Sulfur Dioxide Fumigation of Soybeans: Effect on Yield

In order to determine the influence of SO₂ fumigation of soybean plants on yield, a three-year experiment was conducted on 485 plois of soybeans. Single fumigations of S0₂ were applied at 10 different stages of growth in 1968-69 and 7 stages of growth in 1970. A linear relationship was found to exist beiween the percent of leaf area destroyed and ihe percent crop loss with a significant regression coefficient of b = —0.659, or iwo-thirds of one percent crop loss for each percent of area destroyed. No definite significant stage-of-growth effect was found and no treatment effects were significant for the early stages of growth from the 3-leaf to the 15-leaf stage, nor was there any loss in yield without visible leaf 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.     

Controlled Enrichment System for Experimental Fumigation of Plants in the Field with Sulfur Dioxide

A prototype Free-Air Controlled Enrichment (FACE) system was developed at Brookhaven National "Laboratory (BNL) for the experimental control of gas concentrations in an open field, without any form of enclosure. This FACE system consists of a toroidal plenum chamber, 15 m in diameter, with a series of 32 vertical vent pipes from which the release of a test gas can be controlled. Data on gas concentration at the center of the array and wind velocity are fed to a microprocessor where a proportional, integrative, differential (PID) algorithm is used to regulate a mass-flow controller. Data on wind direction are used to control the opening and closing of the vertical vent pipes to maintain an upwind release. In 72 hours of continuous operation during which wind velocity varied between 0.3 to 8 m sec^-1, the FACE prototype maintained 1 -min averaged concentrations within twenty percent of the 40 ppb set point 94 percent of the time.     

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.     

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}.     

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.     

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.     

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.     

Modeling Evidence of Incloud Transformation Of Sulfur Dioxide to Sulfate

Methylene chloride (CH₂Cl₂) is presently under study by the U.S. EPA and other agencies to determine if the compound presents an unreasonable risk to human health and to determine if regulatory action is needed to reduce the risk. This paper describes one portion of the study which required the development and validation of a method of sampling and analysis for source emission measurements.

Prior to source sampling, laboratory experiments were conducted to determine the best sample container in which to collect an integrated sample. It was found that CH₂Cl₂ remained stable in Tedlar bags for at least four weeks. The analytical method selected was gas chromatography with flame ionization detection (GC/FID). During the field portion of the study, both manufacturer and user emission sources of CH₂Cl₂ were tested. Multiple sets of simultaneous quadruplicate bag samples were collected to determine the precision of both sampling and analysis in the field. All samples were analyzed at the test site after collection and then returned to Research Triangle Park. Samples were subsequently reanalyzed in the laboratories of Radian and the U.S. EPA using three GC/FID instruments and two types of GC columns. The range of concentrations from the sources was 100 ppm to 27,000 ppm CH₂Cl₂. A statistical analysis of samples collected simultaneously showed no difference in the samples, proving good precision In both sampling and analysis. Some of the sample bags returned from the test sites developed leaks indicating that immediate on-site analysis is best. A comparison of results obtained in the field and the two laboratories showed that interand intra-laboratory precision was within 10 percent.     

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.     

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.     

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.     

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.     

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.     

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.