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.     

Carbon Monoxide and Sulfur Dioxide Adsorption on— and Desorption from Glass,Plastic, and Metal Tubings

It was planned to install 305 m (1000 ft) of tubing on a television tower to transport ambient air samples from different height levels to pollutant monitoring instruments at ground level. A feasibility study was undertaken to determine the sorption characteristics of sulfur dioxide and carbon monoxide on various conduit materials. Sorption studies were completed on 30.5 m (100 ft) lengths of 1.3 cm (Y2 in) diam tubings of glass, Teflon, tygon, polypropylene, PVC piping, aluminum, and stainless steel. Final tests were completed on 305 m of 1.9 cm (3/4 in) diam stainless steel tubing. The following variables were investigated: tubing diameter, gas concentration, flowrate through the tubing, temperature, humidity, and the effect of sorption with sulfur dioxide and carbon monoxide alone or together. The parameter ranges studied approximated either atmospheric or air sampling conditions. For carbon monoxide, there was no significant difference between the mean inlet and outlet tubing concentrations under the conditions of the study. With sulfur dioxide, there was neither tubing adsorption nor desorption under the experimental parameters studied, except for tygon, PVC, and aluminum. After a conditioning period with sulfur dioxide, tygon, PVC, and aluminum could also be used as air inlet conduits; tygon is not recommended.     

Standardization of Methods For Measurement of Air Pollutants

Currently available compilations of methods of air analysis are listed. Collaborative testing is urgently needed to reconcile differences and to demonstrate the accuracy of these methods. The Analytical Methods Evaluation Service of the National Center for Air Pollution Control conducted a survey of the instruments and manual methods of analysis in use. Responses are tabulated from about 80 laboratories, in 28 states and 3 foreign countries. Sulfur dioxide was the most widely measured pollutant. The first collaborative study organized by the Analytical Methods Evaluation Service is described. The purpose was to evaluate the permeation tube technique as a primary standard method for generating known sulfur dioxide concentrations for instrument calibration and methods testing. Although a good beginning has been made, the testing of methods for measuring air pollutants has barely begun.     

Transient and Frequency Response of Air Quality Monitors

Results of dynamic or transient tests and steady state calibration of carbon monoxide and sulfur dioxide continuous air quality monitors are reported. Standard gases and permeation tubes were used to establish low level concentrations bpth for the steady-state calibration and the dynamic testing. The steady-state calibration was in excellent agreement with results obtained from grab samples of the calibration gas stream taken with standard gas bubblers and analyzed by the West and Gaeke procedure. Such tests have been carried out by other investigators with similar results. The important contribution of this paper lies in the application of dynamic testing techniques developed by the senior author and co-workers to determine the transient and frequency response characteristics of these air quality monitors.     

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.     

The Compact Sequential Automatic Air Sampler

The body of information presented in this paper is directed to ecologists concerned with the effects and economic impact of sulfur dioxide on forest growth. Investigations were carried out over a ten-year period, 1953–1963, in the Sud-bury smelter district of Ontario, where three large smelters discharge annually approximately 2,000,000 tons of sulfur dioxide gas into the surrounding atmosphere. The study was designed to determine the long-term chronic effects of sulfur dioxide on yield, growth, and survival of plant life. Since eastern white pine is the most susceptible coniferous tree to sulfur dioxide injury, it was selected as the indicator tree to determine the degree and extent of injury in the Sudbury area. Tree data accumulated from the sample plots were correlated with records of atmospheric sulfur dioxide monitored continuously during the growing season by a network of ten strategically-located Thomas autometers. Based on the degree of injuries exhibited by the trees, and on air sampling records of sulfur dioxide, the Sudbury area was segregated into three fume zones: Inner, Intermediate, and Outer. An estimate was made of the loss in income suffered by the owners of wood or the producers of wood products in the Sudbury area as a result of sulfur dioxide air pollution, by utilizing the white pine volume growth loss data     

粉煤灰烧制陶粒过程中二氧化硫的释放规律与形成机理

研究了粉煤灰烧制陶粒过程中烟气二氧化硫的释放规律,同时对烧结前后粉煤灰与陶粒中不同形态硫含量和硫平衡进行了分析,探讨了烟气中二氧化硫的来源和转化机理.结果表明,烟气中约55％的二氧化硫来源于硫酸盐的还原,其余主要来自有机硫燃烧和亚硫酸盐的分解.烧制每千克陶粒所产生的二氧化硫量约为7.8g.高温烧结过程中粉煤灰球内形成的还原性气氛导致了粉煤灰中硫酸盐向二氧化硫的还原转化.     

燃煤手烧炉有害气体生成特征研究

本文对燃煤手烧炉烟气生成特征进行了分析和研究 ,对燃烧过程二氧化硫、一氧化碳及一氧化氮等有害气体的生成规律和浓度值进行了测定和分析     

CALPUFF and AERMOD model validation study in the near field: Martins Creek revisited

This paper describes a near-field validation study involving the steady-state, U.S. Environmental Protection Agency (EPA) guideline model AERMOD and the nonsteady-state puff model CALPUFF. Relative model performance is compared with field measurements collected near Martins Creek, PA-a rural, hilly area along the Pennsylvania-New Jersey border. The principal emission sources in the study were two coal-fired power plants with tall stacks and buoyant plumes. Over 1 yr of sulfur dioxide measurements were collected at eight monitors located at or above the two power plants' stack tops. Concurrent meteorological data were available at two sites. Both sites collected data 10 m above the ground. One of the sites also collected sonic detection and ranging measurements up to 420 m above ground. The ability of the two models to predict monitored sulfur dioxide concentrations was assessed in a four-part model validation. Each part of the validation applied different criteria and statistics to provide a comprehensive evaluation of model performance. Because of their importance in regulatory applications, an emphasis was placed on statistics that demonstrate the model's ability to reproduce the upper end of the concentration distribution. On the basis of the combined results of the four-part validation (i.e., weight of evidence), the performance of CALPUFF was judged to be superior to that of AERMOD.     

Trends in atmospheric sulfur and nitrogen species in the eastern United States for 1989–1995

Emission reductions were mandated in the Clean Air Act Amendments of 1990 with the expectation that they would result in major reductions in the concentrations of atmospherically transported pollutants. This paper investigates the form and magnitude of trends from 1989 to 1995 in atmospheric concentrations of sulfur dioxide, sulfate, and nitrogen at 34 rural sites in the eastern US. Across all sites, there is strong evidence of statistically significant declining trends in sulfur dioxide (median change of -35%) and sulfate concentrations (median change of -26%). In general, trends in nitrogen concentrations were not as pronounced (median change of -8%) as trends in the sulfur compounds. A regional estimate of trend for a cluster of sites in the Ohio River valley showed close correspondence between declining sulfur dioxide concentrations (-35%) and changes in sulfur dioxide emissions (-32%) in this region.     

Comparison of measurement methods for the characterization of the black carbon emissions from a T63 turboshaft engine burning conventional and Fischer-Tropsch fuels

Emission measurements of black carbon (BC) mass were conducted on a T63 turboshaft engine, operated at idle and cruise power with conventional and alternative fuels, using an Artium LII-300 laser-induced incandescence analyzer (LII) and AVL model 483 micro soot sensor (MSS) photoacoustic instrument using the manufacturer’s calibration for both instruments. These measurements were compared with elemental carbon (EC) determined by manual and semicontinuous thermal-optical transmission analyses according to National Institute for Occupational Safety and Health (NIOSH) method 5040 as the reference method. The results indicate that both the LII and MSS instruments show good linear correlation with EC for the two fuels and two engine power conditions evaluated. The LII measurements were observed to be biased high (27–49%) and the MSS measurements were biased low (24–35%) relative to EC. The agreement between the instruments and the reference method was substantially improved by applying a calibration of the instruments against a common BC aerosol source. Test data also suggest that the two instruments show some sensitivity to particle size (or properties related to size), specifically for particles with a geometric mean diameter (GMD) <30 nm. This sensitivity is problematic, since new engines or certain combustion conditions in current engines will produce smaller particles compared with the T63 model tested in this study. Further assessments of instrument performance for particles within this size range are therefore warranted.

Implications: Accurate black carbon emission measurements are needed to certify new and in-production commercial aircraft engines. Both the Artium LII-300 and AVL 483 micro soot sensor are currently approved by the International Civil Aviation Organization for this purpose. This study compares the two instruments against elemental carbon (EC) using NIOSH method 5040 as the reference using a T63 turboshaft engine. The results indicate that both instruments correlate reasonably well with EC, and the correlation substantially improved when applying a calibration against a common aerosol source. Sensitivity to particle size may be an issue for both instruments.     

Measurements of Primary Sulfates with an Acid Condensation System

Two techniques were used to measure primary sulfuric acid and sulfate emissions from two small package boilers burning nominal 0.3% sulfur fuels, one with 11 ppm vanadium and one with 4.3 ppm vanadium. Several of the particulate fractions from both sampling methods were analyzed for sulfuric acid using a selective solvent determination (SSD) procedure. The sulfuric acid present on the filters accounted for a minimum of 11% of the particulate emission rates. The observed conversion of sulfur dioxide to primary sulfate or primary sulfuric acid is reduced considerably when sulfate ion detected in an isopropanol impinger is attributed to sulfur dioxide conversion in the solution rather than to primary sulfuric acid. An additional reduction occurs when the method of calculating the conversion is based solely on sulfur weight. This study gives a fourfold reduction in percent conversion when compared to a similar study conducted earlier. Suggestions are offered for improvements in measurement methods and for a consistent technique for calculating sulfur conversion.     

硫化氢硫醇废气的臭氧氧化试验

介绍了臭氧氧化法去除工业废气中的硫化氢、硫醇的试验情况,考察了臭氧浓度、停留时间和催化作用等不同因素对去除率的影响.试验结果表明能达到较好的去除效果,硫化氢、硫醇的最终氧化产物不是二氧化硫,不会增加二氧化硫的污染.     

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.     

Natural desulfurization in coal-fired units using Greek lignite

This paper analyzes the natural desulfurization process taking place in coal-fired units using Greek lignite. The dry scrubbing capability of Greek lignite appears to be extremely high under special conditions, which can make it possible for the units to operate within the legislative limits of sulfur dioxide (SO2) emissions. According to this study on several lignite-fired power stations in northern Greece, it was found that sulfur oxide emissions depend on coal rank, sulfur content, and calorific value. On the other hand, SO2 emission is inversely proportional to the parameter gammaCO2(max), which is equal to the maximum carbon dioxide (CO2) content by volume of dry flue gas under stoichiometric combustion. The desulfurization efficiency is positively correlated to the molar ratio of decomposed calcium carbonate to sulfur and negatively correlated to the free calcium oxide content of fly ash.     

Asthma and Air Pollution in Two Inner City Areas in New York City

The preliminary analysis of four months of emergency room visits for asthma in two inner city areas containing populations of similar socioeconomic, racial, and ethnic compositions, with similar day to day weather conditions but differing in their day to day levels of air pollution was made, and the relationship of visits to emergency rooms to daily temperature and air pollution levels measured in the areas, are described.

In Harlem no relationship between daily visits to emergency rooms and daily levels of either smokeshade or sulfur dioxide have been observed whereas in Brooklyn a relatively strong correlation between daily visits for asthma and daily levels of sulfur dioxide but not with smokeshade have been observed over and above the effect of temperature. In both areas there was a strong relationship between daily visits for asthma and the first cold spells of the fall season. The average male/female ratio for asthma visits to hospital emergency rooms of both areas in the age group under thirteen years of age was 1.7 and for the over thirteen years of age group was 0.6.

It appears from the data that Brooklyn presents a different picture for the environmental influence on asthma attacks. Even though it has been shown by previous investigators that asthmatics are sensitive to sulfur dioxide, we feel that in our case sulfur dioxide is not necessarily the causative agent, but might rather implicate some other confounding variable (most likely an environmental agent) that is disseminated in the general Bedford-Stuyvesant area in a similar day to day pattern to sulfur dioxide. We infer this from the fact that levels of sulfur dioxide were somewhat higher on the average in the Harlem area than they were in the Brooklyn area.     

A System for Abatement Control Strategy Evaluation

The Air Quality Control Program of the Commonwealth of Massachusetts has developed an implementation plan for the Metropolitan Boston Intrastate Air Quality Control Region as required by PL 90-148. An essential part of the plan was a set of control regulations designed to achieve and maintain an air quality compatible with adopted standards. Control strategy modeling was used as a tool in selecting the most appropriate regulations to achieve this goal. The body of information presented in this paper is directed to those state and county air pollution control officials concerned with the formulation and evaluation of regulations.

The paper details the procedures developed and presents a case history of their use in the region. The system is a synthesis of generally-available software and newly-developed computer programs to provide ahighly automated computational structure. It permits rapid simulation of the emissions resulting from the application of various control regulations. Predictions on the changes expected in ambient air quality levels are then made by the use of the Air Quality Display Model (AQDM).

The initial step in the application was a calibration of the system using predicted and measured annual concentrations. This step yielded correlation coefficients of 0.92 for sulfur dioxide and 0.85 for particulates. Subsequently, the system was used to evaluate the baseline case of uncontrolled sulfur in fuel use. Alternative sulfur control strategies were tested for compatibility with air quality standards. The principal strategies tested were: (a) 1% sulfur uniformly throughout the region; (6) 1% sulfur in core area of region, 2.2% sulfur elsewhere; (c) 0.5% sulfur in core area of region, 2.2% sulfur elsewhere; (d) 0.5% sulfur in core area of region, 1.0% sulfur elsewhere.

Strategies (b) and (d) were implemented into a time phased set of control regulations for the region.

Experience with the system has shown it to be a convenient and rapid method for simulating the effects of control regulations. Furthermore, the utility of this initial model warrants expansion of its application to the other air quality control regions in the Commonwealth.     

Studies on a New Method of Simultaneously Removing Sulfur Dioxide and Oxides of Nitrogen from Combustion Gases

Simultaneous reduction of SO₂ and NO by catalyzed reaction with carbon monoxide at space rates approaching 10⁴ vol/vol/hr has been shown. The reaction of sulfur dioxide with carbon monoxide results in the formation of carbon dioxide and elemental sulfur. Nitric oxide reacts with carbon monoxide to form carbon dioxide and molecular nitrogen. Metals supported on alumina appear to be the preferred catalysts. Among the effective metals are copper, silver, and palladium. A side reaction of carbon monoxide with elemental sulfur to form carbonyl sulfide requires that the initial amount of carbon monoxide be stoichio-metric for the amount of sulfur dioxide plus nitric oxide present. A furnace employing this method would have to be operated at low excess air, near stoichiometric fuel/air, or possibly slightly on the rich side.     

Odor and Fallout Control in a Kraft Pulp Mill

Lead dioxide cylinders are inexpensive sampling devices commonly used for an assessment of sulfur oxides in the atmosphere. This paper will report the results of basic studies intended to characterize some of the critical parameters of this method. The behavior of the system in the region of the critical loading percentages was determined as well as the effects of lead dioxide particle size, presence of reduced sulfur compounds, and use of different binders. From these studies it has been possible to show a definite relationship between allowable exposure times and atmospheric concentrations of sulfur dioxide with particle size as a major parameter     

The redox combustion of carbon monoxide for recovering pure carbon dioxide by using molten (Na+,K+)2(CO32-,SO42-) mixtures

Large-scale combustion systems, such as thermal power plants, emit large amounts of carbon dioxide, which can increase global warming. A molten salt redox combustion system was proposed to recover pure carbon dioxide exhausted from the combustion of fossil fuels. This system is composed of two successive processes by using reactions occurring in a molten salt. The molten salt is the mixture of the molten alkali metal sulfates and carbonates. The sulfate ions oxidize the fuels in first processes, being changed to reductive species such as sulfide ions. In this process, carbon dioxide and water are exclusively exhausted. The reductive species of sulfur compounds are oxidized to regenerate the sulfate ions by air in the second process. In this study, these above two processes were tried by using molten [(Na(+))(0.5),(K(+))(0.5)](2)[(CO(3)(2-))(0.9),(SO(4)(2-))(0.1)] alternatively. The oxidation of carbon monoxide as fuel by sulfate ions and the regeneration of sulfate ions by air were investigated in the temperature range of 700-950 degrees C, respectively. These reactions were exothermic. The rate of the regeneration of the sulfate ions was extremely high. During the oxidation of carbon monoxide, the reaction was first order in carbon monoxide with an activation energy of 101 kJ mol(-1). The optimum condition to recover pure carbon dioxide on practical operation was discussed.