2- have been taken into account, and an upper limit for the conversion rate constant was re-estimated based on plume excess aerosol volume. The estimated upper limit values are 0.069 hr^-1 and 0.034 hr^-1 for the 1998 and 1999 data, respectively. The 1999 rate is comparable with earlier values for nonscrubbed plumes, and although the 1998 upper limit value is higher than expected, these estimates do not provide strong evidence for deviation from a linear relationship between SO₂ emissions and SO₄ ^2- formation.     

A Rapid Titrimetric Method for Sulfate in Lead Dioxide Exposed to Atmospheric Sulfur Pollution

A titrimetric method is described for the analysis of sulfate in lead dioxide candles which have been exposed to atmospheric sulfur pollution. The time taken to analyse one sample is 3 hr. Sixty milliliters of 8% ammonium carbonate solution is used to convert the lead sulfate present on the candle to ammonium sulfate. The solution is filtered lc remove lead dioxide, and an aliquot of the filtrate is heated to remove ammonium carbonate. The solution of ammonium sulfate remaining is titrated directly for sulfate with 0.02 M barium perchlorate, using Thoron as indicator. The accuracy of the method is ±10 and ±6 % of theoretical, for 10 mg, and 40 mg or greater amounts of sulfate, respectively. For 2 mg of sulfate, results are about 20% high. Good agreement has been obtained between results for duplicate field candles, analyzed by the standard sodium carbonate gravimetric method, and the method presented, over a five-month period.     

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.     

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.     

Modeling of Sulfur Dioxide Emissions and Acidic Precipitation at Mesoscale Distances

A steady state mesoscale model developed to predict primary SO₂ concentrations from a single point source is presented. The model was validated with data from the Midwest Interstate Sulfur Transport and Transformation (MISTT) project, with root mean square errors of 9.69 μg m^?3 and 0.42 μg m^?3 for SO₂ and SO₄ respectively. Wet deposition (washout and rainout), eddy dispersivity, dry deposition of SO₂ and mean wind speed were found to be the most important factors controlling sulfur dioxide and sulfate concentrations. Estimation of precipitation acidity was then carried out using scavenging theory. The greatest potential acidification occurred approximately 200 km from the source along plume centerllne, which indicates a rather local effect as opposed to a long distance effect. The cross-plume influence was up to 60 km in width at a distance of 400 km from the source.     

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}.     

A Numerical Modeling Technique for Estimating Sulfur Dioxide Dry Deposition Due to Local Source Emissions

This paper describes a methodology for estimating the effect of local source emissions on dry deposition of sulfur dioxide in regions of complex terrain. Airflow in complex terrain is simulated by a time-dependent dynamical model for the meteorological fields. The results of the dynamical model are used to drive a semi-stochastic Lagrangian dispersion model in order to evaluate concentrations resulting from local source emissions. The Lagrangian dispersion model is coupled with a dry deposition treatment which includes the effects of both surface properties and micrometeoroiogical factors on deposition.

A sample application is discussed for a source in the Shenandoah Valley. The largest concentrations and deposition rates were obtained shortly after sunrise, during the transition from the nocturnal to the daytime flow regime. These results suggest that dry deposition may be episodic.     

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.     

Measurements of Rural Sulfur Dioxide and Particle Sulfate: Analysis of CASTNet Data, 1987 through 1996

ABSTRACT

The Clean Air Status and Trends Network (CASTNet) was implemented by the U.S. Environmental Protection Agency (EPA) in 1991 in response to Title IX of the Clean Air Amendments of 1990, which mandated the deployment of a national ambient air monitoring network to track progress of the implementation of emission reduction programs in terms of deposition, air quality, and changes to affected ecosystems. CASTNet evolved from the National Dry Deposition Network (NDDN). CASTNet currently consists of 45 sites in the eastern United States and 28 sites in the West. Each site measures sulfur dioxide (SO₂), nitric acid (HNO₃), particle sulfate (SO₄ ⁼), particle nitrate (NO₃ ^- ), and ozone. Nineteen sites collect precipitation samples. NDDN/CASTNet uses a uniform set of site-selection criteria which provides the data user with consistent measures to compare each site. These criteria also ensure that, to the extent possible, CASTNet sites are located away from local emission sources.

This paper presents an analysis of SO₂ and SO₄ ⁼ concentration data collected from 1987 through 1996 at rural NDDN/CASTNet sites. Annual and seasonal variability is examined. Gradients of SO₂ and SO₄ ⁼ are discussed. The variability of the atmospheric mix of SO₂ and SO₄ ⁼ is explored spatially and seasonally. Data from CASTNet are also compared to SO₂ and SO₄ ⁼ data from concurrent monitoring studies in rural areas.     

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.     

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.     

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.     

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.     

Monitoring Sulfur Dioxide with Lead Peroxide Cylinders

The results of source tests to demonstrate the applicability of direct-flame incineration for the control of the effluent from a wire-enameling bake oven are presented. The tests were conducted with a portable direct-flame incinerator under actual plant conditions. The efficiency of direct-flame incineration was established at incineration temperatures of 1000F, 1200, and 1400°F. Evaluation of incineration efficiency was performed by both analysis and quantitative odor measurement using an odor panel.     

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.