Distribution of Light Hydrocarbons in Ambient Air

The diversity of hydrocarbons which are present in ambient polluted air provide a potentially rich source of information concerning the nature of this type of pollution. Measurements of the relative amounts of various hydrocarbons can be correlated with the various possible sources. Since hydrocarbon reactivities vary widely it is also possible to estimate the extent to which various individual hydrocarbons have reacted. Except for samples taken deliberately near sources of hydrocarbon pollution these air samples invariably resemble auto exhaust with an addition of natural gas and of C₃–C₅ paraffins which resemble gasoline vapor. Samples taken in industrial areas and near the smoke plume from a brush fire showed distinctive differences in composition. During the smog season in the fall of 1968 good data were obtained of “typical” or “representative” samples of light, medium and heavy smog. These show the expected depletion of more reactive hydrocarbons in a much more convincing way than before. By comparing these distributions with composition in unreacted samples and by making use of data from bottle irradiations, it was possible to estimate the contribution of the various hydrocarbons in terms of “amount reacted.” The amounts of higher hydrocarbons present and reacted were also estimated from gasoline composition.     

Supercritical Fluid Extraction for Forensic Analysis of Hydrocarbons in Soil

Supercritical fluid extraction (SFE) was investigated to evaluate its potential for obtaining high quality chromatographic fingerprints from soils encountered in environmental investigations. While the volatile and semivolatile fractions of light nonaqueous phase liquid (LNAPL) samples can be “fingerprinted” in a single chromatographic run, it is commonly not possible to obtain samples of LNAPL in the locations of interest. For this and other reasons, it was desirable to develop this method (SFE) of soil extraction, which allows chromatographic fingerprinting of the same quality routinely obtained with LNAPL so that environmental forensic investigations could be extended to areas beyond those containing LNAPL in monitoring wells. In this study, SFE was compared to conventional dichloromethane extraction. Both artificially spiked soil and soil from petroleum release sites were tested. Since water can be a problem when using the SFE method, particular attention was given to handling soils with high moisture contents. The SFE extracts showed excellent retention of low molecular components, including pentanes. Gas chromatography of SFE extracts yielded molecular distributions that showed no significant bias toward either low or high molecular weight components. These results show that SFE can be used to obtain an unbiased, single-run chromatographic “fingerprint” of both volatile and semivolatile hydrocarbons in contaminated soil samples.     

Source Fingerprints for Volatile Non-Methane Hydrocarbons

Non-methane hydrocarbon (NMHC) source profiles consisting of 35 hydrocarbon species were measured for vehicle and petroleum refinery emissions. Refueling emissions were found to be sensitive to the grade and volatility class of fuel and to be composed mainly of saturated hydrocarbons such as n-butane and 2-methy I butane. Unsaturated and aromatic hydrocarbons, which are released from the tailpipe of vehicles as products of combustion and unburned fuel, were more prevalent in roadway emissions comprising approximately 34 percent of the total NMHCs. Cold-start emissions were nearly indistinguishable from the roadway emission profile. The only significant differences were in toluene, ethylene and acetylene, which may be related to the efficiency of combustion when the vehicle is initially started. Saturated hydrocarbon distributions of the hot-soak profiles were found to be similar to refueling emissions. The only significant difference in the profiles was in the aromatic content, which may be related to the grade of the gasoline and the effectiveness of evaporative emission control devices. The temporal variation in refinery emissions was significant and may be related to variations in refinery activities such as the production and blending of feed stocks to produce different fuels.     

PANs in the Atmosphere

The types of PANs and PBzNs present or possibly present in the ambient atmosphere are discussed. Biological activities of the PANs and PBzNs are briefly considered. The concentration and composition of PANs in the atmosphere are discussed and calculations made of the production of RGO radicals from precursor alkanes, alkenes and aromatic hydrocarbons present in the atmosphere. Lifetimes of PANs are estimated, and the effects of transport on the composition of PANs is evaluated.     

Methane in the Atmosphere

Methane is present in the troposphere with a volume concentration of about 1.5 ppm. Estimates of Koyama (1963) indicate a predominantly biological origin with a total production rate of about 2.7 × 10¹⁴ g CH₄/yr. From that he estimated the atmospheric lifetime of methane to be around 20 years. Measurements of the C-l4 in methane by Libby and later by Bainbridge, et al. (1961 ) gave a C-l4 content of 75% of recent wood and, therefore, confirm the predominant biological origin, the addition of inactive CH; from industrial sources being only about 25%. Much less is known about sinks of CH₄. Cadle (1966) reported fairly high destruction rates by atomic O, a reaction which should be important at high altitude. Bainbridge (1966) indeed reports a decrease in the measured methane concentration above the tropopause. He, however, considers this decrease too small to account for the destruction rate of 20 years estimated by Koyama. Our measurements on air samples collected on aircraft flights at various altitudes show a high variability of the CH₄ content both with time and altitude.     

Development of a High-Temperature Subtractive Analyzer for Hydrocarbons

This paper discusses the development of a high-temperature subtractive analyzer for separating the hydrocarbons present in gaseous mixtures into two categories— reactive hydrocarbons and unreactive hydrocarbons. The analyzer utilizes the ability of selected substances to absorb certain groups of hydrocarbons and their derivatives from a gas mixture and is designed for operation with a flame ion-ization detector. The body of information presented in this paper is directed to individuals concerned with the analysis of the exhaust gases of gas turbine engines or other combustion sources as stationary power plants. The analyzer grew out of an investigation of a previously reported subtractive analyzer system which operates at ambient temperature. Current state-of-the-art requirements for the accurate determination of total hydrocarbons at the concentrations present in turbine exhaust gases necessitate that sampling and measurements be conducted at elevated temperatures (325-375°F), rather than ambient temperature, to reduce or eliminate condensation and wall adsorption sampling errors. To fulfill this requirement, the sampling lines and flame ionization detector must be heated. After tests determined that the previously reported scrubber system would not remove the same hydrocarbons at elevated temperature levels as it did at ambient temperatures, an investigation of the effectiveness of various absorbents at elevated temperatures was conducted. This led to the development and test of the high-temperature subtractive analyzer concept discussed in this report. In its final form, one path of this unit contains no absorbent, the second contains a column of concentrated H₂SO₄ on Ultraport and a column containing PdSO₄ and H₂SO₄ on Ultraport. The two columns are connected in series. The absorbents remove olefins, aromatics, acetylene, and oxygenated hydrocarbons but pass paraffins. As the final step in this program, a comparison of the two subtractive analyzers was made using the exhaust from a gas turbine combustion system.     

Determination of Volatile Organic Compounds in the Atmosphere Using Two Complementary Analysis Techniques

ABSTRACT

During a preliminary field campaign of volatile organic compound (VOC) measurements carried out in an urban area, two complementary analysis techniques were applied to establish the technical and scientific bases for a strategy to monitor and control VOCs and photochemical oxidants in the Autonomous Community of the Basque Country. Integrated sampling was conducted using Tenax sorbent tubes and laboratory analysis by gas chromatography, and grab sampling and in situ analysis also were conducted using a portable gas chromatograph. With the first technique, monocyclic aromatic hydrocarbons appeared as the compounds with the higher mean concentrations. The second technique allowed the systematic analysis of eight chlorinated and aromatic hydrocarbons. Results of comparing both techniques, as well as the additional information obtained with the second technique, are included.     

Studies on the Analysis of Hydrocarbons From Incinerator Effluents with a Flame Ionization Detector

In January 1966, 483 randomly selected 1963-1966-model automobiles were inspected at the Cincinnati Vehicle Inspection Station to determine the effectiveness of their positive crankcase ventilation systems. All of these automobiles should have had crankcase ventilation systems installed in accord with the voluntary program of the automobile manufacturers. However, 48 of the automobiles inspected had no positive crankcase ventilation system. In addition, 27 cars were equipped with systems which could not readily be tested. Testing of the remaining 408 cars was performed with a combination pressure-vacuum gauge designed to measure the airflow in the crankcase. Results showed that 71% of the positive crankcase ventilation systems tested were operating satisfactorily and impending maintenance of systems was indicated for 29% of the automobiles tested. Although the systems of certain makes of cars performed considerably better than others, a definite decrease in system performance with increasing age and mileage was observed for the cars tested. The performance data indicate that the periodic maintenance required for positive crankcase ventilation systems is not being implemented. Only 47.5% of the drivers questioned were aware of the system and only 10% knew whether their system had been serviced.     

Carbon Monoxide in the Atmosphere

A carbon monoxide analyzer has been developed which is capable of continuous measurement of the carbon monoxide concentration in the atmosphere. The operating principle of the instrument is the reaction of carbon monoxide with hot mercuric oxide followed by the photometric determination of the mercury vapor produced. Oxygenated hydrocarbons and olefins are quantitatively detected. Those normally present are in the ambient atmosphere in low concentrations relative to CO. Hydrogen and methane in the atmosphere do not interfere with the CO analysis. Measurements of atmospheric CO concentrations in California, Greenland, and Oregon seem to indicate that CO content is an air mass characteristic. North Pacific marine air mass concentrations may be as low as about 0.040 parts per million (ppm) CO, while the air mass over continental California seems to be characterized by CO levels of 0.5-1.0 ppm or greater.     

Characterization of Polycyclic Aromatic Hydrocarbons from the

Abstract

Diesel fuels governed by U.S. regulations are based on the index of the total aromatic contents. Three diesel fuels, containing various fractions of light cycle oil (LCO) and various sulfur, total polyaromatic, and total aromatic contents, were used in a heavy-duty diesel engine (HDDE) under transient cycle test to assess the feasibility of using current indices in managing the emissions of polycyclic aromatic hydrocarbons (PAHs) from HDDE. The mean sulfur content in LCO is 20.8 times as much as that of premium diesel fuel (PDF). The mean total polyaromatic content in LCO is 28.7 times as much as that of PDF, and the mean total aromatic content in LCO is 2.53 times as much as that of PDF. The total polyaromatic hydrocarbon emission factors in the exhaust from the diesel engine, as determined using PDF L3.5 (3.5% LCO and 96.5% PDF), L7.5 (7.5% LCO and 92.5% PDF), and L15 (15% LCO and 85% PDF) were 14.3, 25.8, 44, and 101 mg L^?1, respectively. The total benzo(a)pyrene equivalent (BaP_eq) emission factors in the exhaust from PDF, L3.5, L7.5, and L15 were 0.0402, 0.121, 0.219, and 0.548 mg L^?1, respectively. Results indicated that using L3.5 instead of PDF will result in an 80.4% and a 201% increase of emission for total PAHs and total BaP_eq, respectively. The relationships between the total polyaromatic hydrocarbon emission factor and the two emission control indices, including fuel polyaromatic content and fuel aromatic content, suggest that both indices could be used feasibly to regulate total PAH emissions. These results strongly suggest that LCO used in the traveling diesel vehicles significantly influences PAH emissions.     

Particulate Elemental Carbon in the Atmosphere

This report summarizes the important results which were presented at an international symposium on particulate elemental carbon in the atmosphere. The “Particulate Carbon: Atmospheric Life Cycle” symposium was sponsored by General Motors Research Laboratories on October 12–14, 1980. Supplemental background data are included.     

Use of Benzo[a]pyrene Relative Abundance Ratios to Assess Exposure to Polycyclic Aromatic Hydrocarbons in the Ambient Atmosphere in the Vicinity of a Söderberg Aluminum Smelter

ABSTRACT

The purpose of this study was to investigate the use of benzo[a]pyrene (B[a]P) relative abundance ratios (RARs) to assess exposure to polycyclic aromatic hydrocarbons (PAHs) in the urban atmospheric air in the vicinity of a horizontal stud Söderberg aluminum reduction facility. The B[a]P RARs refer to the concentration of individual PAHs measured in a given sample divided by the concentration of B[a]P found in the same sample. This study compared the B[a]P RARs calculated for the facility stack and three sites near the Söderberg aluminum smelter for three different sampling periods. Interperiod differences were significant for many of the PAHs, and the differences between the stations proved insignificant at p < 0.05. The differences between each individual station and the facility stack were significant for all PAHs. B[a]P RARs increased in value at the stations compared with the stack, indicating that B[a]P may be degraded or removed from the atmosphere at a rate greater than that of the majority of the measured PAHs. It is concluded that B[a]P and B[a]P RARs may be poor markers of exposure to PAHs in the vicinity of this Söderberg aluminum refinery for the entire mixture of PAHs present in the ambient atmosphere.     

Using Nanoscale Zero-Valent Iron for the Remediation of Polycyclic Aromatic Hydrocarbons Contaminated Soil

Abstract

The sites contaminated with recalcitrant organic compounds, such as polycyclic aromatic hydrocarbons (PAHs) with multiple benzene rings, are colossal and ubiquitous environmental problems. They are relatively nonbiodegradable and mutagenic, and 16 of them are listed in the U.S. Environment Protection Agency priority pollutants. Thus, the efficient and emerging remediation technologies for removal of PAHs in contaminated sites have to be uncovered urgently. In this decade, the zero-valent iron (ZVI) particles have been used successfully in the laboratory, pilot, and field, such as degradation of chlorinated hydrocarbons and remediation of the other pollutants. Nevertheless, as far as we know, little research has investigated for soil remediation; this study used nanoscale ZVI particles to remove pyrene in the soil. The experimental variables were determined, including reaction time, iron particle size, and dosage. From the results, both the micro- and nanoscales of ZVI were capable of removing the target compound in soil, but the higher removal efficiencies were by nanoscale ZVI because of the massive specific surface area. The optimal operating conditions to attain the best removal efficiency of pyrene were obtained while adding nanoscale ZVI 0.1 g/g soil within 60 min and 150 rpm of mixing. Thus, nanoscale ZVI has proved to be a promising remedy for PAH-contaminated soil in this study, as well as an optimistically predictable application for additional pilot and field studies.     

二维气相色谱法测定空气中的总烃及非甲烷总烃

采用单一进样口六通阀进样、毛细管柱二维气相色谱仪三通路分离塔柱分离系统、采用氢离子化检测器分别产生信号,测定环境空气中的非甲烷总烃。通过柱分离系统将样品平均分配到不同类型的两个毛细管色谱柱,分别测定总烃及甲烷。方法简单、快速,最大程度地保证了进样的一致性,从而保证了分析结果的准确性。     

The Atmosphere as a Sink for Applied Pesticides

Pesticides are removed from the atmosphere by surface deposition, washout, or chemical reaction. The atmosphere is a sink only when the rate of chemical degradation limits the esidence time of the pesticide. Little is known about atmospheric degradation rates, and in many cases, even the reaction pathway may be uncertain. Photochemical conversion is considered a primary reaction mechanism, but reaction with atmospheric oxidants may also be important.     

An Equilibrium Analysis of Some Chlorinated Hydrocarbons in Stoichiometric to Fuel-rich Post-flame Combustion Environments

The equilibrium composition of product gases from the combustion of chlorinated hydrocarbons (CHC) has been studied for varying ratios of C, H, Cl, and O under stoichiometric to fuel-rich conditions. An interactive, PC-compatible FORTRAN program, STANJAN, was utilized in conjunction with thermochemical data sources to calculate equilibrium compositions of gas mixtures as a function of temperature. The predicted results, when judiciously Interpreted, assist in the understanding of the potential for formation of residual organic substance emissions (ROSEs) in post-flame environments of an incinerator.

Arguments are presented for the potential formation of chlorinated species, which are stable at ambient temperature, if locally fuel-rich mixtures penetrate into the lower temperature zones of an incinerator. ROSEs that have been observed in field tests of incinerators burning chlorinated compounds are predicted to form under the fuel-rich condition. Furthermore, when the equivalence ratio is greater than unity by even a slight amount, the degree of chlorination of product gases increases markedly when the Cl/H ratio also exceeds unity. In that case, time, temperature, turbulence and an overall fuel-lean stoichiometry may not be sufficient to guarantee elimination of measurable levels of chlorinated products. Possible implications of the equilibrium calculations are discussed. Further systematic studies with additional CHCs, nitrogen?, sulfur?, and heavy metal-bearing compounds are recommended as well as continued efforts to carry out kinetic studies.