Volatile Organic Compounds from Coal Tar and Soil Vapor Samples at MGP Sites

This study characterized organic compounds found in New York State manufactured gas plant (MGP) coal tar vapors using controlled laboratory experiments from four separate MGP sites. In addition, a limited number of deep (0.3–1.2 m above coal tar) and shallow (1.2–2.4 m above coal tar) soil vapor samples were collected above the in situ coal tar source at three of these sites. A total of 29 compounds were consistently detected in the laboratory-generated coal tar vapors at 50°C, whereas 24 compounds were detected at 10°C. The compounds detected in the field sample results were inconsistent with the compounds found in the laboratory-generated samples. Concentrations of compounds in the shallow soil vapor sample were either non-detectable or substantially lower than those found in deeper samples, suggesting attenuation in the vadose zone. Laboratory-generated data at 50°C compared the (% non-aromatic)/(% aromatic) ratio and indicated that this ratio may provide good discrimination between coal tar vapor and common petroleum distillates.     

Comparison of Selenium and Sulfur at Remote Sites

Abstract

The Interagency Monitoring of Protected Visual Environments (IMPROVE) particulate monitoring network has been collecting aerosols for visibility apportionment at remote sites in the United States since 1988. The measurements include the major PM_2.5 components, such as sulfur, carbon, and nitrate, and trace elements, such as selenium. This paper will examine the relationship between the sulfurs and selenium concentrations at 61 sites for samples collected in the seasonal year 1993. Maps of mean sulfur and selenium measurements in summer 1993 and winter 1993-1994 indicate that there are well-defined regional patterns for both elements, with concentrations in the Appalachian region that are ten times those in areas of the Pacific Northwest. The S/Se ratios of means are relatively uniform across the United States, at around 2000 in summer and 1000 in winter, indicating a strong sulfur-selenium relationship. The role of conversion of S0₂ to sulfate can also be deduced from the means. For individual samples taken during summer 1993, there is a high correlation between the two variables in the East, especially at sites in the Northeast, where the correlation coefficients (r²) are around 0.9. In the West, the correlation is much lower. This is attributed to fewer sources and differing emission factors.     

Effects of Operating Variables on PAH Emissions and Mutagenicity of Emissions from Woodstoves

As part of the Integrated Air Cancer Project, the U.S. Environmental Protection Agency (EPA) has conducted field emission measurement programs in Raleigh, North Carolina, and Boise, Idaho, to identify the potential mutagenic Impact of residential wood burning and motor vehicles on ambient and indoor air. These studies included the collection of emission samples from chimneys serving wood burning appliances. Parallel projects were undertaken in Instrumented woodstove test laboratories to quantify woodstove emissions during operations typical of in-house usage but under more controlled conditions.

Three woodstoves were operated In test laboratories over a range of burnrates, burning eastern oak, southern yellow pine, or western white pine. Two conventional stoves were tested at an altitude of 90 m. One of the conventional stoves and a catalytic stove were tested at an altitude of 825 m.

Decreasing burnrate increased total paniculate emissions from the conventional stoves while the catalytic stove's total particulate emissions were unaffected. There was no correlation of total particulate emissions with altitude whereas total polynuclear aromatic hydrocarbon (PAH) emissions were higher at the lower altitude. Mutagenicity of the catalytic stove emissions was higher than emissions from the conventional stove. Emissions from burning pine were more mutagenic than emissions from oak.     

Light Scattering from Sea-Salt Aerosols at Interagency Monitoring of Protected Visual Environments (IMPROVE) Sites

Abstract

A method is described to estimate light scattering (Bsp) by sea-salt aerosols at coastal locations in the Interagency Monitoring of Protected Visual Environments (IMPROVE) network. Dry mass scattering efficiencies for fine and coarse sea-salt particles were based on previously measured dry sea-salt size distributions. Enhancement of sea-salt particle scattering by hygroscopic growth was based on NaCl water activity data. Sea-salt aerosol mass at the IMPROVE site in the Virgin Islands (VIIS) was estimated from strontium (Sr) concentrations in IMPROVE aerosol samples. Estimated Bsp, including contributions from sea-salt mass based on Sr, agreed well with measured Bsp at the VIIS IMPROVE site. On average, sea salt accounted for 52% of estimated Bsp at this site. Sea-salt aerosol mass cannot be reliably estimated from Sr unless its crustal enrichment factor exceeds 10. Sodium (Na) concentrations are not accurately determined by X-ray fluorescence analysis in IMPROVE samples. It is recommended that Na be measured in the fine and coarse modes by a more appropriate method, such as atomic absorption spectroscopy or ion chromatography, to account for scattering by sea-salt particles at IMPROVE sites where such contributions may be significant.     

Sorption-Desorption of Atrazine and Diuron in Soils from Southern Brazil

The objective of this study was to investigate the behavior of sorption and desorption of the herbicides atrazine (6-chloro-N ²-ethyl-N ⁴-isopropyl-1,3,5-triazine-2,4-diamine) and diuron [3-(3,4-dichlorophenyl)-1,1-dimethyleurea] in soil samples from a typical lithosequence located in the municipality of Mamborê (PR), southern Brazil. Five concentrations of ¹⁴C-atrazine and ¹⁴C-diuron were used for both herbicides (0.48, 0.96, 1.92, 3.84, and 7.69 mg L^?1). Sorption of both herbicides correlated positively with the organic carbon and clay content of the soil samples. Sorption isotherms were well described by the Freundlich model. The slope values of the isotherm (N) ranged from 0.84 to 0.90 (atrazine) and from 0.75 to 0.79 (diuron) for the lithosequence samples. Sorption of diuron was high regardless of the soil texture or the concentration added. The desorption isotherms for atrazine and diuron showed good fit to the Freundlich equation (R ² ≥ 0,87). Atrazine slope values for the desorption isotherms were similar for the different concentrations and were much lower than those observed for the sorption isotherms. Significant hysteresis was observed in the herbicide desorption. When the two herbicides were compared, it was found that diuron (N = 0.06–0.22) presented more pronounced hysteresis than atrazine. The results showed that, quantitatively, a greater atrazine fraction applied to these soils remains available to be leached in the soil profile, as compared to diuron.     

Soil Gas Methane at Petroleum Contaminated Sites: Forensic Determination of Origin and Source

Hydrocarbon vapors associated with spilled petroleum products arouse regulatory concern and can pose a significant health and safety risk. While petroleum products do not contain a significant amount of methane (CH 4 ), high CH 4 contents in soil gas near petroleum spills have been reported. While CH 4 is nontoxic, its accumulation in shallow soil gas represents a potential explosion and asphyxiation hazard, especially in confined spaces. Identifying the source and origin of shallow CH 4 accumulations is an important part of evaluating potential exposure pathways, selecting appropriate remedial measures, and determining environmental liability. This paper discusses the potential nature and anthropogenic sources for shallow CH 4 and how integration of geological, geochemical, and land use data can be used to determine its origin and identify its source. Two case studies are presented, one where CH 4 associated with a gasoline spill is shown to be derived from a natural source rather than the gasoline, and a second where CH 4 associated with spilled crude oil is shown to be produced in the vadose zone by biodegradation of the oil.     

Soil Gas Methane at Petroleum Contaminated Sites: Forensic Determination of Origin and Source

Hydrocarbon vapors associated with spilled petroleum products arouse regulatory concern and can pose a significant health and safety risk. While petroleum products do not contain a significant amount of methane (CH₄), high CH₄contents in soil gas near petroleum spills have been reported. While CH₄is nontoxic, its accumulation in shallow soil gas represents a potential explosion and asphyxiation hazard, especially in confined spaces. Identifying the source and origin of shallow CH₄accumulations is an important part of evaluating potential exposure pathways, selecting appropriate remedial measures, and determining environmental liability. This paper discusses the potential nature and anthropogenic sources for shallow CH₄and how integration of geological, geochemical, and land use data can be used to determine its origin and identify its source. Two case studies are presented, one where CH₄associated with a gasoline spill is shown to be derived from a natural source rather than the gasoline, and a second where CH₄associated with spilled crude oil is shown to be produced in the vadose zone by biodegradation of the oil.     

Day-of-Week Patterns of Particulate Matter and Its Chemical Components at Selected Sites in California

Abstract

This paper analyzes day-of-week variations in concentrations of particulate matter (PM) in California. Because volatile organic compounds (VOCs) and oxides of nitrogen (NO_x) are not only precursors of ozone (O₃) but also of secondary PM, it is useful to know whether the variations by day of week in these precursors are also evident in PM data. Concentrations of PM ≤10 μm (PM₁₀) and ≤2.5[H9262]m in aerodynamic diameter (PM_2.5) were analyzed. PM concentrations exhibit a general weekly pattern, with the maximum occurring late in the workweek and the minimum occurring on weekends (especially Sunday); however, this pattern does not prevail at all sites and areas. PM nitrate (NO₃ ^-) data from Size Selective Inlet (SSI) samplers in the South Coast Air Basin (SoCAB) tend to be somewhat lower on weekends compared with weekdays. During 1988–1991, the weekend average was lower than the weekday average at 8 of 13 locations, with an average decrease of 1%. During 1997–2000, the weekend average was lower than the weekday average at 10 of 13 locations, with an average decrease of 6%. The weekend averages are generally lower than weekday averages for sulfates, organic carbon, and elemental carbon. Because heavy-duty trucks typically represent a major source of elemental carbon, the weekend decrease in heavy-duty truck traffic may also result in a decrease in ambient elemental carbon concentrations.     

Sorption Kinetics of Atrazine and Diuron in Soils from Southern Brazil

Abstract

Sorption kinetics of atrazine and diuron was evaluated in soil samples from a typical landscape in Paraná. Samples were collected (0–20 cm) in a no-tillage area from Mamborê, PR, which has been cultivated under a crop rotation for the last six years. Six sampling points of the slope were selected to represent a wide range of soil chemical and physical properties found in this area. Radiolabeled tracers (¹⁴C-atrazine and ¹⁴C-diuron) were used and the radioactivity was detected by liquid scintillation counting (LSC). Sorption was accomplished for increasing equilibration periods (0.5, 1.5, 3, 6, 12, 24, and 48 h). Kinetics data fitted adequately well to Elovich equation, providing evidences that soil reaction occurs in two distinct stages: a fast, initial one followed by a slower one. During the fast phase, 34–42 and 71–79% of total atrazine and diuron applied were sorbed to soil samples. No important differences were found among combinations of soil and herbicide sorption during the slow phase. The unrealistic conditions under batch experiments should be overestimating sorption in the fast phase and underestimating diffusion in the slow phase. Sorption of both herbicides was positively correlated to organic carbon and clay contents of soils, but atrazine was much less sorbed than diuron, showing its higher potential to contaminate groundwater, specially in sandy, low organic carbon soils.     

Contribution of Primary and Secondary Sources to Organic Aerosol and PM2.5 at SEARCH Network Sites

Abstract

Chemical tracer methods for determining contributions to primary organic aerosol (POA) are fairly well established, whereas similar techniques for secondary organic aerosol (SOA), inherently complicated by time-dependent atmospheric processes, are only beginning to be studied. Laboratory chamber experiments provide insights into the precursors of SOA, but field data must be used to test the approaches. This study investigates primary and secondary sources of organic carbon (OC) and determines their mass contribution to particulate matter 2.5 µm or less in aerodynamic diameter (PM_2.5) in Southeastern Aerosol Research and Characterization (SEARCH) network samples. Filter samples were taken during 20 24-hr periods between May and August 2005 at SEARCH sites in Atlanta, GA (JST); Birmingham, AL (BHM); Centerville, AL (CTR); and Pensacola, FL (PNS) and analyzed for organic tracers by gas chromatography-mass spectrometry. Contribution to primary OC was made using a chemical mass balance method and to secondary OC using a mass fraction method. Aerosol masses were reconstructed from the contributions of POA, SOA, elemental carbon, inorganic ions (sulfate [SO₄ ^2?], nitrate [NO₃ ^?], ammonium [NH₄ ⁺]), metals, and metal oxides and compared with the measured PM_2.5. From the analysis, OC contributions from seven primary sources and four secondary sources were determined. The major primary sources of carbon were from wood combustion, diesel and gasoline exhaust, and meat cooking; major secondary sources were from isoprene and monoterpenes with minor contributions from toluene and β-caryophyllene SOA. Mass concentrations at the four sites were determined using source-specific organic mass (OM)-to-OC ratios and gave values in the range of 12–42 µg m^?3. Reconstructed masses at three of the sites (JST, CTR, PNS) ranged from 87 to 91% of the measured PM_2.5 mass. The reconstructed mass at the BHM site exceeded the measured mass by approximately 25%. The difference between the reconstructed and measured PM_2.5 mass for nonindustrial areas is consistent with not including aerosol liquid water or other sources of organic aerosol.     

Toxicity identification and reduction of wastewaters from a pigment manufacturing factory

In this study, major toxicants in pigment wastewaters (i.e. raw wastewater and effluent) were determined by toxicity identification evaluations (TIEs), and changes in their toxicities due to combined gamma-ray (gamma-ray) and ozone treatments were evaluated. From TIE results using Daphnia magna, Cr(VI) and o-toluidine were identified as major toxicants in the raw wastewater with concentrations of 2.47 and 25.3mg l(-1), respectively. This was confirmed by subsequent spiking and mass balance approaches. For effluent, TIE results suggested that organic anions were likely responsible for the observed toxicities. Toxicity reduction tests showed that gamma-rays with ozone treatment after coagulation was more efficient in reducing toxicities in the raw wastewater (3.9-2.0 TU) than gamma-ray treatment alone (3.9-3.1 TU). For pigment effluent, gamma-ray/O3 treatment resulted in a complete removal of the acute toxicity.     

丙烯腈废水及几种处理工艺出水的毒性

分别利用小麦、发光菌毒性测试技术研究了模拟丙烯腈废水以及几种处理工艺出水对小麦芽伸长、根伸长、发芽率和发光菌发光度的毒性效应差异。结果表明,丙烯腈对小麦芽伸长的毒性影响最大;各类物质对小麦根伸长和发芽率并未造成毒性影响;其他物质对发光菌发光度的毒性最大。模拟废水对小麦芽伸长、根伸长、发芽率和发光菌发光度的毒性效应分别为:部分相加、部分相加、协同和拮抗作用。几种处理工艺出水对上述指标的毒性影响顺序依次是:模拟废水加成出水活性炭吸附出水Fenton法出水;Fenton法出水模拟废水加成出水活性炭吸附出水;Fenton法出水活性炭吸附出水模拟废水加成出水;活性炭吸附出水加成出水Fenton法出水模拟废水。比较几种处理工艺出水的毒性发现,几乎每种废水的毒性都有所降低,这说明几种处理工艺能有效降低模拟废水的毒性,具有深刻的实际指导意义。     

A 13-Week Comparison of Passive and Continuous Ozone Monitors at Forested Sites in North-Central Pennsylvania

ABSTRACT

Ogawa passive O₃ samplers were used in a 13-week study (June 1-September 1, 1999) involving 11 forested and mountaintop sites in north-central Pennsylvania. Four of the sites were collocated with TECO model 49 O₃ analyzers. A significant correlation (p < 0.0001) was found for 24-hr average weekly O₃ concentrations between the two methodologies at the four sites with collocated monitors. As expected, there were positive relationships between increasing elevation of the sites and increasing O₃ concentrations. No O₃ exposure patterns were found on a west-to-east or south-to-north basis; however, the area known for lower O₃ exposures within a smaller subsection of the study area showed consistently lower O₃ exposures. Preliminary results regarding relationships of symptom responses within O₃-sensitive bioindicators are also presented with black cherry (Prunus serotina, Elirli.) and common milkweed (Asclepias syriaca, L.) showing clear evidence of increasing injury with increasing O₃ exposures. Due to the extremely dry conditions encountered in north-central Pennsylvania during the 1999 growing season, O₃-induced symptoms were sporadic and quite delayed until late-season rains during the latter portion of the observation period.     

Mutagenicity of the extract recovered from airborne particles outside and inside a home with an unvented kerosene heater

Samples collected over a one month period outside and inside a home without a smoker, but with an unvented heater, in a suburban residential area in winter, were examined for mutagenicity with Ames' Salmonella typhimurium assay system. The extracts recovered with Soxhlet extractor and benzene-ethanol (4:1) exhibited mutagenic activity towards both TA 100 and TA 98 without metabolic activation and showed linear dose-response relationship up to the dose, 300μg plate⁻¹. Addition of microsomal enzymes, however, reduced this activity to a considerable extent. Although there was little difference of mutagenic activity between TA 100 and TA 98 for both indoor and outdoor sample, much stronger mutagenic activity (2–3 fold) was found in the indoor sample than in the outdoor sample towards both TA 100 and TA 98. The present results suggest that such increase in mutagenic activity may be attributed to substances derived from the kerosene heater and the inhabitants' living activity other than smoking.     

Toxicity of water and sediment from stormwater retarding basins to Hydra hexactinella

Hydra hexactinella was used to assess the toxicity of stormwater and sediment samples from three retarding basins in Melbourne, Australia, using an acute test, a sublethal test, and a pulse test. Stormwater from the Avoca St retarding basins resulted in a LC50 of 613 ml/L, NOEC and LOEC values of 50 ml/L and 100 ml/L, while the 7 h pulse exposure caused a significant increase in the mean population growth rate compared to the control. Water samples from the two other retarding basins were found non-toxic to H. hexactinella. This is the first study to employ sediment tests with Hydra spp. on stormwater sediments and a lower population growth rate was observed for organisms exposed to sediment from the Avoca St retarding basins. The behavioral study showed that H. hexactinella tended to avoid the sediment-water interface when exposed to sediment from all retarding basins, compared to the reference sediment. Further work is needed to determine the long-term effects of stormwater polluted sediments and acute effects due to organism exposure to short-term high concentrations during rain events.     

Field Measurements of Natural and Fertilizer-Induced N2O Release Rates from Soils

The influence of the soil on atmospheric N₂O was studied by In-situ measurements in 1976–1979 at several field stations near Mainz, Germany, where different soil types were located. Measurements were carried out using the closed chamber method and applying stainless steel capillaries allowing soil air sampling down to 60 cm depth. The N2O In soil was found to be produced and consumed simultaneously In the uppermost soil layer resulting In a net flux of N₂O with release rates of 0.5–16 μg N₂O–Nm^?2h^?1 on unfertilized natural as well as agriculturally used soils. After fertilization with mineral fertilizers the N₂O release rates increased to values ≤43 μg N₂O–Nm^?2h^?1. The total amount of fertilizer-N released Into the atmosphere as N₂O was determined to be 0.01–0.05% for nitrate and 0.03–0.09 % for ammonium fertilizer.     

Lead Contamination of Urban Soils and Vegetation by Emissions from Secondary Lead Industries

The degree and extent of lead contamination of urban soils and vegetation in the vicinity of secondary lead industries are provided. These urban industries, a secondary smelter reprocessing lead from used batteries and scrap metal and a manufacturer of new storage batteries, were located near residential communities. Levels as high as 21,000 ppm of lead in the upper 5 cm of soil (based on air dried weight) and 3500 and 2700 ppm in willow foliage (not washed and washed, respectively, based on dry weight) were found adjacent to the secondary smelter, with the levels decreasing exponentially from the sources. The data on lead contamination of soils and vegetation at various distances and directions from the urban secondary lead industries were compared with levels of lead found in control urban and highway locations. In addition, arsenic levels in soil were examined as a tracer for the source of industrial lead emissions. High levels of lead found In both vegetation and soil in the vicinity of the urban industries reflected both historical and current emissions of lead in those areas. These studies were conducted for industrial abatement purposes; to assist medical related epidemiology studies; to define the areas of severe contamination for soil cleanup purposes; and to formulate guidelines for excessive levels of lead in soil and vegetation. Since lead in soil is persistent, concern arises with respect to pica for small children, contamination of edible vegetables grown in high-lead soil, and reentrainment of leaded particulate matter into the air.     

Sorption and transport of iodine species in sediments from the Savannah River and Hanford Sites

Iodine is an important element in studies of environmental protection and human health, global-scale hydrologic processes and nuclear nonproliferation. Biogeochemical cycling of iodine is complex, because iodine occurs in multiple oxidation states and as inorganic and organic species that may be hydrophilic, atmophilic, and biophilic. In this study, we applied new analytical techniques to study the sorption and transport behavior of iodine species (iodide, iodate, and 4-iodoaniline) in sediments collected at the Savannah River and Hanford Sites, where anthropogenic (129)I from prior nuclear fuel processing activities poses an environmental risk. We conducted integrated column and batch experiments to investigate the interconversion, sorption and transport of iodine species, and the sediments we examined exhibit a wide range in organic matter, clay mineralogy, soil pH, and texture. The results of our experiments illustrate complex behavior with various processes occurring, including iodate reduction, irreversible retention or mass loss of iodide, and rate-limited and nonlinear sorption. There was an appreciable iodate reduction to iodide, presumably mediated by the structural Fe(II) in some clay minerals; therefore, careful attention must be given to potential interconversion among species when interpreting the biogeochemical behavior of iodine in the environment. The different iodine species exhibited dramatically different sorption and transport behavior in three sediment samples, possessing different physico-chemical properties, collected from different depths at the Savannah River Site. Our study yielded additional insight into processes and mechanisms affecting the geochemical cycling of iodine in the environment, and provided quantitative estimates of key parameters (e.g., extent and rate of sorption) for risk assessment at these sites.     

Control Technologies for Remediation of Contaminated Soil and Waste Deposits at Superf und Lead Battery Recycling Sites

This paper primarily addresses remediation of contaminated soils and waste deposits at defunct lead-acid battery recycling sites (LBRS) via immobilization and separation processes. A defunct LBRS is a facility at which battery breaking, secondary lead smelting, or both operations were performed for the primary purpose of reclaiming lead from spent lead-acid batteries. Metallic lead and lead compounds are generally the principal contaminants of concern in soils and waste deposits (i.e., buried, piled, landfilled waste) at these sites. Other metals (e.g., cadmium, copper, arsenic, antimony, and selenium) are often present at LBRS, but usually at much lower concentrations than lead and often present below hazardous concentrations. This article is primarily based on experience gained from: (1) Superfund site investigation, removal, and remedial actions, and (2) development and demonstration of control technologies under the Superfund Innovative Technology Evaluation (SITE) Program. The primary remedial options for lead contaminated soils and waste deposits include: (1) no action, (2) off-site disposal, (3) containment, (4) immobilization, (5) separation with resource recovery, and (6) separation without resource recovery. In spite of the toxicity of lead at low concentrations, the relative immobility of lead and site-specific risk assessments can still result in the selection of no action or containment remedies. Solidification/stabilization of lead-contaminated soils has been implemented at three Superfund sites and is the selected remedy at several others. Separation technologies (e.g., screening, extraction) are attractive because, if successful, they actually remove the contaminant from the environmental media. Separation technologies also offer the possibility that a valuable product (e.g., lead, plastic, energy) can be recovered, but careful consideration of economic and technical factors are required. Compared to the implementation of containment and solidification I stabilization remedies, separation technologies tend to be relatively novel, complex, and costly.     

Thermal Immobilization of Lead Contaminants in Soils Treated in a Fixed- and Fluidized-Bed Incinerator at Moderate Temperatures

Abstract

Artificially lead-contaminated soils with different lead contents (200, 450, 600, and 900 ppm) were thermally immobilized in both fixed-bed and fluidized-bed modes at moderate treating temperatures (less than 500 °C) for various retention times. Cement powder and brick powder were added to the artificially contaminated soils to enhance lead immobilization. Results indicate that increasing treating temperature and time increases the extent of lead immobilization, as determined by the U.S. Environmental Protection Agency's (U.S. EPA) Toxicity Characteristics Leachability Procedure (TCLP). The percentage of lead leached from the soil/ cement mixtures was in the range of less than 0.251%, compared with the range between 13.6% and 40.7% for the corresponding soil/brick mixtures. As the amount of brick dust added to the Pb-doped soil was increased, the specific Pb immobilization effectiveness increased from 0.0675 to 0.149 mg Pb/g brick (for the 20- and 50-gram brick addition, respectively). An increase in air flow rate from 2 to 40 L/min caused a slight decrease in the Pb leaching percentage from 14.96% to 11.59%. Both the Freundlich and Langmuir isotherms give a satisfactory fit (r = 0.945 ~ 0.998) for the data derived from a TCLP test of the thermally-treated soil samples (105 °C and 500 °C) that contained lead contaminants. Sorption of lead contaminants in soil and sorbent matrices was the primary type of chemisorption. The kinetic results indicated that the Pb-doped soil system was too complicated to be described by a simple calculation.