Measurements of Sulfur Oxides,Nitrogen Oxides,Haze and Fine Particles at a Rural Site on the Atlantic Coast

During August, 1982 and January and February, 1983, General Motors Research Laboratories operated air monitoring sites on the Atlantic Coast near Lewes, Delaware and 1250 km to the east on the southwest coast of Bermuda. The overall purpose of this project was to study the transformations of the principal acid precipitation precursors, NO _x and SO _x species, as they transport under conditions not complicated by emissions from local sources. In this paper, the measurements of gas and particulate species from Lewes are described and the composition and sources of sulfate aerosol, which is the most important haze-producing species, are investigated.

On the average, the total suspended particulate (TSP) concentration was 27.9 μg/m³ while the PM₁₀ (mass of particles with a diameter less than or equal to 10 μm) concentration was 22.0 μg/m³ or 79 percent of the TSP. The PM₁₀ consisted of 6.1 μg/m³ of coarse particles (CPM, diameter = 2.5 ? 10μm) and 15.9 μg/m³ of fine particles (FPM, diameter < 2.5 μm).

On a mass basis the most important constituents of the fine particulate fraction were sulfate compounds, 50 percent, and organic compounds, 30 percent. The mean light extinction coefficient corresponds to a visual range of 18-20 km. Most of the extinction can be attributed to the sulfate (60 percent) and organic carbon (13 percent). Particle size measurements show that the mass median aerodynamic diameter for both species is 0.43 μm. This is a typical size for a hydrated sulfate aerosol. For carbon, however, this is a larger size than previously reported and results in a more efficient light scattering aerosol. Principal component analyses indicate that coal combustion emissions from the midwestern U.S. are the most significant source of sulfate in Lewes during the summer and winter.     

Lysimeter Test of Coke Plant Effluent Disposal to Land in India

ABSTRACT

From the Indian national point of view, the importance of coal carbonizing industries is great and growing. These industries produce huge quantities of highly polluted effluents and discharge them into rivers without proper treatment. A large coke plant of Bharat Coking Coal Ltd. has been surveyed, and the impact of its effluent on surface water quality is discussed. Approximately 175-200 m³ of effluents are discharged from the plant every day. Land application has been considered as a low-cost means of disposal of coke oven effluents. Column lysimeters were prepared by collecting soil from a nearby agricultural field, putting it layerwise into a column, and compacting it carefully to simulate the original in situ conditions. Raw effluents, diluted effluent, and water (as a blank) were applied to the three lysimeters twice a week with a 5 cm flooding. Upon application of diluted effluent (1:1) into lysimeter No. 2, the leachate collected at 190 cm depth was within the tolerance limit of drinking water standard (IS 10,500). The impact of raw and diluted effluent on groundwater quality and soil are discussed. The renovation efficiency of living filter (lysimeter No. 2) was 99.37% for oil and grease, 86.92% for COD, and 53.22% for TDS, and it is estimated that 2.73 hectares of land can be irrigated with the effluents of the coke plant without deteriorating groundwater and soil quality.     

Deposition of Mn from Automotive Combustion of Methylcyclopentadienyl Manganese Tricarbonyl beside the Major Highways in the Greater Toronto Area,Canada

ABSTRACT

Methylcyclopentadienyl manganese tricarbonyl (MMT) has been used in Canada since 1976 as an antiknock agent in gasoline, completely replacing Pb in 1990. An early study of much higher Mn concentrations in gasoline showed that the combustion of MMT leads to the formation of inorganic manganese oxides, especially Mn₃O₄. Recent emission testing by Lawrence Livermore National Laboratory for Ethyl Corp. has shown that Mn is primarily emitted as a phosphate or sulfate along with minor amounts of oxides. The main objective of this research was to analyze the deposition of Mn from MMT to the terrestrial environment beside the major highways in the greater Toronto area (GTA), Canada. The results were compared with Pb and other trace elements such as Al, Ca, Fe, Mg, Cu, Zn, Na, and the Cl^- ion (water extractable) to study the behavior of Mn in soil. The study area was located near major Toronto highways 401 (urban) and 400 (rural), at 43° 67′ N and 79° 37′ W (latitude and longitude) (278,560 and 47,835 cars/day), respectively. Surface soil samples (0–5 cm depth) were collected at distances up to 40 m from the roadside. Parameters evaluated included total and available Mn and other trace elements, particle size, pH, organic content, and cation exchange capacity.     

Dissociation of Sulfur Hexafluoride Tracer Gas in the Presence of an Indoor Combustion Source

ABSTRACT

As an odorless, nontoxic, and inert compound, sulfur hexafluoride (SF₆) is one of the most widely used tracer gases in indoor air quality studies in both controlled and uncontrolled environments. This compound may be subject to reactions with water vapor under elevated temperature to form acidic inorganic compounds such as HF and H₂SO₄. Thus, in the presence of unvented combustion sources such as kerosene heaters, natural gas heaters, gas log fireplaces, candles, and lamps, the SF₆ dissociation may interfere with measurements of the emissions from these sources. Tests were conducted in a research house with a vent-free natural gas heater to investigate these potential interferences. It was observed that the heater operation caused about a 5% reduction of SF₆ concentration, which can be an error source for the ventilation rate measurement and consequently the estimated pollutant emission rates. Further analysis indicates that this error can be much greater than the observed 5% under certain test conditions because it is a function of the ventilation flow rate. Reducing the tracer gas concentration has no effect on this error. A simple theoretical model is proposed to estimate the magnitude of this error.

The second type of interference comes from the primary and secondary products of the SF₆ dissociation, mainly H₂SO₄, SO₂, HF, and fine particulate matter (PM). In the presence of ~5 ppm SF₆, the total airborne concentrations of these species increased by a factor of 4-10. The tests were performed at relatively high SF₆ concentrations, which is necessary to determine the interferences quantitatively. The second type of interference can be significantly reduced if the SF₆ concentration is kept at a low ppb level.     

Evaluation of Catalyzed and Electrically Heated Filters for Removal of Particulate Emissions from Diesel-A- and JP-8-Fueled Engines

Abstract

In-service diesel engines are a significant source of particulate matter (PM) emissions, and they have been subjected to increasingly strict emissions standards. Consequently, the wide-scale use of some type of particulate filter is expected. This study evaluated the effect of an Engelhard catalyzed soot filter (CSF) and a Rypos electrically heated soot filter on the emissions from in-service diesel engines in terms of PM mass, black carbon concentration, particle-bound polycyclic aromatic hydrocarbon concentration, and size distribution. Both filters capture PM. The CSF relies on the engine's exhaust to reach the catalyst regeneration temperature and oxidize soot, whereas the electrically heated filter contains a heating element to oxidize soot. The filters were installed on several military diesel engines. Particle concentrations and compositions were measured before and after installation of the filter and again after several months of operation. Generally, the CSF removed at least 90% of total PM, and the removal efficiency improved or remained constant after several months of operation. In contrast, the electrical filters removed 44-69% of PM mass. In addition to evaluating the soot filters, the sampling team also compared the results of several real-time particle measurement instruments to traditional filter measurements of total mass.     

Modeling of Indoor Air Treatment of Polychlorinated Dibenzo-p-Dioxins and Dibenzofurans Using High-Efficiency Particulate Air-Carbon Filtration

Abstract

A high-efficiency particulate air (HEPA)-carbon filtration system was developed by the Access Business Group, LLC, to reduce the indoor levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). The HEPA filter removes the particle-bound PCDD/Fs, and the carbon filter removes the gaseous fraction. Because of the toxicity of PCDD/Fs, it is very difficult to handle them in the laboratory. In this study, mathematical modeling was performed to evaluate the performance of the HEPA-carbon filtration system for PCDD/Fs removal and to optimize its design and operation. The model was calibrated with experimental data conducted with toluene in a sealed room. Model simulations with four selected congeners demonstrated that it takes ～1 hr for the indoor air treatment system to reach the maximum removal efficiency and that the carbon air filter has a life time of 10⁷ yr for dioxin removal. Given a zero emission from the HEPA filter, the overall removal efficiency is 78.7% for 2,3,7,8-tetrachloro dibenzo-p-dioxins, 89.8% for octa-chlorodibenzodioxin, 78% for tetra-chlorodibenzofuran, and 89.8% for octachlorodibenzofuran. The larger the mass emission from the HEPA filter, the lower the overall removal efficiency, and the larger the ratio of the filter flow rate (Q_f) to the room flow rate (Q), the higher the overall removal efficiency. When the ratio of Q_f/Q is 15, an overall removal efficiency of 90% can be reached for all four of the selected compounds. The removal of the four selected compounds does not change as the relative humidity increases ≤90%.     

Comparison of Emission of Dioxins and Furans from Gasohol- and Ethanol-Powered Vehicles

ABSTRACT

The exhaust emissions of 17 polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) were investigated in two spark-ignition light-duty vehicles, one gasohol-fueled and a flexible-fuel one fueled with hydrated ethanol. Gasohol is a mixture of gasoline and 22% ethanol. The influence of fuel type and quality, lubricant oil type, and use of fuel additives on the formation of these compounds was tested using standardized U.S. Federal Test Procedure (FTP)-75 cycle tests. The sampling of the PCDD/Fs followed the recommendations of a modified U.S. Environmental Protection Agency (EPA) Method 23 (http://www.epa.gov/ttn/emc/promgate/m-23.pdf) and the analysis basically followed the U.S. EPA Method 8290 (http://www.epa.gov/osw/hazard/testmethods/sw846/pdfs/8290a.pdf). Results showed that emission factors of PCDD/Fs for the gasohol vehicle varied from undetected to 0.068 pg international toxic equivalency (I-TEQ) km^?1 (average of 0.0294 pg I-TEQ km^?1), whereas in the ethanol vehicle they varied from 0.004 to 0.157 pg (I-TEQ) km^?1 (average of 0.031 pg I-TEQ km^?1). In the gasohol-powered vehicle, the use of fuel additive diminished the emission of Octachlorodibenzo-p-dioxin (OCDD) significantly, whereas in the ethanol vehicle no significant associations were observed between the investigated variables and the emissions.

IMPLICATIONS The objective of this work was to analyze differences in emissions from a traditional fossil fuel (gasoline) and an alternative renewable fuel (ethanol from sugarcane), and the influence of fuel additives and lubricant oils on the formation of chlorinated dioxins and furans in spark-ignition light-duty gasohol and ethanol vehicles. Renewable fuels are very important in terms of climate change but the risk to the population's health must not increase. Thus the results of this work could help in the development of environmental impact studies as well as orienting policy-makers in formulating strategies for air pollution control.     

Photochemical modeling in California with two chemical mechanisms: model intercomparison and response to emission reductions

An updated version of the Statewide Air Pollution Research Center (SAPRC) chemical mechanism (SAPRC07C) was implemented into the Community Multiscale Air Quality (CMAQ) version 4.6. CMAQ simulations using SAPRC07C and the previously released version, SAPRC99, were performed and compared for an episode during July-August, 2000. Ozone (O3) predictions of the SAPRC07C simulation are generally lower than those of the SAPRC99 simulation in the key areas of central and southern California, especially in areas where modeled concentrations are greater than the federal 8-hr O3 standard of 75 parts per billion (ppb) and/or when the volatile organic compound (VOC)/nitrogen oxides (NOx) ratio is less than 13. The relative changes of ozone production efficiency (OPE) against the VOC/NOx ratio at 46 sites indicate that the OPE is reduced in SAPRC07C compared with SAPRC99 at most sites by as much as approximately 22%. The SAPRC99 and SAPRC07C mechanisms respond similarly to 20% reductions in anthropogenic VOC emissions. The response of the mechanisms to 20% NOx emissions reductions can be grouped into three cases. In case 1, in which both mechanisms show a decrease in daily maximum 8-hr O3 concentration with decreasing NOx emissions, the O3 decrease in SAPRC07C is smaller. In case 2, in which both mechanisms show an increase in O3 with decreasing NOx emissions, the O3 increase is larger in SAPRC07C. In case 3, SAPRC07C simulates an increase in O3 in response to reduced NOx emissions whereas SAPRC99 simulates a decrease in O3 for the same region. As a result, the areas where NOx controls would be disbeneficial are spatially expanded in SAPRC07C. Although the results presented here are valuable for understanding differences in predictions and model response for SAPRC99 and SAPRC07C, the study did not evaluate the impact of mechanism differences in the context of the U.S. Environmental Protection Agency's guidance for using numerical models in demonstrating air quality attainment. Therefore, additional study is required to evaluate the full regulatory implications of upgrading air quality models to SAPRC07.     

Comparison of emission of dioxins and furans from gasohol- and ethanol-powered vehicles

The exhaust emissions of 17 polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) were investigated in two spark-ignition light-duty vehicles, one gasohol-fueled and a flexible-fuel one fueled with hydrated ethanol. Gasohol is a mixture of gasoline and 22% ethanol. The influence of fuel type and quality, lubricant oil type, and use of fuel additives on the formation of these compounds was tested using standardized U.S. Federal Test Procedure (FTP)-75 cycle tests. The sampling of the PCDD/Fs followed the recommendations of a modified U.S. Environmental Protection Agency (EPA) Method 23 (www.epa.gov/ttn/ emc/promgate/m-23.pdf) and the analysis basically followed the U.S. EPA Method 8290 (http://www.epa.gov/osw/ hazard/testmethods/sw846/pdfs/8290a.pdf). Results showed that emission factors of PCDD/Fs for the.gasohol vehicle varied from undetected to 0.068 pg international toxic equivalency (I-TEQ) km(-1) (average of 0.0294 pg I-TEQ km(-1)), whereas in the ethanol vehicle they varied from 0.004 to 0.157 pg (I-TEQ) km(-1) (average of 0.031 pg I-TEQ km(-1)). In the gasohol-powered vehicle, the use of fuel additive diminished the emission of Octachlorodibenzo-p-dioxin (OCDD) significantly, whereas in the ethanol vehicle no significant associations were observed between the investigated variables and the emissions.     

Nondestructive characterization of municipal-solid-waste-contaminated surface soil by energy-dispersive X-ray fluorescence and low-Z (atomic number) particle electron probe X-ray microanalysis

The long-term environmental impact of municipal solid waste (MSW) landfilling is still under investigation due to the lack of detailed characterization studies. A MSW landfill site, popularly known as Dhapa, in the eastern fringe of the metropolis of Kolkata, India, is the subject of present study. A vast area of Dhapa, adjoining the current core MSW dump site and evolving from the raw MSW dumping in the past, is presently used for the cultivation of vegetables. The inorganic chemical characteristics of the MSW-contaminated Dhapa surface soil (covering a 2-km stretch of the area) along with a natural composite (geogenic) soil sample (from a small countryside farm), for comparison, were investigated using two complementary nondestructive analytical techniques, energy-dispersive X-ray fluorescence (EDXRF) for bulk analysis and low-Z (atomic number) particle electron probe X-ray microanalysis (low-Z particle EPMA) for single-particle analysis. The bulk concentrations of K, Rb, and Zr remain almost unchanged in all the soil samples. The Dhapa soil is found to be polluted with heavy metals such as Cu, Zn, and Pb (highly elevated) and Ti, Cr, Mn, Fe, Ni, and Sr (moderately elevated), compared to the natural countryside soil. These high bulk concentration levels of heavy metals were compared with the Ecological Soil Screening Levels for these elements (U.S. Environment Protection Agency) to assess the potential risk on the immediate biotic environment. Low-Z particle EPMA results showed that the aluminosilicate-containing particles were the most abundant, followed by SiO2, CaCO3-containing, and carbonaceous particles in the Dhapa samples, whereas in the countryside sample only aluminosilicate-containing and SiO2 particles were observed. The mineral particles encountered in the countryside sample are solely of geogenic origin, whereas those from the Dhapa samples seem to have evolved from a mixture of raw dumped MSW, urban dust, and other contributing factors such as wind, precipitation, weather patterns, farming, and water logging, resulting in their diverse chemical compositions and the abundant observation of carbonaceous species. Particles containing C and P were more abundant in the Dhapa samples than in the countryside soil sample, suggesting that MSW-contaminated soils are more fertile. However, the levels of particles containing potentially toxic heavy metals such as Cr, Mn, Ni, Cu, Zn, and/or Pb in the Dhapa samples were significant, corroborated by their high bulk concentration levels (EDXRF), causing deep concern for the immediate environment and contamination of the food chain through food crops.