Reif, Andrew G.; Sloto, Ronald A.
1997-01-01
The Schuylkill River flows through Valley Forge National Historical Park in Lower Providence and West Norriton Townships in Montgomery County, Pa. The concentration of selected metals, pesticides, semivolatile organic compounds, and total carbon in stream-bottom sediments from Valley Forge National Historical Park were determined for samples collected once at 12 sites in and around the Schuylkill River.Relatively low concentrations of arsenic, chromium, copper, and lead were detected in all samples. The concentrations of these metals are similar to concentrations in other stream-bottom sediment samples collected in the region. The concentrations of iron, manganese, and zinc were elevated in samples from four sites in the Schuylkill River, and the concentration of mercury was elevated in a sample from an impoundment along the river.The organophosphorus insecticide diazinon was detected in relatively low concentrations in half of the 12 samples analyzed. The organo-chlorine insecticide DDE was detected in all 12 samples analyzed; dieldrin was detected in 10 samples, chlordane, DDD, and DDT were detected in 9 samples, and heptachlor epoxide was detected in one sample. The concentrations of organo-chlorine and organophosphorus insecticides were relatively low and similar to concentrations in samples collected in the region.Detectable concentrations of 17 semivolatile organic compounds were measured in the 12 samples analyzed. The most commonly detected compounds were fluoranthene, phenanthrene, and pyrene. The maximum concentration detected was 4,800 micrograms per kilogram of phenanthrene. The highest concentrations of compounds were detected in Lamb Run, a small tributary to the Schuylkill River with headwaters in an industrial corporate center. The concentration of compounds in the Schuylkill River below Lamb Run is higher than the Schuylkill River above Lamb Run, indicating that sediment from Lamb Run is increasing the concentration of semivolatile organic compounds in sediment from the Schuylkill River. Concentrations of semivolatile organic compounds are lower in sediment from the Schuylkill River below Myer's Run than above Myer's Run because of the addition of relatively clean sediment from Myer's Run. Samples collected from the floodplain, impounding basin, and wetland along the Schuylkill River contained the lowest concen-trations of semivolatile organic compounds.Detectable concentrations of polychlorinated biphenyls (PCB's) were measured in 11 of the 12 samples analyzed. The maximum PCB concentration was 37 micrograms per kilogram. Sediment samples from Lamb Run contained the highest concentrations of semivolatile organic compounds and PCB's.
ESTIMATING TRANSPORT AND DEPOSITION OF A SEMI-VOLATILE COMPOUND WITH A REGIONAL PHOTOCHEMICAL MODEL
To simulate the fate of compounds that are considered semi-volatile and toxic, we have modified a model for regional particulate matter. Our changes introduce a semi-volatile compound into the atmosphere as gaseous emissions from an area source. Once emitted, the gas can transf...
Nagle, Doug D.; Guimaraes, Wladmir B.
2012-01-01
An assessment of the quantity and quality of stormwater runoff associated with industrial activities at Fort Gordon was conducted from January through December 2011. The assessment was provided to satisfy the requirements from a general permit that authorizes the discharge of stormwater under the National Pollutant Discharge Elimination System from a site associated with industrial activities. The stormwater quantity refers to the runoff discharge at the point and time of the runoff sampling. The study was conducted by the U.S. Geological Survey, in cooperation with the U.S. Department of the Army Environmental and Natural Resources Management Office of the U.S. Army Signal Center and Fort Gordon. The initial scope of this study was to sample stormwater runoff from five stations at four industrial sites (two landfills and two heating and cooling sites). As a consequence of inadequate hydrologic conditions during 2011, no samples were collected at the two landfills; however, three samples were collected from the heating and cooling sites. The assessment included the collection of physical properties, such as water temperature, specific conductance, dissolved oxygen, and pH; the detection of suspended materials (total suspended solids, total fixed solids, total volatile solids), nutrients and organic compounds, and major and trace inorganic compounds (metals); and the detection of volatile and semivolatile organic compounds. Nutrients and organic compounds, major and trace inorganic compounds, and volatile and semivolatile organic compounds were detected above the laboratory reporting levels in all samples collected from the three stations. The detection of volatile and semivolatile organic compounds included anthracene, benzo[a]anthracene, benzo[a]pyrene, benzo[ghi]perylene, cis,1, 2-dichloroethene, dimethyl phthalate, fluoranthene, naphthalene, pyrene, acenaphthylene (station SWR11-3), and di-n-butyl phthalate (station SWR11-4).
The potential of the anaerobic, expanded bed granular activated carbon (GAC) reactor in treating a high strength waste containing RCRA semivolatile organic compounds (VOCs) was studied. Six semivolatiles, orthochlorophenol, nitrobenzene, naphthalene, para-nitrophenol, lindane, a...
Potential Signatures of Semi-volatile Compounds Associated With Nuclear Processing
DOE Office of Scientific and Technical Information (OSTI.GOV)
Probasco, Kathleen M.; Birnbaum, Jerome C.; Maughan, A. D.
2002-06-01
Semi-volatile chemicals associated with nuclear processes (e.g., the reprocessing of uranium to produce plutonium for nuclear weapons, or the separation of actinides from processing waste streams), can provide sticky residues or signatures that will attach to piping, ducting, soil, water, or other surface media. Volatile compounds, that are more suitable for electro-optical sensing, have been well studied. However, the semi-volatile compounds have not been well documented or studied. A majority of these semi-volatile chemicals are more robust than typical gaseous or liquid chemicals and can have lifetimes of several weeks, months, or years in the environment. However, large data gapsmore » exist concerning these potential signature compounds and more research is needed to fill these data gaps so that important signature information is not overlooked or discarded. This report investigates key semi-volatile compounds associated with nuclear separations, identifies available chemical and physical properties, and discusses the degradation products that would result from hydrolysis, radiolysis and oxidation reactions on these compounds.« less
MODEL DEVELOPMENT AND TESTING FOR SEMI-VOLATILES (ATRAZINE)
The Community Multi-Scale Air Quality (CMAQ) model, air quality model within EPA's Models-3 system, can be adapted to simulate the fate of semi-volatile compounds that are emitted into the atmosphere. "Semi-volatile" refers to compounds that partition their mass between two ph...
Cost Effective, Ultra Sensitive Groundwater Monitoring for Site Remediation and Management
2015-05-01
feasibility studies. ................... 30 Table 5. Compounds screened in the laboratory for IS2 sampling...tank SVOC semivolatile organic compound TCE trichloroethene TPH total petroleum hydrocarbon USEPA U.S. Environmental Protection Agency UST...underground storage tank V volt VOA volatile organic analysis VOC volatile organic compound Technical material contained in this report has
Cost-Effective, Ultra-Sensitive Groundwater Monitoring for Site Remediation and Management
2015-05-01
Example anion concentrations in groundwater used for feasibility studies. ................... 30 Table 5. Compounds screened in the laboratory for IS2...phase extraction ST storage tank SVOC semivolatile organic compound TCE trichloroethene TPH total petroleum hydrocarbon USEPA U.S. Environmental...Protection Agency UST underground storage tank V volt VOA volatile organic analysis VOC volatile organic compound Technical material
Petrich, Nicholas T.; Spak, Scott N.; Carmichael, Gregory R.; Hu, Dingfei; Martinez, Andres; Hornbuckle, Keri C.
2013-01-01
Passive air samplers (PAS) including polyurethane foam (PUF) are widely deployed as an inexpensive and practical way to sample semi-volatile pollutants. However, concentration estimates from PAS rely on constant empirical mass transfer rates, which add unquantified uncertainties to concentrations. Here we present a method for modeling hourly sampling rates for semi-volatile compounds from hourly meteorology using first-principle chemistry, physics, and fluid dynamics, calibrated from depuration experiments. This approach quantifies and explains observed effects of meteorology on variability in compound-specific sampling rates and analyte concentrations; simulates nonlinear PUF uptake; and recovers synthetic hourly concentrations at a reference temperature. Sampling rates are evaluated for polychlorinated biphenyl congeners at a network of Harner model samplers in Chicago, Illinois during 2008, finding simulated average sampling rates within analytical uncertainty of those determined from loss of depuration compounds, and confirming quasi-linear uptake. Results indicate hourly, daily and interannual variability in sampling rates, sensitivity to temporal resolution in meteorology, and predictable volatility-based relationships between congeners. We quantify importance of each simulated process to sampling rates and mass transfer and assess uncertainty contributed by advection, molecular diffusion, volatilization, and flow regime within the PAS, finding PAS chamber temperature contributes the greatest variability to total process uncertainty (7.3%). PMID:23837599
Indoor Semi-volatile Organic Compounds (i-SVOC) Version 1.0
i-SVOC Version 1.0 is a general-purpose software application for dynamic modeling of the emission, transport, sorption, and distribution of semi-volatile organic compounds (SVOCs) in indoor environments.
Semi-volatile compounds present special analytical challenges not met by conventional methods for analysis of ambient particulate matter (PM). Accurate quantification of PM-associated organic compounds requires validation of the laboratory procedures for recovery over a wide v...
DOE Office of Scientific and Technical Information (OSTI.GOV)
Not Available
This interim notice covers the following: extractable organic halides in solids, total organic halides, analysis by gas chromatography/Fourier transform-infrared spectroscopy, hexadecane extracts for volatile organic compounds, GC/MS analysis of VOCs, GC/MS analysis of methanol extracts of cryogenic vapor samples, screening of semivolatile organic extracts, GPC cleanup for semivolatiles, sample preparation for GC/MS for semi-VOCs, analysis for pesticides/PCBs by GC with electron capture detection, sample preparation for pesticides/PCBs in water and soil sediment, report preparation, Florisil column cleanup for pesticide/PCBs, silica gel and acid-base partition cleanup of samples for semi-VOCs, concentrate acid wash cleanup, carbon determination in solids using Coulometrics` CO{submore » 2} coulometer, determination of total carbon/total organic carbon/total inorganic carbon in radioactive liquids/soils/sludges by hot persulfate method, analysis of solids for carbonates using Coulometrics` Model 5011 coulometer, and soxhlet extraction.« less
Thomas, Lashun K.; Journey, Celeste A.; Stringfield, Whitney J.; Clark, Jimmy M.; Bradley, Paul M.; Wellborn, John B.; Ratliff, Hagan; Abrahamsen, Thomas A.
2011-01-01
A spatial survey of streams was conducted from February to April 2010 to assess the concentrations of major ions, selected trace elements, semivolatile organic compounds, organochlorine pesticides, and polychlorinated biphenyls associated with the bed sediments of surface waters at Fort Gordon military installation near Augusta, Georgia. This investigation expanded a previous study conducted in May 1998 by the U.S. Geological Survey, in cooperation with the U.S. Department of the Army Environmental and Natural Resources Management Office of the U.S. Army Signal Center and Fort Gordon, that evaluated the streambed sediment quality of selected surface waters at Fort Gordon. The data presented in this report are intended to help evaluate bed sediment quality in relation to guidelines for the protection of aquatic life, and identify temporal trends in trace elements and semivolatile organic compound concentrations at streambed sites previously sampled. Concentrations of 34 major ions and trace elements and 102 semivolatile organic, organochlorine pesticide, and polychlorinated biphenyl compounds were determined in the fine-grained fraction of bed sediment samples collected from 13 of the original 29 sites in the previous study, and 22 additional sites at Fort Gordon. Three of the sites were considered reference sites as they were presumed to be located away from potential sources of contaminants and were selected to represent surface waters flowing onto the fort, and the remaining 32 nonreference sites were presumed to be located within the contamination area at the fort. Temporal trends in trace elements and semivolatile organic compound concentrations also were evaluated at 13 of the 32 nonreference sites to provide an assessment of the variability in the number of detections and concentrations of constituents in bed sediment associated with potential sources, accumulation, and attenuation processes. Major ion and trace element concentrations in fine-grained bed sediment samples from most nonreference sites exceeded concentrations in samples from reference sites at Fort Gordon. Bed sediments from one of the nonreference sites sampled contained the highest concentrations of copper and lead with elevated levels of zinc and chromium relative to reference sites. The percentage change of major ions, trace elements, and total organic carbon that had been detected at sites previously sampled in May 1998 and current bed sediment sites ranged from -4 to 8 percent with an average percentage change of less than 1 percent. Concentrations of major ions and trace elements in bed sediments exceeded probable effect levels for aquatic life (based on the amphipod Hyalella azteca) established by the U.S. Environmental Protection Agency at 46 and 69 percent of the current and previously sampled locations, respectively. The greatest frequency of exceedances for major ions and trace elements in bed sediments was observed for lead. Concentrations of semivolatile organic compounds, organochlorine pesticides, and polychlorinated biphenyls were detected in bed sediment samples at 94 percent of the sites currently sampled. Detections of these organic compounds were reported with greater frequency in bed sediments at upstream sampling locations, when compared to downstream locations. The greatest number of detections of these compounds was reported for bed sediment samples collected from two creeks above a lake. The percentage change of semivolatile organic compounds detected at previously sampled and current bed sediment sites ranged from -68 to 100 percent with the greatest percentage increase reported for one of the creeks above the lake. Concentrations of semivolatile organic compounds and polychlorinated biphenyls in bed sediments exceeded aquatic life criteria established by the U.S. Environmental Protection Agency at three sites. Contaminant compounds exceeding aquatic life criteria included fluoranthene, phenanthrene, anthracene, benzo(a)anthracene
FACTORS IN GEOTROPOSPHERIC PARTICLE-GAS TRANSPORT OF SEMIVOLATILE ORGANIC COMPOUNDS
Semivolatile organic compounds (SVOCs) can exist in solid, liquid, or gas phases under ambient environmental conditions. The geotropospheric transport of SVOCs varies according to the particle type. Two classes of SVOCs and two types of particles were analyzed to determine possib...
SUPERCRITICAL FLUID EXTRACTION OF SEMI-VOLATILE ORGANIC COMPOUNDS FROM PARTICLES
A nitrogen oxide flux chamber was modified to measure the flux of semi-volatile organic compounds (SVOCs). Part of the modification involved the development of methods to extract SVOCs from polyurethane foam (PUF), sand, and soil. Breakthroughs and extraction efficiencies were ...
Concentrations of over 25 polar semi-volatile and non-volatile organic compounds were measured in Lower Manhattan, New York using a high capacity Integrated Organic Gas and Particle sampler, after the initial destruction of the World Trade Center. The polar organic compounds in...
Indoor Residence Times of Semivolatile Organic Compounds: Model Estimation and Field Evaluation
Indoor residence times of semivolatile organic compounds (SVOCs) are a major and mostly unavailable input for residential exposure assessment. We calculated residence times for a suite of SVOCs using a fugacity model applied to residential environments. Residence times depend on...
NASA Astrophysics Data System (ADS)
Wernis, R. A.; Yee, L.; Isaacman-VanWertz, G. A.; Kreisberg, N. M.; de Sá, S. S.; Liu, Y.; Martin, S. T.; Alexander, M. L. L.; Palm, B. B.; Hu, W.; Campuzano-Jost, P.; Day, D. A.; Jimenez, J. L.; Artaxo, P.; Viegas, J.; Manzi, A. O.; Souza, R. A. F. D.; Hering, S. V.; Goldstein, A. H.
2016-12-01
Aerosols are a source of great uncertainty in radiative forcing predictions and have poorly understood impacts on human health. In many environments, biomass burning contributes a significant source of primary aerosol as well as reactive gas-phase precursors that can form secondary organic aerosol (SOA). One class of these precursors, semi-volatile organic compounds (SVOCs), has been shown to have a large contribution to the amount of SOA formed from fire emissions. At present, SVOC emissions from biomass burning are poorly constrained and understanding their contributions to SOA formation is an important research challenge. In the Amazonian dry season, biomass burning is a major source of gases and aerosols reducing regional air quality. As part of the GoAmazon 2014/5 field campaign, we deployed the Semi-Volatile Thermal desorption Aerosol Gas Chromatograph (SV-TAG) instrument at the rural T3 site, 60 km to the west of Manaus, Brazil to measure hourly concentrations of SVOCs in the gas and particle phases. This comprehensive technique detects thousands of compounds, enabling the discovery of previously unidentified compounds. In this work we explore compounds for which a correlation with well-known biomass burning tracers is observed to discover the identities of new markers. We discuss contributions to the total organic aerosol from over 30 well-known, rarely reported and newly identified biomass burning markers. We examine the relationship between biomass burning aerosol composition and aerosol physical properties as measured at the T3 site. Additionally, we report gas-particle partitioning of all identified compounds with comparison to theoretical predictions. We find that the commonly used biomass burning tracer levoglucosan existed entirely in the particle phase and contributed 0.6% and 0.3% of total organic aerosol mass in the dry and wet seasons, respectively.
The Measurement of Atmospheric Concentrations and Deposition of Semi-Volatile Organic Compounds.
ERIC Educational Resources Information Center
Lee, David S.; Nicholson, Ken W.
1994-01-01
Provides a physical description of semivolatile organic compounds (SVOCs), both in terms of their characteristic nature in the atmosphere and the processes which control their deposition. Contains a summary of the requirements for a full assessment of atmospheric SVOCs and their deposition. (LZ)
SOIL SORPTION OF VOLATILE AND SEMIVOLATILE ORGANIC COMPOUNDS IN A MIXTURE
Studies were conducted to evaluate lipophilicity as a predictor sorption for a mixture of organic compounds with high vapor pressures commonly present at hazardous waste sites. Sorption partition coefficients (
Mounting evidence from field and laboratory observations coupled with atmospheric model analyses shows that primary combustion emissions of organic compounds dynamically partition between the vapor and particulate phases, especially as near-source emissions dilute and cool to amb...
Chan, A. W. H.; Kreisberg, N. M.; Hohaus, T.; ...
2016-02-02
Understanding organic composition of gases and particles is essential to identifying sources and atmospheric processing leading to organic aerosols (OA), but atmospheric chemical complexity and the analytical techniques available often limit such analysis. Here we present speciated measurements of semivolatile and intermediate volatility organic compounds (S/IVOCs) using a novel dual-use instrument (SV-TAG-AMS) deployed at Manitou Forest, CO, during the Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H 2O, Organics & Nitrogen – Rocky Mountain Biogenic Aerosol Study (BEACHON-RoMBAS) 2011 campaign. This instrument provides on-line speciation of ambient organic compounds with 2 h time resolution. The species in this volatility range aremore » complex in composition, but their chemical identities reveal potential sources. Observed compounds of biogenic origin include sesquiterpenes with molecular formula C 15H 24 (e.g., β-caryophyllene and longifolene), which were most abundant at night. A variety of other biogenic compounds were observed, including sesquiterpenoids with molecular formula C 15H 22, abietatriene and other terpenoid compounds. Many of these compounds have been identified in essential oils and branch enclosure studies but were observed in ambient air for the first time in our study. Semivolatile polycyclic aromatic hydrocarbons (PAHs) and alkanes were observed with highest concentrations during the day and the dependence on temperature suggests the role of an evaporative source. Using statistical analysis by positive matrix factorization (PMF), we classify observed S/IVOCs by their likely sources and processes, and characterize them based on chemical composition. The total mass concentration of elutable S/IVOCs was estimated to be on the order of 0.7 µg m –3 and their volatility distributions are estimated for modeling aerosol formation chemistry.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Chan, A. W. H.; Kreisberg, N. M.; Hohaus, T.
Understanding organic composition of gases and particles is essential to identifying sources and atmospheric processing leading to organic aerosols (OA), but atmospheric chemical complexity and the analytical techniques available often limit such analysis. Here we present speciated measurements of semivolatile and intermediate volatility organic compounds (S/IVOCs) using a novel dual-use instrument (SV-TAG-AMS) deployed at Manitou Forest, CO, during the Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H 2O, Organics & Nitrogen – Rocky Mountain Biogenic Aerosol Study (BEACHON-RoMBAS) 2011 campaign. This instrument provides on-line speciation of ambient organic compounds with 2 h time resolution. The species in this volatility range aremore » complex in composition, but their chemical identities reveal potential sources. Observed compounds of biogenic origin include sesquiterpenes with molecular formula C 15H 24 (e.g., β-caryophyllene and longifolene), which were most abundant at night. A variety of other biogenic compounds were observed, including sesquiterpenoids with molecular formula C 15H 22, abietatriene and other terpenoid compounds. Many of these compounds have been identified in essential oils and branch enclosure studies but were observed in ambient air for the first time in our study. Semivolatile polycyclic aromatic hydrocarbons (PAHs) and alkanes were observed with highest concentrations during the day and the dependence on temperature suggests the role of an evaporative source. Using statistical analysis by positive matrix factorization (PMF), we classify observed S/IVOCs by their likely sources and processes, and characterize them based on chemical composition. The total mass concentration of elutable S/IVOCs was estimated to be on the order of 0.7 µg m –3 and their volatility distributions are estimated for modeling aerosol formation chemistry.« less
This study measured semivolatile organic compounds (SVOCs) in particle matter (PM) emitted from three heavy-duty trucks equipped with modern after-treatment technologies. Emissions testing was conducted as described by the George et al. VOC study also presented as part of this se...
Klohe, Cheryl A.; Debrewer, Linda M.
2007-01-01
The U.S. Geological Survey, in cooperation with the District Department of the Environment (formerly the District of Columbia, Department of Health, Environmental Health Administration), conducted a ground-water-quality investigation in the Anacostia River watershed within Washington, D.C. Samples were collected and analyzed from 17 ground-water monitoring wells located within the study area from September through December 2005. Samples were analyzed for a variety of constituents including major ions, nutrients, volatile organic compounds, semivolatile organic compounds, pesticides and degradates, oil and grease, phenols, total polychlorinated biphenyls, and other selected constituents. The concentrations of major ions in the study area indicate that the ground water is predominantly calcium-bicarbonate type water, with some wells containing a higher percentage of milliequivalents per liter of iron (cation), and chloride or sulfate (anions). Concentrations of nitrogen were generally less than 1 milligram per liter, and concentrations of phosphorus were generally less than 0.5 milligrams per liter. Twelve of 79 pesticides and degradates were detected at 6 out of 17 wells. Volatile organic compounds (predominantly gasoline oxygenates and solvents) were detected in 9 of the 17 wells. Two semivolatile organic compounds, (bis(2-ethylhexyl) phthalate and total phenols), out of the 51 analyzed, were detected in the study area.
Federal Register 2010, 2011, 2012, 2013, 2014
2012-06-28
... of semivolatile organic compounds in finished drinking water. The method analytes are extracted and... semivolatile organic contaminants: Alachlor, atrazine, polychlorinated biphenyls (PCBs), benzo[a]pyrene... approved EPA Method 525.2, Revision 2.0 for each of the 17 regulated semivolatile organic contaminants. EPA...
Contaminants in Liquid Organic Fertilizers Used for Agriculture in Japan.
Hai, Dao M; Qiu, Xuchun; Xu, Hai; Honda, Masato; Yabe, Mitsuyasu; Kadokami, Kiwao; Shimasaki, Yohei; Oshima, Yuji
2017-07-01
To provide an overview of anthropogenic contaminants in liquid organic fertilizers (LOFs), products from four biogas plants in Kyushu, Japan, were analyzed for a wide range of contaminants, including copper, cadmium, tributyltin (TBT), dibutyltin (DBT), perfluorooctane sulfonate, 952 semi-volatile organic compounds, and 89 antibiotics. The highest concentrations of copper (31.1 mg/L) and cadmium (0.08 mg/L) were found in LOFs from the Hita biogas plant. Only ofloxacin and sulfapyridine were detected in total 89 antibiotics screened. TBT, DBT, and perfluorooctane sulfonate were present at low concentrations in the LOFs from all four locations. Among the 952 semi-volatile organic compounds, 78 compounds were detected in at least one sample and were present at concentrations between 1.2 and 139.6 mg/L. On the basis of comparisons with previous studies and quality standards for the use of organic fertilizers, the concentrations of contaminants in the studied LOFs indicate that they might be safe for agricultural purposes.
This paper describes a method for dynamic modeling of the interactions of semivolatile organic compounds (SVOCs) with airborne and settled particulate matter in the indoor environment. This method is fully compatible with the other components within the framework. Despite the unc...
Pesticides and other semi-volatile organic compounds (SOCs) undergo regional and longrange atmospheric transport. One such example is the transport of current-use pesticides from the intensely cultivated Central Valley of California into the adjacent Sierra Nevada and Cascade Mou...
Analytical methods capable of trace measurement of semi-volatile organic compounds (SOCs) are necessary to assess the exposure of tadpoles to contaminants as a result of long-range and regional atmospheric transport and deposition. The following study compares the results of two ...
A research project was initiated to address a recurring problem of elevated detection limits above required risk-based concentrations for the determination of semivolatile organic compounds in high moisture content solid samples. This project was initiated, in cooperation with t...
Huang, Zhi; Zhou, Wen; Yu, Ya-juan; Zhang, Ai-qian; Han, Shuo-kui; Wang, Lian-sheng
2004-01-01
Enrichment of volatile organic compounds(VOC) and semi-volatility organic compounds(SVOC) in surface microlayer(SM) of three drinking water sources were studied. The enrichment factor(EFs) were 0.67 to 13.37 and 0.16 to 136, respectively. The results showed some VOC and most SVOC could enrich in SM. Some EFs of SVOC was quite high. Suspension and temperature could affect EFs of SVOC, slim wind and water movement do not destroy enrichment of organic in SM.
Fine particulate matter (PM) in urban atmospheres contains substantial amounts of semi-volatile material (e.g. ammonium nitrate and semi-volatile organic compounds), some of which is lost when PM is sampled with a filter. This study addresses the hypothesis that the concentratio...
Semi-volatile organic compounds and trace elements in the Yangtze River source of drinking water.
Wu, Bing; Zhang, Xuxiang; Zhang, Xiaolin; Yasun, Aishangjiang; Zhang, Yan; Zhao, Dayong; Ford, Tim; Cheng, Shupei
2009-08-01
Determination of 24 semi-volatile organic compounds (SVOCs) and 24 trace elements in water samples was conducted in order to investigate the quality of the Nanjing source of drinking water taken from Yangtze River. The total concentrations of SVOCs and trace elements were in the range of 1,951-11,098 ng/l and 51,274-72,384 microg/l, respectively. No significant seasonal changes were found for the pollutants' concentrations. A primary health risk assessment was carried out to evaluate potential health effects. Risk quotients involving carcinogenic effects for benzo(a)anthracene, benzo(a)pyrene, benzo(b)fluoranthene, dibenz(a,h)anthracene, bis(2-ethylhexyl)phthalate and arsenic were >1 under the worst-case scenario. The results of this study demonstrate the importance of further studies on the environmental health effects of exposure to the source water.
Concentrations of over 60 non-polar semi-volatile and non-volatile organic compounds were measured in Lower Manhattan, New York using a high capacity Integrated Organic Gas and Particle Sampler, after the initial destruction of the World Trade Center. The results indicate that th...
Concentrations of over 60 non-polar semi-volatile and non-volatile organic compounds were measured in Lower Manhattan, New York using a high capacity Integrated Organic Gas an Particle Sampler, after the initial destruction of the World Trade Center. The results indicate that t...
Concentrations of over 60 non-polar semi-volatile and non-volatile organic compounds were measured in Lower Manhattan, New York using a high capacity Integrated Organic Gas and Particle Sampler, after the initial destruction of the World Trade Center. The results indicate that ...
1.1. This is a gas chromatography/mass spectrometry (GC/MS) method for the determination of selected semivolatile organic compounds in drinking waters. Accuracy and precision data have been generated in reagent water, and in finished ground and surface waters for the compounds li...
Measurements of particulate semi-volatile material
NASA Astrophysics Data System (ADS)
Pang, Yanbo
2000-10-01
A new innovative sampling system, PC-BOSS, was developed by the combination of particle concentrator and BOSS denuder techniques in response to the new EPA PM2.5 standard and to meet top research priorities for particulate matter that were identified by the National Research Council. The PC-BOSS (P_article C_oncentrator- B_righam Young University O_rganic S_ampling S_ystem) can accurately determine not only PM2.5 stable mass and species such as sulfate, but also particulate semi- volatile material. Several field comparison studies of the PC-BOSS with the EPA PM2.5 reference method and state-of-the-art fine particle measurement methods confirm the capability of the PC-BOSS to accurately determine particulate semi-volatile material, especially organic compounds. This is the first routine sampling system for the determination of both particulate semi-volatile inorganic and organic material. Two other denuder system samplers for the determination of PM2.5 total mass including semi-volatile material were also developed for PM2.5 research and exposure monitoring. Results of studies around the United States indicate that the EPA PM2.5 FRM (Federal Reference Method) under- measured PM2.5 mass by 20-30% compared to PC-BOSS results due to the loss of particulate nitrate and semi-volatile organic compounds during sampling. Organic material is mostly responsible for this under- measurement by the FRM. Using our new sampling system in epidemiological and exposure studies will be essential to providing answers to some top research priorities for particulate matter and promote a better PM2.5 standard for the protection of human health because some fractions of particulate semi-volatile organic compounds are toxic and are possibly responsible for health effects associated with exposure to particulate matter. The atmospheric chemistry of organic aerosols in the troposphere and stratosphere is still largely unknown because of the lack of detailed organic aerosol information. The importance of organic aerosols might also be underestimated because current data on organic aerosols in the troposphere and stratosphere were mostly obtained by traditional methods, like the FRM method. Using PC-BOSS to study organic aerosols in the troposphere and stratosphere will provide not only more but also more accurate information about organic aerosols, and significantly improve the understanding of the role of aerosols in global warming, ozone depletion, and atmospheric heterogenous chemistry.
Economic Development Threatens Groundwater in Puerto Rico: Results of a Field Study.
ERIC Educational Resources Information Center
Arbona, Sonia I.; Hunter, John M.
1995-01-01
Presents the results of a field study done on 7 wells providing 37% of the total aquifer production for 4 municipalities in Puerto Rico. Each sampled well showed signs of contamination by heavy metals, nitrate, and semivolatile organic compounds. Although found in low concentrations, current development threatens groundwater quality. (MJP)
Over the past two decades, more than 20 mass transfer models have been developed for the sources, sinks, and barriers for volatile and semivolatile organic compounds (VOCs and SVOCs) in the indoor environment. While these models have greatly improved our understanding of VOC and ...
Evaluation of organic compounds and trace elements in Amazon Creek Basin, Oregon, September 1990
Rinella, F.A.
1993-01-01
Water and bottom sediment were collected from Amazon Creek, Oregon during a summer low-flow condition and analyzed for different classes of organic compounds, including many from the U.S. Environmental Protection Agency's priority pollutant list. Bottom sediment also was analyzed for trace elements typically associated with urban runoff. Trace-element concentrations in the less than 63 micrometer fraction of Amazon Creek bottom-sediment samples were compared with baseline concentrations (expected 95 percent confidence range) for soils from the Western United States and with concen- trations found in bottom sediment from the Willamette River Basin. Total-digestion concentrations of antimony, arsenic, cadmium, chromium, cobalt, copper, lead, manganese, mercury, nickel, silver, titanium, and zinc were enriched at some or all sites sampled. Whole-water samples from some sites contained concentrations of several chlorophenoxy-acid herbicides, the organophosphorus insecticide diazinon, and several semivolatile priority pollutants. Classes of compounds not detected in whole-water samples included carbamate insecticides, triazine and other nitrogen-containing herbicides, and purgeable organic compounds. Bottom-sediment samples contained many organochlorine compounds, including chlordane, DDT plus metabolites, dieldrin, endrin, heptachlor epoxide (a metabolite of heptachlor), and PCBs at some or all sites sampled. Twenty-four of 54 semivolatile compounds were detected in bottom- sediment samples at some or all sites sampled.
NASA Astrophysics Data System (ADS)
Holzinger, Rupert; Khan, Anwar; Misztal, Pawel; Goldstein, Allen
2016-04-01
A serial 3-stage denuder system has been developed and for the first time deployed during the Southern Oxidant and Aerosol Study (SOAS) in Centreville, Alabama, USA, for one month during the summer of 2013. Volatile organic compounds (VOCs) were collected on an activated carbon denuder and thermally desorbed to be measured with PTR-MS (PTR-TOF800, Ionicon Analytik GmbH). Comparison with a second PTR-MS instrument operated under standard conditions at the same site revealed poor recovery for the majority of the VOCs while individual species measured by the different PTR-MS systems still exhibited excellent correlation. Semivolatile organic compounds (SVOCs) in the gas phase were collected and thermally desorbed on a denuder coated with Methylsiloxane (Agilent DB-1). More than 100 SVOCs have been detected at levels in the range 0.05-3 pmmol/mol and only a few species exhibited maximum mixing ratios above 5 pmol/mol. Many of the detected species exhibited a clear diurnal profile while the concentration of some was clearly dominated by pollution events. Carboxylic acids, (oxidized) polycyclic aromatic compounds, and monoterpene oxidation products were compound groups that provided most of the mass and a typical total concentration of the measured burden of SVOCs was 5 microgram per cubic meter.
Health risk assessment of semi-volatile organic pollutants in Lhasa River China.
Liu, Feng; Liu, Yan; Jiang, Dongsheng; Zhang, Rongfei; Cui, Yibin; Li, Mei
2014-05-01
The semi-volatile organic compounds in Lhasa River were determined qualitatively and quantitatively by gas chromatography method with mass spectrometric detection. Total concentrations of 23 organic pollutants in samples from five sites ranged from 1.56 to 2.78 μg/L. The average concentrations for ΣPAEs, ΣPAHs and ΣBTEXs obtained in this study were 1.53, 0.33 and 0.51 μg/L, respectively. Moreover, the results of analysis of variable showed that there were significant differences (P < 0.05) among the sites for levels of ΣPAHs, ΣPAEs and ΣBTEXs. Cluster analysis was applied to detect spatial similarity for grouping of sites under the monitoring network. The results indicated that the five sites in this study could be divided into two significant groups, i.e. low and high pollutant groups. Health risk assessment was conducted by multimedia environmental goals (MEG), risk quotient (RQ) for each pollutant and hazard quotient (HQ) approach from USA ecological risk assessment (ERA) for screening stage. Calculated both total ambient severity and RQ were less than 1 and therefore minimal risk to human and ecological health. For analysis results of HQ, whether for the ingestion exposure or dermal adsorption pathway were all less than 1, the results also agreed with the RQ model and MEG model for evaluating the potential for adverse health effects due to exposure semi-volatile organic compounds from surface water. Therefore, SVOCs in Lhasa River posed little or no threat to the health of local consumers and ecological environment.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Hagaraty, G.; Johnson, J.; Middlebrooks, P.
The Phase II EBS results document the extent of environmental contamination believed to be present on McCormick Ranch. Explosive test areas having the greatest potential for containing soil contaminants were identified using several geophysical survey methods: EM 31 terrain conductivity meter, magnetometer/gradiometer, and ground penetrating radar. From the geophysical surveys, five areas selected to conduct further environmental analysis. A total of 310 soil samples were collected from the five areas and 13 specific high explosive test sites. The samples were screened for semi-volatile organic compounds, PETN, TNT, TNT-degradation products, nitrates and radioactivity. Laboratory analyses were performed and no explosives ormore » degradation products were identified. Semi-volatile organic compounds were in 2 samples, manganese was detected in 3 samples, nitrates were discovered below soil action levels, and radiation levels were below background. Consequently, it is unlikely that significant contamination exists.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Hagaraty, G.; Johnson, J.; Middlebrooks, P.
The Phase II EBS results document the extent of environmental contamination believed to be present on McCormick Ranch. Explosive test areas having the greatest potential for containing soil contaminants were identified using several geophysical survey methods: EM 31 terrain conductivity meter, magnetometer/gradiometer, and ground penetrating radar. From the geophysical surveys, five areas were selected to conduct further environmental analysis. A total of 310 soil samples were collected from the five areas and 13 specific high explosive test sites. The samples were screened for semi-volatile organic compounds, PETN, TNT, TNT-degradation products, nitrates and radioactivity. Laboratory analyses were and no explosives ormore » degradation products were identified. Semi-volatile organic compounds were in 2 samples, manganese was detected in 3 samples, nitrates were discovered below soil action levels, and radiation levels were below background. Consequently, it is unlikely that significant contamination exists.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Hagaraty, G.; Johnson, J.; Middlebrooks, P.
The Phase II EBS results document the extent of environmental contamination believed to be present on McCormick Ranch. Explosive test areas having the greatest potential for containing soil contaminants were identified using several geophysical survey methods: EM 31 terrain conductivity meter, magnetometer/gradiometer, and ground penetrating radar. From the geophysical surveys, five areas were selected to conduct further environmental analysis. A total of 310 soil samples were collected from the five areas and 13 specific high explosive test sites. The samples were screened for semi-volatile organic compounds, PETN, TNT, TNT-degradation products, nitrates and radioactivity. Laboratory analyses were performed and no explosivesmore » or degradation products were identified. Semi-volatile organic compounds were found in 2 samples, manganese was detected in 3 samples, nitrates were discovered below soil action levels, and radiation levels were below background. Consequently, it is unlikely that significant contamination exists.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Hagaraty, G.; Johnson, J.; Middlebrooks, P.
The Phase II EBS results document the extent of environmental contamination believed to be present on McCormick Ranch. Explosive test areas having the greatest potential for containing soil contaminants were identified using several geophysical survey methods: EM 31 terrain conductivity meter, magnetometer/gradiometer, and ground penetrating radar. From the geophysical surveys, five areas were selected to conduct further environmental analysis. A total of 310 soil samples were collected from the areas and 13 specific high explosive test sites. The samples were screened for semi-volatile organic compounds, PETN, TNT, TNT-degradation products, nitrates and radioactivity. Laboratory analyses were performed and no explosives ormore » degradation products were identified. Semi-volatile organic compounds were in 2 samples, manganese was detected in 3 samples, nitrates were discovered below soil action levels and radiation levels were below background. Consequently, it is unlikely that significant contamination exists.« less
ANALYSIS OF VOLATILES AND SEMIVOLATILES BY DIRECT AQUEOUS INJECTION
Direct aqueous injection analysis (DAI) with gas chromatographic separation and ion trap mass spectral detection was used to analyze aqueous samples for g/L levels of 54 volatile and semivolatile compounds, and problematic non-purgeables and non-extractables. The method reduces ...
Leaching of organic contaminants from storage of reclaimed asphalt pavement.
Norin, Malin; Strömvall, A M
2004-03-01
Recycling of asphalt has been promoted by rapid increases in both the use and price of petroleum-based bitumen. Semi-volatile organic compounds in leachates from reclaimed asphalt pavement, measured in field samples and in laboratory column test, were analysed through a GC/MS screen-test methodology. Sixteen PAH (polyaromatic hydrocarbons) were also analysed in leachates from the column study. The highest concentrations of semi-volatile compounds, approximately 400 microg l(-1), were measured in field samples from the scarified stockpile. Naphthalene, butylated hydroxytoluene (BHT) and dibutyl phthalate (DBP) were the most dominant of the identified semi-volatiles. The occurrence of these compounds in urban groundwater, also indicate high emission rates and persistent structures of the compounds, making them potentially hazardous. Car exhausts, rubber tires and the asphalt material itself are all probable emission sources, determined from the organic contaminants released from the stockpiles. The major leaching mechanism indicated was dissolution of organic contaminants from the surface of the asphalt gravels. In the laboratory column test, the release of high-molecular weight and more toxic PAH was higher in the leachates after two years than at the commencement of storage. The concentrations of semi-volatiles in leachates, were also several times lower than those from the field stockpile. These results demonstrate the need to follow up laboratory column test with real field measurements.
High Throughput Exposure Modeling of Semi-Volatile Chemicals in Articles of Commerce (SOT)
Chemical components of consumer products and articles of commerce such as carpet and clothing are key drivers of exposure in the near-field environment. These chemicals include semi-volatile organic compounds (SVOCs), some of which have been shown to alter endocrine functionality...
AUDIT MATERIALS FOR SEMIVOLATILE ORGANIC MEASUREMENTS DURING HAZARDOUS WASTE TRIAL BURNS
Two new performance audit materials utilizing different sorbents have neen developed to assess the overall accuracy and precision of the sampling, desorption, and analysis of semivolatile organic compounds by EPA, SW 846 Method 0010 (i.e., the Modified Method 5 sampling train). h...
Mashburn, Shana L.; Smith, S. Jerrod
2007-01-01
The U.S. Geological Survey, in cooperation with the Absentee Shawnee Tribe of Oklahoma, began a reconnaissance study of a site in Pottawatomie County, Oklahoma, in 2005 by testing soil, shallow ground water, and plant material for the presence of trace elements and semivolatile organic compounds. Chemical analysis of plant material at the site was investigated as a preliminary tool to determine the extent of contamination at the site. Thirty soil samples were collected from 15 soil cores during October 2005 and analyzed for trace elements and semivolatile organic compounds. Five small-diameter, polyvinyl-chloride-cased wells were installed and ground-water samples were collected during December 2005 and May 2006 and analyzed for trace elements and semivolatile organic compounds. Thirty Johnsongrass samples and 16 Coralberry samples were collected during September 2005 and analyzed for 53 constituents, including trace elements. Results of the soil, ground-water, and plant data indicate that the areas of trace element and semivolatile organic compound contamination are located in the shallow (A-horizon) soils near the threading barn. Most of the trace-element concentrations in the soils on the study site were either similar to or less than trace-element concentrations in background soils. Several trace elements and semivolatile organic compounds exceeded the U.S. Environmental Protection Agency, Region 6, Human Health Medium-Specific Screening Levels 2007 for Tap Water, Residential Soils, Industrial Indoor Soils, and Industrial Outdoor Soils. There was little or no correlation between the plant and soil sample concentrations and the plant and ground-water concentrations based on the current sample size and study design. The lack of correlation between trace-element concentrations in plants and soils, and plants and ground water indicate that plant sampling was not useful as a preliminary tool to assess contamination at the study site.
Volatile and semivolatile organic compounds in laboratory peat fire emissions
NASA Astrophysics Data System (ADS)
George, Ingrid J.; Black, Robert R.; Geron, Chris D.; Aurell, Johanna; Hays, Michael D.; Preston, William T.; Gullett, Brian K.
2016-05-01
In this study, volatile and semi-volatile organic compound (VOCs and SVOCs) mass emission factors were determined from laboratory peat fire experiments. The peat samples originated from two National Wildlife Refuges on the coastal plain of North Carolina, U.S.A. Gas- and particle-phase organic compounds were quantified by gas chromatography-mass spectrometry and by high pressure liquid chromatography. Hazardous air pollutants (HAPs) accounted for a large fraction (∼60%) of the speciated VOC emissions from peat burning, including large contributions of acetaldehyde, formaldehyde, benzene, toluene, and chloromethane. In the fine particle mass (PM2.5), the following organic compound classes were dominant: organic acids, levoglucosan, n-alkanes, and n-alkenes. Emission factors for the organic acids in PM2.5 including n-alkanoic acids, n-alkenoic acids, n-alkanedioic acids, and aromatic acids were reported for the first time for peat burning, representing the largest fraction of organic carbon (OC) mass (11-12%) of all speciated compound classes measured in this work. Levoglucosan contributed to 2-3% of the OC mass, while methoxyphenols represented 0.2-0.3% of the OC mass on a carbon mass basis. Retene was the most abundant particulate phase polycyclic aromatic hydrocarbon (PAH). Total HAP VOC and particulate PAH emissions from a 2008 peat wildfire in North Carolina were estimated, suggesting that peat fires can contribute a large fraction of state-wide HAP emissions.
Sedman, R M; Esparza, J R
1991-01-01
The public health impacts associated with stack emissions from hazardous waste incinerators have become a major concern in recent years. Most evaluations of incinerator stack emissions have focused on three classes of compounds: metals, semivolatile, and volatile compounds. These investigations have been complicated by the difficulty and expense of analyzing the emissions and the limited amount of toxicity information for many of the compounds that have been detected. The results of over 20 trial burns at hazardous waste incinerators were assembled in an attempt to determine which compounds may pose a significant threat to the public health. The risks associated with semivolatile emissions were found to be inconsequential, although further study of dioxins and dibenzofurans emissions appears to be warranted. The risk associated with the emission of cadmium and perhaps chromium (VI) may pose a significant risk to public health at certain facilities. Controls on waste feed or air pollution control devices should be employed to reduce the emission of these metals. Any monitoring of metal emissions from hazardous waste incinerators should focus on cadmium and chromium (VI). PMID:1954929
Moring, J. Bruce
2002-01-01
A public-health assessment conducted for the Texas Department of Health and the Agency for Toxic Substances and Disease Registry concluded that exposure to contaminants through the aquatic food chain is an indeterminate human-health hazard in Lake Worth, Fort Worth, Texas. In 1999, the U.S. Geological Survey, in cooperation with the U.S. Air Force and in collaboration with the Texas Department of Health, collected samples of edible fish tissues from Lake Worth for analysis of selected trace metals, organochlorines, and semivolatile organic compounds to support a human-health risk assessment. Left-side, skin-off fillet samples were collected from 10 individuals each of channel catfish, common carp, freshwater drum (gaspergou), largemouth bass, and white crappie but only from five smallmouth buffalo. The U.S. Geological Survey National Water Quality Laboratory analyzed the samples for 22 trace metals, 40 organochlorine pesticides and polychlorinated biphenyls, and 75 semivolatile organic compounds.
Mixing of secondary organic aerosols versus relative humidity
Ye, Qing; Robinson, Ellis Shipley; Ding, Xiang; Ye, Penglin
2016-01-01
Atmospheric aerosols exert a substantial influence on climate, ecosystems, visibility, and human health. Although secondary organic aerosols (SOA) dominate fine-particle mass, they comprise myriad compounds with uncertain sources, chemistry, and interactions. SOA formation involves absorption of vapors into particles, either because gas-phase chemistry produces low-volatility or semivolatile products that partition into particles or because more-volatile organics enter particles and react to form lower-volatility products. Thus, SOA formation involves both production of low-volatility compounds and their diffusion into particles. Most chemical transport models assume a single well-mixed phase of condensing organics and an instantaneous equilibrium between bulk gas and particle phases; however, direct observations constraining diffusion of semivolatile organics into particles containing SOA are scarce. Here we perform unique mixing experiments between SOA populations including semivolatile constituents using quantitative, single-particle mass spectrometry to probe any mass-transfer limitations in particles containing SOA. We show that, for several hours, particles containing SOA from toluene oxidation resist exchange of semivolatile constituents at low relative humidity (RH) but start to lose that resistance above 20% RH. Above 40% RH, the exchange of material remains constant up to 90% RH. We also show that dry particles containing SOA from α-pinene ozonolysis do not appear to resist exchange of semivolatile compounds. Our interpretation is that in-particle diffusion is not rate-limiting to mass transfer in these systems above 40% RH. To the extent that these systems are representative of ambient SOA, we conclude that diffusion limitations are likely not common under typical ambient boundary layer conditions. PMID:27791066
Mixing of secondary organic aerosols versus relative humidity.
Ye, Qing; Robinson, Ellis Shipley; Ding, Xiang; Ye, Penglin; Sullivan, Ryan C; Donahue, Neil M
2016-10-24
Atmospheric aerosols exert a substantial influence on climate, ecosystems, visibility, and human health. Although secondary organic aerosols (SOA) dominate fine-particle mass, they comprise myriad compounds with uncertain sources, chemistry, and interactions. SOA formation involves absorption of vapors into particles, either because gas-phase chemistry produces low-volatility or semivolatile products that partition into particles or because more-volatile organics enter particles and react to form lower-volatility products. Thus, SOA formation involves both production of low-volatility compounds and their diffusion into particles. Most chemical transport models assume a single well-mixed phase of condensing organics and an instantaneous equilibrium between bulk gas and particle phases; however, direct observations constraining diffusion of semivolatile organics into particles containing SOA are scarce. Here we perform unique mixing experiments between SOA populations including semivolatile constituents using quantitative, single-particle mass spectrometry to probe any mass-transfer limitations in particles containing SOA. We show that, for several hours, particles containing SOA from toluene oxidation resist exchange of semivolatile constituents at low relative humidity (RH) but start to lose that resistance above 20% RH. Above 40% RH, the exchange of material remains constant up to 90% RH. We also show that dry particles containing SOA from α-pinene ozonolysis do not appear to resist exchange of semivolatile compounds. Our interpretation is that in-particle diffusion is not rate-limiting to mass transfer in these systems above 40% RH. To the extent that these systems are representative of ambient SOA, we conclude that diffusion limitations are likely not common under typical ambient boundary layer conditions.
Radulović, Niko S; Blagojević, Polina D
2012-01-01
Unfortunately, contaminants of synthetic/artificial origin are sometimes identified as major constituents of essential oils or plant extracts and considered to be biologically active native plant metabolites. To explore the possibility of early recognition and to create a list of some of the most common semi-volatile contaminants of essential oils and plant extracts. Detailed GC and GC-MS analyses of the evaporation residues of six commercially available diethyl ethers and of a plastic bag hydrodistillate were performed. Average mass scans of the total ion chromatogram profiles of the analysed samples were performed. Almost 200 different compounds, subdivided into two groups, were identified in the analysed samples: (i) compounds that could be only of a synthetic/artificial origin, such as butylated hydroxytoluene and o-phthalic acid esters, i.e. requiring exclusion from the list of identified plant constituents; (ii) compounds possibly of synthetic and/or natural plant origin, i.e. compounds derived from the fatty acid metabolism or products of anaerobic intracellular/microbial fermentation. Average mass scans of the total ion chromatogram profiles provide meaningful and convenient information on uncovering important solvent-derived contamination. A database of the most common semi-volatile contaminants of essential oils and plant extracts has been generated that provides information on the likelihood of rejection or acceptance of contaminants as possible plant constituents. The suggested average mass scan approach enables fast and easy profiling of solvents, allowing even inexperienced researchers to pinpoint contaminants. Copyright © 2011 John Wiley & Sons, Ltd.
Saito, Hiroshi H; Calloway, T Bond; Ferrara, Daro M; Choi, Alexander S; White, Thomas L; Gibson, Luther V; Burdette, Mark A
2004-10-01
After strontium/transuranics removal by precipitation followed by cesium/technetium removal by ion exchange, the remaining low-activity waste in the Hanford River Protection Project Waste Treatment Plant is to be concentrated by evaporation before being mixed with glass formers and vitrified. To provide a technical basis to permit the waste treatment facility, a relatively organic-rich Hanford Tank 241-AN-107 waste simulant was spiked with 14 target volatile, semi-volatile, and pesticide compounds and evaporated under vacuum in a bench-scale natural circulation evaporator fitted with an industrial stack off-gas sampler at the Savannah River National Laboratory. An evaporator material balance for the target organics was calculated by combining liquid stream mass and analytical data with off-gas emissions estimates obtained using U.S. Environmental Protection Agency (EPA) SW-846 Methods. Volatile and light semi-volatile organic compounds (<220 degrees C BP, >1 mm Hg vapor pressure) in the waste simulant were found to largely exit through the condenser vent, while heavier semi-volatiles and pesticides generally remain in the evaporator concentrate. An OLI Environmental Simulation Program (licensed by OLI Systems, Inc.) evaporator model successfully predicted operating conditions and the experimental distribution of the fed target organics exiting in the concentrate, condensate, and off-gas streams, with the exception of a few semi-volatile and pesticide compounds. Comparison with Henry's Law predictions suggests the OLI Environmental Simulation Program model is constrained by available literature data.
Kennedy, Ben W.; Hall, Cassidee C.
2009-01-01
In 2002-03, the U.S. Geological Survey collected samples of streambed sediment at 18 sites in the lower Chena River watershed for analysis of selected nutrients, traces elements, and organic compounds. The purpose of the project was to provide Federal, State, and local agencies as well as neighborhood committees, with information for consideration in plans to improve environmental conditions in the watershed. The exploratory sampling program included analysis of streambed sediment from the Chena River and Chena Slough, a tributary to the Chena River. Results were compared to streambed-sediment guidelines for the protection of aquatic life and to 2001-02 sediment data from Noyes Slough, a side channel of the lower Chena River. The median total phosphorus concentration in Chena Slough sediment samples, 680 milligrams per kilogram (mg/kg), was two orders of magnitude greater than median total phosphorus concentration in Chena River sediment samples of 5.2 mg/kg. Median concentrations of chloride and sulfate also were greater in Chena Slough samples. Low concentrations of nitrate were detected in most of the Chena Slough samples; nitrate concentrations were below method reporting limits or not detected in Chena River sediment samples. Streambed-sediment samples were analyzed for 24 trace elements. Arsenic, nickel, and zinc were the only trace elements detected in concentrations that exceeded probable-effect levels for the protection of aquatic life. Concentrations of arsenic in Chena Slough samples ranged from 11 to 70 mg/kg and concentrations in most of the samples exceeded the probable-effect guideline for arsenic of 17 mg/kg. Arsenic concentrations in samples from the Chena River ranged from 9 to 12 mg/kg. The background level for arsenic in the lower Chena River watershed is naturally elevated because of significant concentrations of arsenic in local bedrock and ground water. Sources of elevated concentrations of zinc in one sample, and of nickel in two samples, are unknown. With the exception of elevated arsenic levels in samples from Chena Slough, the occurrence and concentration of trace elements in the streambed sediments of Chena Slough and Chena River were similar to those in Noyes Slough sediment. Sediment samples were analyzed for 78 semivolatile organic compounds and 32 organochlorine pesticides and polychlorinated biphenyls (PCBs). Low concentrations of dimethylnaphthalene and p-Cresol were detected in most Chena Slough and Chena River sediment samples. The number of semivolatile organic compounds detected ranged from 5 to 21 in most Chena Slough sediment samples. In contrast, three or fewer semivolatile organic compounds were detected in Chena River sediment samples, most likely because chemical-matrix interference resulted in elevated reporting limits for organochlorine compounds in the Chena River samples. Low concentrations of fluoranthene, pyrene, and phenanthrene were detected in Chena Slough sediment. Relatively low concentrations of DDT or its degradation products, DDD and DDE, were detected in all Chena Slough samples. Concentrations of total DDT (DDT+DDD+DDE) in two Chena Slough sediment samples exceeded the effectsrange median aquatic-life criteria of 46.1 micrograms per kilogram (ug/kg). DDT concentrations in Chena River streambed-sediment samples were less than 20 ug/kg. Low concentrations of PCB were detected in two Chena Slough streambed-sediment samples. None of the concentrations of the polychlorinated biphenyls or semivolatile organic compounds for which the samples were analyzed exceeded available guidelines for the protection of aquatic life. With the exception of elevated total DDT in two Chena Slough samples, the occurrence and concentration of organochlorine compounds in Chena Slough and Chena River sediment were similar to those in samples collected from Noyes Slough in 2001-02.
Miller, Cherie V.; Klohe, Cheryl A.
2003-01-01
This data report is a summary of chemical analyses conducted by the U.S. Geological Survey on ground water and sediment in the tidal Anacostia River watershed, Washington, D.C. during July-August 2002. Cores were drilled and wells were established at three shoreline sites: two wells at the New York Avenue overpass, two wells at the Kenilworth Aquatic Gardens, and one well at Anacostia Park. Additionally, two cores were collected by hoverprobe in mudflats on the river: one by Benning Road and one in the mouth of Beaverdam Creek. Chemical analyses included volatile organic compounds, semi-volatile organic compounds or polyaromatic hydrocarbons, organochlorine pesticides, aroclors and total polychlorinated biphenyls, metals, nutrients, biochemical and chemical oxygen demands, total phenols, total cyanide, oil and grease, and total suspended and dissolved solids in aqueous phases.
Riederer, Markus; Daiss, Andreas; Gilbert, Norbert; Köhle, Harald
2002-08-01
The behaviour of (semi-)volatile organic compounds at the interface between the leaf surface and the atmosphere was investigated by finite-element numerical simulation. Three model systems with increasing complexity and closeness to the real situation were studied. The three-dimensional model systems were translated into appropriate grid structures and diffusive and convective transport in the leaf/atmosphere interface was simulated. Fenpropimorph (cis-4-[3-(4-tert-butylphenyl)-2-methylpropyl]-2,6-dimethylmorpholine) and Kresoxim-methyl ((E)-methyl-2-methoxyimino-2-[2-(o-tolyloxy-methyl)phenyl] acetate) were used as model compounds. The simulation showed that under still and convective conditions the vapours emitted by a point source rapidly form stationary envelopes around the leaves. Vapour concentrations within these unstirred layers depend on the vapour pressure of the compound in question and on its affinity to the lipoid surface layers of the leaf (cuticular waxes, cutin). The rules deduced from the numerical simulation of organic vapour behaviour in the leaf/atmosphere interface are expected to help in assessing how (semi-)volatile plant products (e.g. hormones, pheromones, secondary metabolites) and xenobiotics (e.g. pesticides, pollutants) perform on plant surfaces.
Assessment of semi-volatile organic compounds in drinking water sources in Jiangsu, China.
Wu, Yifeng; Jia, Yongzhi; Lu, Xiwu
2013-08-01
Many xenobiotic compounds, especially organic pollutants in drinking water, can cause threats to human health and natural ecosystems. The ability to predict the level of pollutants and identify their source is crucial for the design of pollutant risk reduction plans. In this study, 25 semi-volatile organic compounds (SVOCs) were assessed at 16 monitoring sites of drinking water sources in Jiangsu, east China, to evaluate water quality conditions and source of pollutants. Four multivariate statistical techniques were used for this analysis. The correlation test indicated that 25 SVOCs parameters variables had a significant spatial variability (P<0.05). The results of correlation analysis, principal component analysis (PCA) and cluster analysis (CA) suggested that at least four sources, i.e., agricultural residual pesticides, industrial sewage, water transportation vehicles and miscellaneous sources, were responsible for the presence of SVOCs in the drinking water sites examined, accounting for 89.6% of the total variance in the dataset. The analysis of site similarity showed that 16 sites could be divided into high, moderate, and low pollutant level groups at (D(link)/D(max))×25<10, and each group had primary typical SVOCs. These results provide useful information for developing appropriate strategies for contaminants control in drinking water sources. Copyright © 2013 Elsevier Inc. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Not Available
1994-08-22
The Pasley Solvents and Chemicals site, which is on the National Priorities List, is situated between the borders of the Village of Garden City and Uniondale in the Town of Hempstead, Nassau County, New York. Soils at the site are contaminated with volatile organic compounds (VOCs), primarily solvent constituents and petroleum hydrocarbons compounds; semi-volatile compounds (primarily polycyclic aromatic hydrocarbon compounds); and several metals. Groundwater in the shallow and deep aquifers under the site is contaminated with VOCs, primarily solvent constituents and petroleum hydrocarbons compounds, and two semi-volatile compounds at the concentrations exceeding public health assessment comparison values. Limited information ismore » available on soil gas intrusion and indoor air contamination, and this pathway is of concern since occupied buildings are nearby and above contaminated groundwater plumes.« less
Gill, Amy C.; Robinson, John A.; Redmond, Jymalyn E.; Bradley, Michael W.
2008-01-01
The watershed of Fivemile Creek (FMC), a tributary to the Locust Fork of the Black Warrior River, is located north of Birmingham, Alabama. Areas that have been previously coal-mined border the creek, and portions of the upper watershed have been and are currently (2007) being used for industrial and urban uses. The U.S. Geological Survey (USGS), in cooperation with the City of Tarrant, the Freshwater Land Trust, and the Jefferson County Commission, conducted a water-quality assessment of 12 sites along FMC during 2003?2005. Water samples were analyzed for basic physical and chemical properties and concentrations of major ions, nutrients, fecal indicator bacteria, organic wastewater compounds, pesticides, trace elements, and semivolatile organic compounds. Streambed-sediment samples were analyzed for concentrations of trace elements and semivolatile organic compounds. Benthic invertebrate communities were evaluated for taxonomic composition and relation to water-quality conditions. Nutrient concentrations in the FMC watershed reflect the influences of natural and anthropogenic sources. Concentrations of total nitrogen in all samples and total Kjeldahl nitrogen in at least one sample each collected from FMC at Hewitt Park, FMC below Springdale Road, FMC at Lewisburg, FMC near Republic, FMC at Brookside, and FMC at Linn Crossing exceeded U.S. Environmental Protection Agency (USEPA) ecoregion nutrient criteria. Total phosphorus concentrations in about 58 percent of all samples were above the ecoregion nutrient criteria. Concentrations of chlorophyll a, an indicator of algal biomass, in the FMC watershed were below the appropriate USEPA ecoregion criteria. Fecal indicator bacteria concentrations occasionally exceeded criteria established by the Alabama Department of Environmental Management (ADEM) and the USEPA to protect human health and aquatic life. Median fecal-coliform concentrations equaled or exceeded USEPA criteria at four of the six sites with multiple samples. Maximum Escherichia coli (E. coli) concentrations usually occurred during high-flow conditions and exceeded the single-sample criterion for infrequently-used whole-body contact (576 colonies per 100 milliliters) at all but one site. Median E. coli concentrations for two of the seven sites with multiple samples exceeded USEPA criteria. Twenty-nine samples were collected from sites along FMC and analyzed by the USGS National Water Quality Laboratory for the presence of 57 organic wastewater compounds. Forty-six of the 57 organic wastewater compounds, representing all 11 general-use categories, were detected in samples from FMC. All detections of organic wastewater compounds were estimated below laboratory reporting limits except for several detections of the herbicide bromacil. Herbicides accounted for approximately 62 percent of the number of pesticide detections in the FMC study area. Two herbicides, atrazine and simazine, were detected most frequently, in 100 percent of the surface-water samples. Fipronil sulfide was the most commonly detected insecticide-derived compound, occurring in 52 percent of the surface-water samples. Concentrations of one insecticide, dieldrin, exceeded the USEPA?s health advisory level for drinking water in one sample at FMC at Hewitt Park and in one sample at FMC below Springdale Road. Concentrations of carbaryl in two samples and malathion in one sample exceeded aquatic-life criteria. Only a few trace element concentrations measured in FMC exceeded established standards or criteria. Some concentrations of aluminum and manganese were above secondary drinking-water standards. One cadmium concentration and three selenium concentrations measured at FMC at Lewisburg exceeded ADEM chronic aquatic-life criteria. Streambed-sediment samples were collected at seven sites along FMC, and analyzed for selected semivolatile organic compounds and trace elements. Forty-nine of 98 semivolatile organic compounds were detected in stre
Yang, Cui; Wang, Juan; Li, Donghao
2013-10-17
Vegetables and fruits are necessary for human health, and traditional Chinese medicine that uses plant materials can cure diseases. Thus, understanding the composition of plant matrix has gained increased attention in recent years. Since plant matrix is very complex, the extraction, separation and quantitation of these chemicals are challenging. In this review we focus on the microextraction techniques used in the determination of volatile and semivolatile organic compounds (such as esters, alcohols, aldehydes, hydrocarbons, ketones, terpenes, sesquiterpene, phenols, acids, plant secondary metabolites and pesticides) from plants (e.g., fruits, vegetables, medicinal plants, tree leaves, etc.). These microextraction techniques include: solid phase microextraction (SPME), stir-bar sorptive extraction (SBSE), single drop microextraction (SDME), hollow fiber liquid phase microextraction (HF-LPME), dispersive liquid liquid microextraction (DLLME), and gas purge microsyringe extraction (GP-MSE). We have taken into consideration papers published from 2008 to the end of January 2013, and provided critical and interpretative review on these techniques, and formulated future trends in microextraction for the determination of volatile and semivolatile compounds from plants. Copyright © 2013 Elsevier B.V. All rights reserved.
Mendes, Berta; Gonçalves, João; Câmara, José S
2012-01-15
In this study the feasibility of different extraction procedures was evaluated in order to test their potential for the extraction of the volatile (VOCs) and semi-volatile constituents (SVOCs) from wines. In this sense, and before they could be analysed by gas chromatography-quadrupole first stage masss spectrometry (GC-qMS), three different high-throughput miniaturized (ad)sorptive extraction techniques, based on solid phase extraction (SPE), microextraction by packed sorbents (MEPS) and solid phase microextraction (SPME), were studied for the first time together, for the extraction step. To achieve the most complete volatile and semi-volatile signature, distinct SPE (LiChrolut EN, Poropak Q, Styrene-Divinylbenzene and Amberlite XAD-2) and MEPS (C(2), C(8), C(18), Silica and M1 (mixed C(8)-SCX)) sorbent materials, and different SPME fibre coatings (PA, PDMS, PEG, DVB/CAR/PDMS, PDMS/DVB, and CAR/PDMS), were tested and compared. All the extraction techniques were followed by GC-qMS analysis, which allowed the identification of up to 103 VOCs and SVOCs, distributed by distinct chemical families: higher alcohols, esters, fatty acids, carbonyl compounds and furan compounds. Mass spectra, standard compounds and retention index were used for identification purposes. SPE technique, using LiChrolut EN as sorbent (SPE(LiChrolut EN)), was the most efficient method allowing for the identification of 78 VOCs and SVOCs, 63 and 19 more than MEPS and SPME techniques, respectively. In MEPS technique the best results in terms of number of extractable/identified compounds and total peak areas of volatile and semi-volatile fraction, were obtained by using C(8) resin whereas DVB/CAR/PDMS was revealed the most efficient SPME coating to extract VOCs and SVOCs from Bual wine. Diethyl malate (18.8±3.2%) was the main component found in wine SPE(LiChrolut EN) extracts followed by ethyl succinate (13.5±5.3%), 3-methyl-1-butanol (13.2±1.7%), and 2-phenylethanol (11.2±9.9%), while in SPME(DVB/CAR/PDMS) technique 3-methyl-1-butanol (43.3±0.6%) followed by diethyl succinate (18.9±1.6%), and 2-furfural (10.4±0.4%), are the major compounds. The major VOCs and SVOCs isolated by MEPS(C8) were 3-methyl-1-butanol (26.8±0.6%, from wine total volatile fraction), diethyl succinate (24.9±0.8%), and diethyl malate (16.3±0.9%). Regardless of the extraction technique, the highest extraction efficiency corresponds to esters and higher alcohols and the lowest to fatty acids. Despite some drawbacks associated with the SPE procedure such as the use of organic solvents, the time-consuming and tedious sampling procedure, it was observed that SPE(LiChrolut EN), revealed to be the most effective technique allowing the extraction of a higher number of compounds (78) rather than the other extraction techniques studied. Copyright © 2011 Elsevier B.V. All rights reserved.
Rogge, Wolfgang F; Ondov, John M; Bernardo-Bricker, Anna; Sevimoglu, Orhan
2011-12-01
As part of the Baltimore PM2.5 Supersite study, intensive three-hourly continuous PM2.5 sampling was conducted for nearly 4 weeks in summer of 2002 and as well in winter of 2002/2003. Close to 120 individual organic compounds have been quantified separately in filter and polyurethane foam (PUF) plug pairs for 17 days for each sampling period. Here, the focus is on (1) describing briefly the new sampling system, (2) discussing filter/PUF plugs breakthrough experiments for semi-volatile compounds, (3) providing insight into phase distribution of semi-volatile organic species, and (4) discussing the impact of air pollution sampling time on human exposure with information on maximum 3- and 24-h averaged ambient concentrations of potentially adverse health effects causing organic pollutants. The newly developed sampling system consisted of five electronically controlled parallel sampling channels that are operated in a sequential mode. Semi-volatile breakthrough experiments were conducted in three separate experiments over 3, 4, and 5 h each using one filter and three PUF plugs. Valuable insight was obtained about the transfer of semi-volatile organic compounds through the sequence of PUF plugs and a cut-off could be defined for complete sampling of semi-volatile compounds on only one filter/PUF plug pair, i.e., the setup finally used during the seasonal PM2.5 sampling campaign. Accordingly, n-nonadecane (C19) with a vapor pressure (vp) of 3.25 × 10(-4) Torr is collected with > 95% on the filter/PUF pair. Applied to phenanthrene, the most abundant the PAH sampled, phenanthrene (vp, 6.2 × 10(-5) Torr) was collected completely in wintertime and correlates very well with three-hourly PM2.5 ambient concentrations. Valuable data on the fractional partitioning for semi-volatile organics as a function of season is provided here and can be used to differentiate the human uptake of an organic pollutant of interest via gas- and particle-phase exposure. Health effects studies often relay on PM2.5 exposure measurements taken over 24 h or longer. We found that maximum 3-h concentrations are frequently two to five times higher than that found for maximum 24-h concentrations, an important aspect when considering that short-term exposure to higher air pollution levels are more likely to overpower defense mechanisms in the human lung with subsequent adverse effects even at lower pollutant levels.
Contribution of particulate brown carbon to light absorption in the rural and urban Southeast US
NASA Astrophysics Data System (ADS)
Devi, J. Jai; Bergin, Michael H.; Mckenzie, Michael; Schauer, James J.; Weber, Rodney J.
2016-07-01
Measurements of wavelength dependent aerosol light absorption coefficients were carried out as part of the Southern Oxidant and Aerosol Study (SOAS) during the summer of 2013 to determine the contribution of light absorbing organic carbon (BrC) to total aerosol light absorption in a rural location (Centreville, AL) and an urban area (Atlanta, GA). The light absorption coefficients in the near UV and visible wavelengths were measured for both ambient air, as well as ambient air heated in a thermal denuder to 200 °C to remove the semi-volatile organic compounds. Atlanta measurements show dominance of semi-volatile brown carbon with an average absorption angstrom exponent (AAE) of 1.4 before heating and about 1.0 after heating. In urban Atlanta, a decrease of about ∼35% in the light absorption coefficient at 370 nm after heating indicates that light absorbing organic compounds are a substantial fraction of the light absorption budget. Furthermore, a considerable increase in the fraction of light absorption by the semi-volatile aerosol occurs during the daytime, likely linked with photochemistry. Measurements at rural Centerville, on the other hand, do not show any major change in AAE with values before and after heating of 0.99 and 0.98, respectively. Overall the results suggest that photochemical aged urban emissions result in the presence of light absorbing BrC, while at rural locations which are dominated by aged aerosol and local biogenic emissions (based on measurements of Angstrom exponents) BrC does not significantly contribute to light absorption.
NASA Astrophysics Data System (ADS)
Oliveira, Vanessa; Santos, Ana L.; Aguiar, Claúdia; Santos, Luisa; Salvador, Ângelo C.; Gomes, Newton C. M.; Silva, Helena; Rocha, Sílvia M.; Almeida, Adelaide; Cunha, Ângela
2012-09-01
The aim of this study was to investigate the influence of monospecific colonization of sediment stands by Spartina maritima or Halimione portulacoides on benthic prokaryote assemblages in a salt marsh located in Ria de Aveiro (Portugal). The distribution of Bacteria, Archaea and sulfate-reducing bacteria (SRB) in sediments with monospecific plant stands and in unvegetated sediments was characterized by Fluorescence In Situ Hybridization (FISH). Total prokaryote abundance (0.4 × 109-1.7 × 109 cells gdw-1) was highest in sediments from the surface layer. The domain Bacteria comprised approximately 40% of total prokaryote communities with the highest percentages occurring in the surface layer. Archaeal cells corresponded to an average of 25% of total prokaryote population, with higher abundance in the vegetation banks, and displaying homogeneous vertical distribution. The relative abundance of SRB represented approximately 3% of total 4', 6-diamidino-2-phenylindole dihydrochloride (DAPI) stained cells at unvegetated sediment and H. portulacoides stand and 7% at S. maritima stand. Headspace solid-phase microextraction (HS-SPME) combined with Comprehensive Two-Dimensional Gas Chromatography-Time-of-Flight Mass Spectrometry (GC × GC-ToFMS) was used to analyse the volatile and semi-volatile fraction of root exudates. A total of 171 compounds were identified and Principal Component Analysis showed a clear separation between the chemical composition (volatile and semi-volatile organic compounds) of the exudates of the two plants. The patterns of vertical distribution and differences in the proportion of SRB and Archaea in the prokaryote communities developing in sediments colonized by Spartina maritima or Halimione portulacoides suggest the existence of plant-specific interactions between halophyte vegetation and estuarine sediment bacteria in Ria de Aveiro salt marshes, exerted via sediment lithology and root-derived exudates.
The partitioning of a diverse set of semivolatile organic compounds (SOCs) on a variety of organic aerosols was studied using smog chamber experimental data. Existing data on the partitioning of SOCs on aerosols from wood combustion, diesel combustion, and the Quantity and quality of stormwater collected from selected stormwater outfalls at industrial sites, Fort Gordon, Georgia, 2012
Nagle, Doug D.
2013-01-01
Samples from sites SWR11–3, SWR11–4, and SWR11–5 were analyzed for 83 volatile and semivolatile organic compounds. Eight polycyclic aromatic hydrocarbon compounds, benzo[a]pyrene, benzo[b]fluoranthene, benzo[ghi]perylene, benzo[k]fluoranthene, chrysene, indeno[1,2,3-cd]pyrene, phenanthrene, and pyrene, were detected at all three sites. Of the 86 volatile and semivolatile organic compounds that were analyzed in stormwater samples from heating and cooling sites, 15 (18 percent) were detected at site SWR11–3, 12 (14 percent) were detected at site SWR11–4, and 17 (20 percent) were detected at site SWR11–5.
Speciated Chemical Composition of Biomass Burning Aerosol from Various Fuels during FIREX
NASA Astrophysics Data System (ADS)
Jen, C.; Hatch, L. E.; Kreisberg, N. M.; Selimovic, V.; Yokelson, R. J.; Barsanti, K.; Goldstein, A. H.
2017-12-01
Biomass burning is the largest global source of atmospheric primary carbonaceous aerosols and the second largest global source of non-methane organic compounds, including volatile and semi-volatile organic compounds that are now understood to be major contributors to secondary particle formation in the atmosphere. As wildfires in forested regions such as the western United States become larger and more frequent, understanding the chemical composition of biomass burning organic aerosol is needed to better predict their increasing impact on human health, air quality, and climate. This study presents emission profiles of chemically speciated intermediate and semi-volatile organic compounds present in biomass burning aerosol particles ≤1.0 μm. Biomass burning organic aerosol (BBOA) samples from a variety of fuel types and burning conditions were collected during the FIREX campaign at the USDA Fire Lab (Missoula, MT). Fuels were primarily selected from vegetation commonly found in the western United States, such as ponderosa pine, lodgepole pine, ceanothus, and chaparral. Collected BBOA was thermally desorbed from the filters and analyzed using online derivatization and 2-dimensional gas chromatography with an electron impact (70 eV) and vacuum ultra violet light (10.5 eV) high resolution time of flight mass spectrometer for compound identification. Emission profiles for specific compounds (e.g., levoglucosan) and families of compounds (e.g., sugars and methoxyphenols) show distinct variations between different fuel types, with major differences between fresh and partially decomposed fuels. Results also illustrate the variability in chemical species between burns conducted under similar conditions. Furthermore, chemical fingerprints, representing ratios of normalized emissions for key chemical compounds, were measured for specific fuels/conditions and could be used in future field studies to help identify contributions of various vegetation to total BBOA and in models to estimate the chemical composition of BBOA emissions.
USDOE Top-of-Rail Lubricant Project
DOE Office of Scientific and Technical Information (OSTI.GOV)
Mohumad F. Alzoubi; George R. Fenske; Robert A. Erck
2002-02-01
Lubrication of wheel/rail systems has been recognized for the last two decades as a very important issue for railroads. Energy savings and less friction and wear can be realized if a lubricant can be used at the wheel/rail interface. On the other hand, adverse influences are seen in operating and wear conditions if improper or excessive lubrication is used. Also, inefficiencies in lubrication need to be avoided for economic and environmental reasons. The top-of-rail (TOR) lubricant concept was developed by Texaco Corporation to lubricate wheels and rails effectively and efficiently. Tranergy Corporation has been developing its SENTRAEN 2000{trademark} lubrication systemmore » for the last ten years, and this revolutionary new high-tech on-board rail lubrication system promises to dramatically improve the energy efficiency, performance, safety, and track environment of railroads. The system is fully computer-controlled and ensures that all of the lubricant is consumed as the end of the train passes. Lubricant quantity dispensed is a function of grade, speed, curve, and axle load. Tranergy also has its LA4000{trademark} wheel and rail simulator, a lubrication and traction testing apparatus. The primary task of this project was collecting and analyzing the volatile and semivolatile compounds produced as the lubricant was used. The volatile organic compounds were collected by Carbotrap cartridges and analyzed by adsorption and gas chromatography/mass spectrometry (GC/MS). The semivolatile fraction was obtained by collecting liquid that dripped from the test wheel. The collected material was also analyzed by GC/MS. Both of these analyses were qualitative. The results indicated that in the volatile fraction, the only compounds on the Environmental Protection Agency's (EPA) Superfund List of Analytes detected were contaminants either in the room air or from other potential contamination sources in the laboratory. Similarly, in the semivolatile fraction none of the detected compounds are on the EPA's Superfund List of Analytes. The major compound in the semivolatile fraction is 1,2-propanediol, which was also found as the major component of the TOR lubricant before testing. Other compounds found in trace quantities either were present in the TOR lubricant or were small fragments from the polymeric component of the TOR lubricant. The second task for Argonne in this project was to investigate the effects of axle load, angle of attack, and quantity of lubricant on lateral friction forces, as well as the consumption time of the TOR lubricant. The second task was to collect and qualitatively identify any volatile and semivolatile compounds produced upon use of the TOR lubricant.« less
Arnold, Karen; Teixeira, João Paulo; Mendes, Ana; Madureira, Joana; Costa, Solange; Salamova, Amina
2018-05-31
The occurrence of five groups of semivolatile organic compounds (SVOCs) (total of ∼120 distinct chemicals) was investigated in senior care facilities in the United States and in Portugal. Indoor settled dust samples were collected from fourteen facilities, and the concentrations of organophosphate esters (OPEs), brominated flame retardants (BFRs), polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs), and polychlorinated biphenyls (PCBs) were measured in these samples. Overall, OPEs, PAHs, and BFRs were the most abundant, and OCPs and PCBs were the least abundant SVOC groups in dust collected from both U.S. and Portuguese facilities. ∑OPE, ∑PAH, and ∑BFR concentrations were significantly higher in U.S. facilities than those in Portuguese facilities (P < 0.001), while ∑OCP and ∑PCB concentrations were not different between the two countries (P < 0.05). The samples were collected from three different microenvironments, including bedrooms, living rooms, and corridors. ∑OPE, ∑PAH, and ∑BFR concentrations were up to five times higher in corridors compared to bedrooms and living rooms. ∑OCP and ∑PCB concentrations were overall higher in bedrooms and in living rooms and lower in corridors. Copyright © 2018 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Pecault, Isabelle Tovena
2017-11-01
High-power laser facilities, such as Laser MegaJoule, are currently being operated for inertial confinement fusion experiments. Emission of volatile organic compounds (VOC) and moreover semivolatile organic compounds (SVOCs) from seals in laser environment is of tremendous importance for the optics lifetime and laser performance. That is why all the seals were screening in the same conditions: 48 h at 30°C and three successive cycle of 1.5 h at 50°C. This paper focuses on the qualification test performed on three seals: two ethylene propylene diene monomer (EPDM) and one fluoropolymer (FPM). It is shown that the molded and the extruded EPDM do not outgas the same amount neither the same molecules whereas EPDM and FPM outgas nearly the same level of phthalates.
Liu, Benhua; Li, Yuehua; Ma, Jianfeng; Huang, Linxian; Chen, Liang
2016-01-01
China is suffering from serious water and soil pollution, especially in the North China Plain. This work investigated semi-volatile organic compounds (SVOCs) in surface water, groundwater and soil within a chemical industrial park in Eastern China, for which the volatile organic compound (VOC) results have been previously reported. A total of 20 samples were collected from the field, and analyzed in the laboratory. A 100% detection frequency of SVOCs in samples from this chemical industrial park was observed (same as VOCs). Moreover, the detection frequency of 113 SVOCs in each sample reached 15.93, 12.39 and 20.35% for surface water, groundwater and soil, respectively. The most detected SVOCs in the park included N-containing SVOCs, polycyclic aromatic hydrocarbons, phthalates, organic pesticides and polychlorodiphenyls. The elevated detecting frequencies and concentration levels of SVOCs identified in the groundwater were attributed to the intensive chemical production activities in the park. In addition, the agricultural activities in the area might also have contributed to the SVOCs to the groundwater. The results of VOCs and SVOCs from this and previous studies suggest that the groundwater in this industrial park has been severely contaminated, and the contamination likely spreads beyond the park. Imminent hydrogeological assessments and remedial actions are warranted to eliminate the source and mitigate the potential plume expansion beyond the park boundary.
NASA Astrophysics Data System (ADS)
Goldstein, A. H.; Isaacman, G. A.; Misztal, P. K.; Yee, L.; Olson, K. F.; Moss, J.; Kreisberg, N. M.; Hering, S. V.; Park, J. H.; Kaser, L.; Seco, R.; Guenther, A. B.; Su, L.; Mak, J. E.; Holzinger, R.; Hu, W.; Campuzano Jost, P.; Palm, B. B.; Day, D. A.; Jimenez, J. L.; Koss, A.; De Gouw, J. A.
2014-12-01
Our overarching goals in the SOAS 2013 campaign were to 1) quantify biogenic VOC emission and VOC deposition to understand the processes controlling these bi-directional exchanges, 2) observe a broad suite of primary VOC and their oxidation products in the field and in controlled laboratory experiments, and 3) investigate their fate to understand how anthropogenic pollution alters oxidation pathways and secondary organic aerosol (SOA) formation. We pursued these goals through measurement of atmospheric organics ranging from very volatile (using in-situ GC-MS and proton transfer reaction time-of-flight MS, PTR-ToF-MS) to semi-volatile gas and particle phase compounds (using the Semi-Volatile Thermal desorption Aerosol Gas chromatograph, SV-TAG). Measured concentrations and fluxes of VOCs at the top of the SEARCH tower were coordinated with concentration gradients and fluxes at the AABC flux tower site, and vertical profiles using the Long-EZ aircraft to provide equivalent observations across sites. These results are informed through measurements using the same instrument during the FIXIT controlled laboratory oxidation study at CalTech that investigated oxidation pathways of BVOC with varying levels of anthropogenic pollutants. Measurements by SV-TAG of particle-phase and total gas-plus-particle-phase compounds at the SEARCH tower provide hourly quantification of semi-volatile compounds, including the oxidation products of measured VOCs. Derivatization of hydroxyl groups prior to GC analysis allows analysis of highly oxidized chemicals, including most known tracers. Methyl tetrols, an oxidation product of isoprene, had a significant day-time gas-phase component, and their abundance was strongly correlated with particle-phase sulfate, indicative of anthropogenic influence on the formation or partitioning processes. Similar observations of pinic acid (monterpene oxidation product) and many other BVOC oxidation products were made in both the gas and particle phases. Through measurements of specific chemical tracers across a wide range of volatilities, we explore the chemical lifecycle of BVOCs to understand anthropogenic-biogenic interactions in aerosol formation.
Xie, M; Barsanti, K C; Hannigan, M P; Dutton, S J; Vedal, S
2013-01-01
Gas-phase concentrations of semi-volatile organic compounds (SVOCs) were calculated from gas/particle (G/P) partitioning theory using their measured particle-phase concentrations. The particle-phase data were obtained from an existing filter measurement campaign (27 January 2003-2 October 2005) as a part of the Denver Aerosol Sources and Health (DASH) study, including 970 observations of 71 SVOCs (Xie et al., 2013). In each compound class of SVOCs, the lighter species (e.g. docosane in n alkanes, fluoranthene in PAHs) had higher total concentrations (gas + particle phase) and lower particle-phase fractions. The total SVOC concentrations were analyzed using positive matrix factorization (PMF). Then the results were compared with source apportionment results where only particle-phase SVOC concentrations were used (particle only-based study; Xie et al., 2013). For the particle only-based PMF analysis, the factors primarily associated with primary or secondary sources ( n alkane, EC/sterane and inorganic ion factors) exhibit similar contribution time series ( r = 0.92-0.98) with their corresponding factors ( n alkane, sterane and nitrate+sulfate factors) in the current work. Three other factors (light n alkane/PAH, PAH and summer/odd n alkane factors) are linked with pollution sources influenced by atmospheric processes (e.g. G/P partitioning, photochemical reaction), and were less correlated ( r = 0.69-0.84) with their corresponding factors (light SVOC, PAH and bulk carbon factors) in the current work, suggesting that the source apportionment results derived from particle-only SVOC data could be affected by atmospheric processes. PMF analysis was also performed on three temperature-stratified subsets of the total SVOC data, representing ambient sampling during cold (daily average temperature < 10 °C), warm (≥ 10 °C and ≤ 20 °C) and hot (> 20 °C) periods. Unlike the particle only-based study, in this work the factor characterized by the low molecular weight (MW) compounds (light SVOC factor) exhibited strong correlations ( r = 0.82-0.98) between the full data set and each sub-data set solution, indicating that the impacts of G/P partitioning on receptor-based source apportionment could be eliminated by using total SVOC concentrations.
NASA Astrophysics Data System (ADS)
Khlystov, A.; Grieshop, A. P.; Saha, P.; Subramanian, R.
2013-12-01
Semi-volatile compounds, including particle-bound water, comprise a large part of aerosol mass and have a significant influence on aerosol lifecycle and its optical properties. Understanding the properties of semi-volatile compounds, especially those pertaining to gas/aerosol partitioning, is of critical importance for our ability to predict concentrations and properties of ambient aerosol. A set of state-of-the-art instruments was deployed at the SEARCH site near Centerville, AL during the Southern Oxidant and Aerosol Study (SOAS) campaign in summer 2013 to measure the effect of temperature and relative humidity on aerosol size distribution, composition and optical properties. Light scattering and absorption by temperature- and humidity-conditioned aerosols was measured using three photo-acoustic extinctiometers (PAX) at three wavelengths (405 nm, 532 nm, and 870 nm). In parallel to these measurements, a long residence time temperature-stepping thermodenuder and a variable residence time constant temperature thermodenuder in combination with three SMPS systems and an Aerosol Chemical Speciation Monitor (ACSM) were used to assess aerosol volatility and kinetics of aerosol evaporation. It was found that both temperature and relative humidity have a strong effect on aerosol optical properties. The variable residence time thermodenuder data suggest that aerosol equilibrated fairly quickly, within 2 s, in contrast to other ambient observations. Preliminary analysis show that approximately 50% and 90% of total aerosol mass evaporated at temperatures of 100 C and 180C, respectively. Evaporation varied substantially with ambient aerosol loading and composition and meteorology. During course of this study, T50 (temperatures at which 50% aerosol mass evaporates) varied from 60 C to more than 120 C.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Hagaraty, G.; Johnson, J.; Middlebrooks, P.
The Phase II EBS results document the extent of environmental contamination believed to be present on McCormick Ranch. Explosive test areas having the greatest potential for containing soil contaminants were identified using several geophysical survey methods: EM 31 terrain conductivity meter, magnetometer/gradiometer, and ground penetrating radar. From the geophysical surveys, five areas were selected to conduct further environmental analysis. A total of 310 soil samples were collected from the and 13 specific high explosive test sites. The samples were screened for semi-volatile organic PETN, TNT, TNT-degradation products, nitrates and radioactivity. Laboratory analyses were and no explosives or degradation products weremore » identified. Semi-volatile organic compounds were in 2 samples, manganese was detected in 3 samples, nitrates were discovered below soil action levels, and radiation levels were below background. Consequently, it is unlikely that significant contamination exists.« less
NASA Astrophysics Data System (ADS)
Zuend, A.; Marcolli, C.; Peter, T.; Seinfeld, J. H.
2010-08-01
Semivolatile organic and inorganic aerosol species partition between the gas and aerosol particle phases to maintain thermodynamic equilibrium. Liquid-liquid phase separation into an organic-rich and an aqueous electrolyte phase can occur in the aerosol as a result of the salting-out effect. Such liquid-liquid equilibria (LLE) affect the gas/particle partitioning of the different semivolatile compounds and might significantly alter both particle mass and composition as compared to a one-phase particle. We present a new liquid-liquid equilibrium and gas/particle partitioning model, using as a basis the group-contribution model AIOMFAC (Zuend et al., 2008). This model allows the reliable computation of the liquid-liquid coexistence curve (binodal), corresponding tie-lines, the limit of stability/metastability (spinodal), and further thermodynamic properties of multicomponent systems. Calculations for ternary and multicomponent alcohol/polyol-water-salt mixtures suggest that LLE are a prevalent feature of organic-inorganic aerosol systems. A six-component polyol-water-ammonium sulphate system is used to simulate effects of relative humidity (RH) and the presence of liquid-liquid phase separation on the gas/particle partitioning. RH, salt concentration, and hydrophilicity (water-solubility) are identified as key features in defining the region of a miscibility gap and govern the extent to which compound partitioning is affected by changes in RH. The model predicts that liquid-liquid phase separation can lead to either an increase or decrease in total particulate mass, depending on the overall composition of a system and the particle water content, which is related to the hydrophilicity of the different organic and inorganic compounds. Neglecting non-ideality and liquid-liquid phase separations by assuming an ideal mixture leads to an overestimation of the total particulate mass by up to 30% for the composition and RH range considered in the six-component system simulation. For simplified partitioning parametrizations, we suggest a modified definition of the effective saturation concentration, Cj*, by including water and other inorganics in the absorbing phase. Such a Cj* definition reduces the RH-dependency of the gas/particle partitioning of semivolatile organics in organic-inorganic aerosols by an order of magnitude as compared to the currently accepted definition, which considers the organic species only.
NASA Astrophysics Data System (ADS)
Zuend, A.; Marcolli, C.; Peter, T.; Seinfeld, J. H.
2010-05-01
Semivolatile organic and inorganic aerosol species partition between the gas and aerosol particle phases to maintain thermodynamic equilibrium. Liquid-liquid phase separation into an organic-rich and an aqueous electrolyte phase can occur in the aerosol as a result of the salting-out effect. Such liquid-liquid equilibria (LLE) affect the gas/particle partitioning of the different semivolatile compounds and might significantly alter both particle mass and composition as compared to a one-phase particle. We present a new liquid-liquid equilibrium and gas/particle partitioning model, using as a basis the group-contribution model AIOMFAC (Zuend et al., 2008). This model allows the reliable computation of the liquid-liquid coexistence curve (binodal), corresponding tie-lines, the limit of stability/metastability (spinodal), and further thermodynamic properties of the phase diagram. Calculations for ternary and multicomponent alcohol/polyol-water-salt mixtures suggest that LLE are a prevalent feature of organic-inorganic aerosol systems. A six-component polyol-water-ammonium sulphate system is used to simulate effects of relative humidity (RH) and the presence of liquid-liquid phase separation on the gas/particle partitioning. RH, salt concentration, and hydrophilicity (water-solubility) are identified as key features in defining the region of a miscibility gap and govern the extent to which compound partitioning is affected by changes in RH. The model predicts that liquid-liquid phase separation can lead to either an increase or decrease in total particulate mass, depending on the overall composition of a system and the particle water content, which is related to the hydrophilicity of the different organic and inorganic compounds. Neglecting non-ideality and liquid-liquid phase separations by assuming an ideal mixture leads to an overestimation of the total particulate mass by up to 30% for the composition and RH range considered in the six-component system simulation. For simplified partitioning parametrizations, we suggest a modified definition of the effective saturation concentration, C*j, by including water and other inorganics in the absorbing phase. Such a C*j definition reduces the RH-dependency of the gas/particle partitioning of semivolatile organics in organic-inorganic aerosols by an order of magnitude as compared to the currently accepted definition, which considers the organic species only.
DETERMINATION OF SORPTION PARAMETERS FOR 36 VOC/MATERIAL COMBINATIONS
EPA's Air Pollution Prevention and Control Division is currently investigating sorptive interactions (sink effects) of volatile organic compounds and semi-volatile organic compounds when exposed to common indoor surface materials. The objective is to recommend the best sink mode...
Li, Chunmei; Wang, Donghong; Li, Na; Luo, Qian; Xu, Xiong; Wang, Zijian
2016-11-01
Improvements in extraction and detection technologies have increased our abilities to identify new disinfection by-products (DBPs) over the last 40 years. However, most previous studies combined DBP identification and measurement efforts with toxicology to address concerns on a few expected DBPs, making it difficult to better define the health risk from the individual DBPs. In this study, a nontargeted screening method involving comprehensive two-dimensional gas chromatography-quadrupole mass spectrometry (GC × GC-qMS) combined with OECD QSAR Toolbox Ver. 3.2 was developed for identifying and prioritizing of volatile and semi-volatile DBPs in drinking water. The method was successfully applied to analyze DBPs formed during chlorination, chloramination or ozonation of the raw water. Over 500 compounds were tentatively identified in each sample, showing the superior performance of this analytical technique. A total of 170 volatile and semi-volatile DBPs representing fourteen chemical classes were then identified, according to the criteria that the DBP was presented in the duplicate treated samples. The genotoxicity and carcinogenicity of the DBPs were evaluated using Toolbox, and 58 DBPs were found to be actual or potential genotoxicants. The accuracy of the compound identification was determined by comparing 47 identified compounds with commercially available standards. About 90% (41 of the 47) of the compounds that were automatically identified using the library were correct. The results show that GC×GC-qMS coupled with a quantitative structure-activity relationship model is a powerful and fast nontargeted screening technique for compounds. The method and results provide us a new idea for identification and prioritization of DBPs. Copyright © 2016 Elsevier Ltd. All rights reserved.
Organic aerosol sources an partitioning in CMAQv5.2
We describe a major CMAQ update, available in version 5.2, which explicitly treats the semivolatile mass transfer of primary organic aerosol compounds, in agreement with available field and laboratory observations. Until this model release, CMAQ has considered these compounds to ...
REGIONAL METHODS INITIATIVE RESEARCH PROJECTS AT HEASD
EPA Regional Laboratories are currently using high volume samplers with a combination of filter and sorbent vapor trap to collect large volume samples (250 liter/min for 24 hours) of semi-volatile organic compounds (SVOCs) and non-volatile organic compounds (NVOCs). These are su...
CWM PO*WW*ER™ EVAPORATION-CATALYTIC OXIDATION TECHNOLOGY - APPLICATIONS ANALYSIS REPORT
This report evaluates the Chemical Waste Management, Inc. (CWM), PO*WW*ER™ technology’s ability to remove volatile organic compounds (VOC), semivolatile organic compounds (SVOC), ammonia, cyanide, metals, and other inorganic contaminants from aqueous wastes. This evaluation is ba...
The relationship between onsite manufacture of spray polyurethane foam insulation (SPFI) and potential exposures to diisocyanate compounds, amine catalysts, flame retardants, and blowing agents, as well as aldehydes and other volatile or semivolatile organic compounds that may be...
Li, Zekai; Chang, Fangyu; Shi, Peng; Chen, Xun; Yang, Feng; Zhou, Qing; Pan, Yang; Li, Aimin
2018-09-01
Semi-volatile organic compounds (SVOCs) in drinking water have been considered a severe threat to public health worldwide. However, SVOC contamination and the associated human health risks of the drinking water from cities along tributaries of the Yangtze River and Huaihe River in China have been seldom reported. Here, we focused on the occurrence and distribution of a series of SVOCs, mainly including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) and phthalate esters (PAEs), in drinking water of this region. In brief, a total of 31 SVOCs were detectable in all of the drinking water samples, and the total concentrations ranged from 0.92 ng/L to 266.16 ng/L in March and from 24.82 ng/L to 643.93 ng/L in August, with the highest concentrations in Dongtai (DT) and Xinghua (XH), respectively. Spatial and temporal differences of the SVOCs were also observed in drinking water samples, demonstrating the linkage between pollutant profiles and geographical locations, as well as exogenous wastewater discharge. Moreover, PAEs occupied 79.17-100.00% of the total concentrations of SVOCs in drinking water samples collected from the tributaries of the Yangtze River in March, while OCPs were the predominant SVOCs in most of drinking water samples from the tributaries of the Huaihe River. The human health assessment indicated that SVOCs posed negligible non-carcinogenic risks, but residents living in DT, Dafeng (DF), Chengdong (CD), Guanyun (GY) and Lianyungang (LY) may suffer carcinogenic health risks, which could be mainly induced by benzene hexachloride and heptachlor in August. Copyright © 2018 Elsevier Ltd. All rights reserved.
Ulloa-Benítez, Á; Medina-Romero, Y M; Sánchez-Fernández, R E; Lappe-Oliveras, P; Roque-Flores, G; Duarte Lisci, G; Herrera Suárez, T; Macías-Rubalcava, M L
2016-08-01
To evaluate the phytotoxic, antifungal and antioomycete activity; and, determine the chemical composition of the volatile organic compounds (VOCs) and semi-volatile metabolites produced by the endophyte Hypoxylon anthochroum strain Blaci isolated from Bursera lancifolia. Based on its macro- and micro-morphological features, the strain Blaci was identified as Nodulisporium sp.; partial analysis of its ITS1-5.8-ITS2 ribosomal gene sequence revealed the identity of the teleomorphic stage of the fungus as H. anthochroum. Phytotoxic and antimicrobial activities of VOCs, and culture medium and mycelium organic extracts from H. anthochroum Blaci were determined by simple and multiple antagonism bioassays, and gas phase and agar dilution bioassays respectively. The volatile and semi-volatile metabolites were identified by gas chromatography-mass spectrometry. VOCs from a 5-day H. anthochroum strain Blaci culture caused the inhibition of seed germination, root elongation and seedling respiration on Amaranthus hypochondriacus, Panicum miliaceum, Trifolium pratense and Medicago sativa. In addition, extracts, phenylethyl alcohol and eucalyptol main compounds present in the VOCs and extract displayed a high phytotoxic activity, inhibiting the three physiological processes on the four test plants in a concentration-dependent manner. The results revealed that H. anthochroum strain Blaci produces a mixture of VOCs. These VOCs showed a strong phytotoxic activity on seed germination, root elongation, and seedling respiration of four plants and slightly affected the growth of phytopathogenic fungi and oomycetes. Also, the culture medium and mycelium extracts of H. anthochroum showed a high phytotoxic activity on the four test plants and, generally, the culture medium extract was more phytotoxic than the mycelium extracts. This work firstly reports the phytotoxic activity of volatile and semi-volatile compounds produced by the endophyte H. anthochroum strain Blaci on seed germination, root elongation, and seedling respiration of four different plants; consequently, these compounds could be useful in biocontrol of weeds and plant pathogens. Journal of Applied Microbiology © 2016 The Society for Applied Microbiology.
Selected organic pollutant emissions from unvented kerosene space heaters
DOE Office of Scientific and Technical Information (OSTI.GOV)
Traynor, G.W.; Apte, M.G.; Sokol, H.A.
1990-08-01
An exploratory study was performed to assess the semivolatile and nonvolatile organic pollutant emissions rates from unvented kerosene space heaters. A well-tuned radiant heater and maltuned convective heater were tested for semivolatile and nonvolatile organic pollutant emissions. Each heater was operated in a 27-m{sup 3} chamber with a prescribed on/off pattern. Organic compounds were collected on Teflon-impregnated glass filters backed by XAD-2 resin and analyzed by gas chromatography/mass spectrometry. Pollutant source strengths were calculated by use of a mass balance equation. The results show that kerosene heaters can emit polycyclic aromatic hydrocarbons (PAHs); nitrated PAHs; alkylbenzenes, phthalates; hydronaphthalenes; aliphatic hydrocarbons,more » alcohols, and ketones; and other organic compounds, some of which are known mutagens.« less
DEMONSTRATION BULLETIN: IN SITU STEAM ENHANCED RECOVERY PROCESS - HUGHES ENVIRONMENTAL SYSTEMS, INC.
The Steam Enhanced Recovery Process (SERP) is designed to remove volatile compounds such as halogenated solvents and petroleum hydrocarbons, and semi-volatile compounds from contaminated soils in situ. The vapor pressures of most contaminants will increase by the addition of ste...
Volatile and semivolatile organic compounds in laboratory peat fire emissions
Speciated volatile organic compounds (VOCs) and organic fine particulate matter (PM2.5) mass emission factors were determined from laboratory peat fire experiments. Peat samples originated from two wildlife reserves located near the coast of North Carolina, U.S. Gas and particula...
METHOD OF LIQUID-LIQUID EXTRACTION OF BLOOD SURROGATES FOR ASSESSING HUMAN EXPOSURE TO JET FUEL
A baseline method of liquid?liquid extraction for assessing human exposure to JP-8 jet fuel was established by extracting several representative compounds ranging from very volatile to semi-volatile organic compounds, including benzene, toluene, nonane, decane, undecane, tridec...
Voelker, David C.
2014-01-01
Aquatic-biology and sediment-chemistry data were collected at seven sites on the White River and at six tributary sites in the Indianapolis metropolitan area of Indiana during the period 2009 through 2012. Data collected included benthic-invertebrate and fish-community information and concentrations of metals, insecticides, herbicides, and semivolatile organic compounds adsorbed to streambed sediments. A total of 120 benthic-invertebrate samples were collected, of which 16 were replicate samples. A total of 26 fish-community samples were collected in 2010 and 2012. Thirty streambed-sediment chemistry samples were collected in 2009 and 2011, of which four were concurrent duplicate samples
The U.S. EPA's current regulatory approach for combustion and incineration sources emphasizes the use of real-time continuous emission monitors (CEMs) for particulate, Metals, and volatile, semivolatile, and of nonvolatile organic compounds to monitor source emissions. Currently...
DOE Office of Scientific and Technical Information (OSTI.GOV)
B. L. Tiller; T. E. Marceau
2006-01-25
This report documents concentrations of radionuclides, trace metals, and semivolatile organic compounds measured in shell samples of the western pearl shell mussel collected along the Hanford Reach of the Columbia River.
NASA Astrophysics Data System (ADS)
Zuend, A.; Marcolli, C.; Peter, T.
2009-04-01
The chemical composition of organic-inorganic aerosols is linked to several processes and specific topics in the field of atmospheric aerosol science. Photochemical oxidation of organics in the gas phase lowers the volatility of semi-volatile compounds and contributes to the particulate matter by gas/particle partitioning. Heterogeneous chemistry and changes in the ambient relative humidity influence the aerosol composition as well. Molecular interactions between condensed phase species show typically non-ideal thermodynamic behavior. Liquid-liquid phase separations into a mainly polar, aqueous and a less polar, organic phase may considerably influence the gas/particle partitioning of semi-volatile organics and inorganics (Erdakos and Pankow, 2004; Chang and Pankow, 2006). Moreover, the phases present in the aerosol particles feed back on the heterogeneous, multi-phase chemistry, influence the scattering and absorption of radiation and affect the CCN ability of the particles. Non-ideal thermodynamic behavior in mixtures is usually described by an expression for the excess Gibbs energy, enabling the calculation of activity coefficients. We use the group-contribution model AIOMFAC (Zuend et al., 2008) to calculate activity coefficients, chemical potentials and the total Gibbs energy of mixed organic-inorganic systems. This thermodynamic model was combined with a robust global optimization module to compute potential liquid-liquid (LLE) and vapor-liquid-liquid equilibria (VLLE) as a function of particle composition at room temperature. And related to that, the gas/particle partitioning of semi-volatile components. Furthermore, we compute the thermodynamic stability (spinodal limits) of single-phase solutions, which provides information on the process type and kinetics of a phase separation. References Chang, E. I. and Pankow, J. F.: Prediction of activity coefficients in liquid aerosol particles containing organic compounds, dissolved inorganic salts, and water - Part 2: Consideration of phase separation effects by an XUNIFAC model, Atmos. Environ., 40, 6422-6436, 2006. Erdakos, G. B. and Pankow, J. F.: Gas/particle partitioning of neutral and ionizing compounds to single- and multi-phase aerosol particles. 2. Phase separation in liquid particulate matter containing both polar and low-polarity organic compounds, Atmos. Environ., 38, 1005-1013, 2004. Zuend, A., Marcolli, C., Luo, B. P., and Peter, T.: A thermodynamic model of mixed organic-inorganic aerosols to predict activity coefficients, Atmos. Chem. Phys., 8, 4559-4593, 2008.
Frenzel, Steven A.; Dorava, Joseph M.
1999-01-01
Five streams in the Cook Inlet Basin, Alaska, were sampled in 1998 to provide the National Park Service with baseline information on water quality. Four of these streams drain National Park Service land: Costello and Colorado Creeks in Denali National Park and Preserve, Johnson River in Lake Clark National Park and Preserve, and Kamishak River in Katmai National Park and Preserve. The fifth site was on the Talkeetna River, outside of national park boundaries. Samples of stream water, streambed sediments, and fish tissues were collected for chemical analyses. Biological and geomorphic information was also collected at each site. Nutrient concentrations in stream water were low and commonly were less than analytical detection limits. Analyses of fish tissues for 28 organochlorine compounds at Talkeetna River and Costello Creek produced just one detection. Hexachlorobenzene was detected at a concentration of 5.70 micrograms per kilogram in slimy sculpin from the Talkeetna River. Streambed sediment samples from the Talkeetna River had three organochlorine compounds at detectable levels; hexachlorobenzene was measured at 13 micrograms per kilogram and two other compounds were below the minimum reporting levels. At Colorado Creek, Johnson River, and Kamishak River, where fish samples were not collected, no organochlorine compounds were detected in streambed sediment samples. Several semivolatile organic compounds were detected at Colorado Creek and Costello Creek. Only one compound, dibenzothiophene, detected at Costello Creek at a concentration of 85 micrograms per kilogram was above the minimum reporting limit. No semivolatile organic compounds were detected at the Talkeetna, Kamishak, or Johnson Rivers. Trace elements were detected in both fish tissues and streambed sediments. Macroinvertebrate and fish samples contained few taxa at all sites. Total numbers of macroinvertebrate taxa ranged from 19 at the Johnson River to 38 at the Talkeetna River. Diptera were the most abundant and diverse order of macroinvertebrates at all sites. Total numbers of diptera taxa ranged from 8 at the Kamishak River to 19 at the Talkeetna River. Fish communities were represented by a maximum of nine taxa at the Talkeetna River and were absent at Colorado Creek. The Johnson River sampling site produced small numbers of juvenile Dolly Varden, and Costello Creek produced small numbers of both juvenile Dolly Varden and slimy sculpin.
Ebner, Donna Belval; Cherry, Donald S.; Currie, Rebecca J.
2004-01-01
A study was done of the effects of a closed landfill on the quality of water and streambed sediment and the benthic macroinvertebrate community of an unnamed stream and its tributary that flow through Blue Ridge Parkway lands in west-central Virginia. The primary water source for the tributary is a 4-inch polyvinyl chloride (PVC) pipe that protrudes from the slope at the base of the embankment bordering the landfill. An unusual expanse of precipitate was observed in the stream near the PVC pipe. Stream discharge was measured and water and streambed sediment samples were collected at a nearby reference site and at three sites downstream of the landfill in April and September 1999. Water samples were analyzed for major ions, nitrate, total and dissolved metals, total dissolved solids, total organic carbon, and volatile and semivolatile organic compounds, including organochlorine pesticides and polychlorinated biphenyls (PCBs). Streambed sediment samples were analyzed for total metals, total organic carbon, percent moisture, and volatile and semivolatile organic compounds, including organochlorine pesticides and PCBs. The benthic macroinvertebrate community within the stream channel also was sampled at the four chemical sampling sites and at one additional site in April and September. Each of the five sites was assessed for physical habitat quality. Water collected periodically at the PVC pipe discharge between November 1998 and November 1999 was used to conduct 48-hour acute and 7-day chronic toxicity tests using selected laboratory test organisms. Two 10-day chronic toxicity tests of streambed sediments collected near the discharge pipe also were conducted. Analyses showed that organic and inorganic constituents in water from beneath the landfill were discharged into the sampled tributary. In April, 79 percent of inorganic constituents detected in water had their highest concentrations at the site closest to the landfill; at the same site, 59 percent of inorganic constituents detected in streambed sediments were at their lowest concentration. The low dissolved-oxygen concentration and relatively low pH in ground water from beneath the landfill probably had a direct effect on the solubility of metals and other constituents, resulting in the high concentration of inorganic constituents in water, low concentration in sediment, and the development of the precipitate. Most constituents in water in April were progressively lower in concentration from the landfill site downstream. The highest concentrations for 59 percent of constituents detected in sediment were at the farthest downstream site, suggesting that the inorganic constituents came out of solution as the stream water was exposed to the atmosphere. In September, 52 percent of inorganic constituents detected in water were at their highest concentrations at the site nearest the landfill. Of inorganic constituents detected in streambed sediments in September, 60 percent were at their highest concentrations near the landfill. A storm that occurred a few days prior to the September sampling probably affected the preceding steady-state conditions and the distribution of constituents in sediment along the stream. Concentrations of many inorganic constituents in water remained elevated at the farthest downstream site in comparison to the reference site in April and September, indicating that concentrations did not return to background concentrations. In April and September, most of the 17 organic compounds detected in water, including volatile organic and semivolatile organic compounds, were collected in samples near the landfill, and most concentrations were below their respective reporting limits. Probably because of their volatility, few organic compounds were detected at sites downstream of that site. A total of 17 discrete organic compounds were detected in sediment samples in either April or September, including trichloroethene and tetrachloroethene along with their degrad
Hydrologic and water-quality data from Mountain Island Lake, North Carolina, 1994-97
Sarver, K.M.; Steiner, B.C.
1998-01-01
Continuous-record water-level gages were established at three sites on Mountain Island Lake and one site downstream from Mountain Island Dam. The water level of Mountain Island Lake is controlled by Duke Power Company releases at Cowans Ford Dam (upstream) and Mountain Island Dam (downstream). Water levels on Mountain Island Lake measured just downstream from Cowans Ford Dam fluctuated 11.15 feet during the study. Water levels just upstream from the Mountain Island Lake forebay fluctuated 6.72 feet during the study. About 3 miles downstream from Mountain Island Dam, water levels fluctuated 5.31 feet. Sampling locations included 14 sites in Mountain Island Lake, plus one downstream river site. At three sites, automated instruments recorded water temperature, dissolved-oxygen concentration, and specific conductance at 15-minute intervals throughout the study. Water temperatures recorded continuously during the study ranged from 4.2 to 35.2 degrees Celsius, and dissolved-oxygen concentrations ranged from 2.1 to 11.8 milligrams per liter. Dissolved-oxygen concentrations generally were inversely related to water temperature, with lowest dissolved-oxygen concentrations typically recorded in the summer. Specific conductance values recorded continuously during the study ranged from 33 to 89 microsiemens per centimeter; however, mean monthly values were fairly consistent throughout the study at all sites (50 to 61 microsiemens per centimeter). In addition, vertical profiles of water temperature, dissolved-oxygen concentration, specific conductance, and pH were measured at all sampling locations during 24 site visits. Water-quality constituent concentrations were determined for seven reservoir sites and the downstream river site during 17 sampling trips. Water-quality samples were routinely analyzed for biochemical oxygen demand, fecal coliform bacteria, hardness, alkalinity, total and volatile suspended solids, nutrients, total organic carbon, chlorophyll, iron, calcium, and magnesium; the samples were analyzed less frequently for trace metals, volatile organic compounds, semivolatile organic compounds, and pesticides. Maximum dissolved nitrite plus nitrate concentrations determined during the study were 0.348 milligram per liter in the mainstem sites and 2.77 milligrams per liter in the coves. Maximum total phosphorus concentrations were 0.143 milligram per liter in the mainstem sites and 0.600 milligram per liter in the coves. Fecal coliform and chlorophyll a concentrations were less than or equal to 160 colonies per 100 milliliters and 13 micrograms per liter, respectively, in all samples. Trace metals detected in at least one sample included arsenic, chromium, copper, lead, nickel, zinc, and antimony. Concentrations of all trace metals (except zinc) were 5.0 micrograms per liter or less; the maximum zinc concentration was 80 micrograms per liter. One set of bottom material samples was collected from Gar Creek and McDowell Creek for chemical analysis and analyzed for nutrients, trace metals, organochlorine pesticides, and semivolatile organic compounds. The only organochlorine pesticide identified in either sample was p,p'-DDE at an estimated concentration of 0.8 microgram per kilogram. Twenty semivolatile organic compounds, mainly polyaromatic hydrocarbons and plasticizers, were identified.
Pollutant emissions during the pyrolysis and combustion of flexible polyurethane foam.
Garrido, María A; Font, Rafael; Conesa, Juan A
2016-06-01
Thermal decomposition of flexible polyurethane foam (FPUF) was studied under nitrogen and air atmospheres at 550°C and 850°C using a laboratory scale reactor to analyse the evolved products. Ammonia, hydrogen cyanide and nitrile compounds were obtained in high yields in pyrolysis at the lower temperature, whereas at 850°C polycyclic aromatic hydrocarbons (PAHs) and other semivolatile compounds, especially compounds containing nitrogen (benzonitrile, aniline, quinolone and indene) were the most abundant products. Different behaviour was observed in the evolution of polychlorodibenzo-p-dioxins and furans (PCDD/Fs) at 550°C and 850°C. At 550°C, the less chlorinated congeners, mainly PCDF, were more abundant. Contrarily, at 850°C the most chlorinated PCDD were dominant. In addition, the total yields of PCDD/Fs in the pyrolysis and combustion runs at 850°C were low and quite similar. Copyright © 2016 Elsevier Ltd. All rights reserved.
USDA-ARS?s Scientific Manuscript database
Some species of actinomycetes, fungi, and bluegreen algae produce semivolatile off-flavor compounds responsible for earthy-musty odorants in water from aquaculture facilities and tend to bioaccumulate within fish flesh. Although these off-flavor compounds are harmless to human health, high levels wi...
A thermal extraction-gas chromatography-mass spectrometry (TE-GC-MS) method was used to quantitatively examine organic compounds in fine particulate matter (PM2.5) collected from light-duty, gasoline-powered vehicle (LDGV) exhaust. Emissions were analyzed from a subset of 18 vehi...
USDA-ARS?s Scientific Manuscript database
Electronic nose technology has historically been utilized for the detection of volatile organic compounds (VOCs) and semi-volatile compounds in air, soil, water, and for quality control in food, beverage and cosmetic industries. Breath analysis has been used experimentally in humans and animals to ...
Collection and analysis of NASA clean room air samples
NASA Technical Reports Server (NTRS)
Sheldon, L. S.; Keever, J.
1985-01-01
The environment of the HALOE assembly clean room at NASA Langley Research Center is analyzed to determine the background levels of airborne organic compounds. Sampling is accomplished by pumping the clean room air through absorbing cartridges. For volatile organics, cartridges are thermally desorbed and then analyzed by gas chromatography and mass spectrometry, compounds are identified by searching the EPA/NIH data base using an interactive operator INCOS computer search algorithm. For semivolatile organics, cartridges are solvent entracted and concentrated extracts are analyzed by gas chromatography-electron capture detection, compound identification is made by matching gas chromatogram retention times with known standards. The detection limits for the semivolatile organics are; 0.89 ng cu m for dioctylphlhalate (DOP) and 1.6 ng cu m for polychlorinated biphenyls (PCB). The detection limit for volatile organics ranges from 1 to 50 parts per trillion. Only trace quantities of organics are detected, the DOP levels do not exceed 2.5 ng cu m and the PCB levels do not exceed 454 ng cu m.
Shin, Hyeong-Moo; McKone, Thomas E.; Nishioka, Marcia G.; Fallin, M. Daniele; Croen, Lisa A.; Hertz-Picciotto, Irva; Newschaffer, Craig J.; Bennett, Deborah H.
2014-01-01
Consumer products and building materials emit a number of semivolatile organic compounds (SVOCs) in the indoor environment. Because indoor SVOCs accumulate in dust, we explore the use of dust to determine source strength and report here on analysis of dust samples collected in 30 U.S. homes for six phthalates, four personal care product ingredients, and five flame retardants. We then use a fugacity-based indoor mass-balance model to estimate the whole house emission rates of SVOCs that would account for the measured dust concentrations. Di-2-ethylhexyl phthalate (DEHP) and di-iso-nonyl phthalate (DiNP) were the most abundant compounds in these dust samples. On the other hand, the estimated emission rate of diethyl phthalate (DEP) is the largest among phthalates, although its dust concentration is over two orders of magnitude smaller than DEHP and DiNP. The magnitude of the estimated emission rate that corresponds to the measured dust concentration is found to be inversely correlated with the vapor pressure of the compound, indicating that dust concentrations alone cannot be used to determine which compounds have the greatest emission rates. The combined dust-assay modeling approach shows promise for estimating indoor emission rates for SVOCs. PMID:24118221
Steyaert, Nils L L; Hauck, Mara; Van Hulle, Stijn W H; Hendriks, A Jan
2009-10-01
A model was developed for gaseous plant-air exchange of semi-volatile organic compounds. Based on previous soil-plant modelling, uptake and elimination kinetics were scaled as a function of plant mass and octanol-air partition ratios. Exchange of chemicals was assumed to be limited by resistances encountered during diffusion through a laminar boundary layer of air and permeation through the cuticle of the leaf. The uptake rate constant increased and the elimination rate constant decreased with the octanol-air partition ratio both apparently levelling off at high values. Differences in kinetics between species could be explained by their masses. Validation on independent data showed that bio-concentration factors of PCBs, chlorobenzenes and other chemicals were predicted well by the model. For pesticides, polycyclic aromatic hydrocarbons and dioxins deviations occurred.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Mumford, J.L.; Williams, R.W.; Walsh, D.B.
1991-01-01
The study was conducted to assess human exposure to air pollutants resulting from the use of kerosene heaters in mobile homes. It has been estimated that 15-17 million unvented kerosene heaters have been sold in the United States, and 33% of these heaters have been sold to mobile home residents. The emissions from kerosene heaters can result in high pollutants levels in mobile homes that have a small air volume and low ventilation rate. Eight totally electric mobile homes with no smokers living in the homes were monitored for indoor air particles < 10 micrometer (PM10), semivolatile organics, carbon monoxidemore » (CO), and mutagenicity of semivolatile and particle-phase organics in Salmonella typhimurium TA98 without S9 using a microsuspension reverse-mutation assay. Each home was monitored for an average of 6.5 h/day, 3 days/week, for 4 weeks (2 weeks with the heater on and 2 weeks with the heater off) during the heating season of 1989. Indoor air exchange rate, temperature, and humidity were measured. Chemical analyses, including polycyclic aromatic hydrocarbon (PAH) and nitro PAH, also were performed on the indoor air samples from a selected home with the kerosene heater on and off. Increases in CO and organic concentrations resulting from the use of kerosene heaters were found in most homes monitored. Chemical analysis data also suggested the presence of evaporated, unburned kerosene fuel present in semivolatile organics collected in the XAD samples. In comparison with the U.S. national ambient air standards, four out of the eight heaters investigated in the study emitted pollutants that exceeded the ambient air standards some days. These data suggested that emissions from unvented kerosene heaters can significantly impact indoor air quality in mobile homes and that these emissions contain carcinogenic compounds and can be potentially carcinogenic in humans.« less
The Salt Lake City EPA Environmental Monitoring for Public Access and Community Tracking (EMPACT) project, initiated in October 1999, is designed to evaluate the usefulness of a newly developed real-time continuous monitor (RAMS) for total (non-volatile plus semi-volatile) PM<...
Olson, Joelle F; Vers, Leonard M Ver; Moon, Roger D; Kells, Stephen A
2017-01-01
After feeding, bed bugs aggregate in cracks and crevices near a host. Aggregation and arrestment are mediated by tactile and chemical stimuli associated with the bugs' feces and exuviae. Volatiles derived from fecally stained filter papers were analyzed by solid-phase microextraction (SPME) and evaluated using a multichoice behavioral assay to determine their impact on bed bug aggregation. In addition, crude fecal extracts were collected in methanol, analyzed by gas chromatography coupled with electroantennogram detection (GC-EAD) and mass spectrometry (GC-MS) and evaluated in open-air multichoice behavioral assays. The SPME method was used to detect (E)-2-hexenal and (E)-2-octenal in heated bed bug feces. The presence of these two volatile components did not affect aggregation. Analysis of the crude fecal extracts revealed several semi-volatile nitrogenous compounds, a carboxylic acid and a sulfur-based compound. Adult antennae responded to compounds eluted from three regions of the crude extract using GC-EAD. A combination of two compounds, dimethyl trisulfide and methyldiethanolamine, resulted in aggregation responses equivalent to the original crude extract. Bed bug aggregation is mediated by semi-volatile compounds derived from fecal extracts, and two compounds are sufficient to elicit aggregation. The two compounds identified here could be used to enhance the effectiveness of insecticidal applications or improve monitoring techniques. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.
Bravo, Manuel; Lespes, Gaëtane; De Gregori, Ida; Pinochet, Hugo; Gautier, Martine Potin
2005-12-01
A method based on Headspace solid-phase microextraction (HS-SPME, with a 100 mum PDMS-fiber) in combination with gas-chromatography and pulsed flame-photometric detection (GC-PFPD) has been investigated for simultaneous determination of eight organotin compounds. Monobutyltin (MBT), dibutyltin (DBT), tributyltin (TBT), monophenyltin (MPhT), and the semi-volatile diphenyltin (DPhT), triphenyltin (TPhT), monooctyltin (MOcT), and dioctyltin (DOcT) were determined after derivatization with sodium tetraethylborate. The conditions used for the extraction and preconcentration step were optimised by experimental design methodology. Tripropyltin (TPrT) and diheptyltin (DHepT) were used as internal standards for quantification of volatile and semi-volatile organotin compounds, respectively. The analytical precision (RSD) for ten successive injections of a standard mixture containing all the organic tin compounds ranged between 2 and 11%. The limits of detection for all the organotin compounds were sub ng (Sn) L(-1) in water and close to ng (Sn) kg(-1) in sediments. The accuracy of the method was evaluated by analysis of two certified reference material (CRM) sediment samples. The HS-SPME-GC-PFPD was then applied to the analysis of three harbour sediment samples. The results showed that headspace SPME is an attractive tool for analysis of organotin compounds in solid environmental matrices.
Although PM2.5 can be directly introduced into the atmosphere through primary emissions, its mass concentration is also strongly affected by secondary processes such as nucleation or condensation of nonvolatile and semivolatile compounds on pre-existing aerosols. Chemical modules...
ENGINEERING BULLETIN: COMPOSTING
Composting is an emerging ex situ biological technology that is potentially applicable to nonvolatile and semivolatile organic compounds (SVOCs) in soils. It has been applied to polycyclic aromatic hydrocarbons (PAHs) and explosives. It has been found to be potentially effectiv...
NASA Astrophysics Data System (ADS)
Ye, Penglin; Zhao, Yunliang; Chuang, Wayne K.; Robinson, Allen L.; Donahue, Neil M.
2018-05-01
We have investigated the production of secondary organic aerosol (SOA) from pinanediol (PD), a precursor chosen as a semi-volatile surrogate for first-generation oxidation products of monoterpenes. Observations at the CLOUD facility at CERN have shown that oxidation of organic compounds such as PD can be an important contributor to new-particle formation. Here we focus on SOA mass yields and chemical composition from PD photo-oxidation in the CMU smog chamber. To determine the SOA mass yields from this semi-volatile precursor, we had to address partitioning of both the PD and its oxidation products to the chamber walls. After correcting for these losses, we found OA loading dependent SOA mass yields from PD oxidation that ranged between 0.1 and 0.9 for SOA concentrations between 0.02 and 20 µg m-3, these mass yields are 2-3 times larger than typical of much more volatile monoterpenes. The average carbon oxidation state measured with an aerosol mass spectrometer was around -0.7. We modeled the chamber data using a dynamical two-dimensional volatility basis set and found that a significant fraction of the SOA comprises low-volatility organic compounds that could drive new-particle formation and growth, which is consistent with the CLOUD observations.
Indoor airborne particle sources and semi-volatile partitioning effect of outdoor fine PM in offices
NASA Astrophysics Data System (ADS)
Sangiorgi, G.; Ferrero, L.; Ferrini, B. S.; Lo Porto, C.; Perrone, M. G.; Zangrando, R.; Gambaro, A.; Lazzati, Z.; Bolzacchini, E.
2013-02-01
To date, few studies have focused on PM air quality in offices, despite the fact that a lot of people spend many working hours a day in such offices. The aim of the present study is to investigate PM1 and PM2.5 in offices in Milan (Northern Italy) and in the air outside those offices. The PM samples were analyzed to determine the entity of certain compounds with possible direct or indirect adverse effects on human health: PAHs, BpA, and water soluble inorganic ions. A good correlation between outdoor and indoor PM mass concentrations emerged (R2 ˜0.87). The maximum I/O concentration ratio was 0.92, suggesting that the indoor PM level was always lower than the outdoor level. The average infiltration factor, FINF, was 0.55, showing that about a half of the outdoor PM had come indoors. The indoor-generated particles, Cig, had values ranging from 0 to 4.4 μg m-3 (<25% of the indoor PM), showing that PM indoor sources had only made a limited contribution to total indoor PM. The results of the indoor-to-outdoor comparisons for the aforementioned chemical compounds demonstrate that the offices were characterized by the absence of effective indoor sources of particulate-bound PAHs and inorganic ions, whereas Cig was around 58% of the indoor concentration for BpA. Our analysis of the FINF data pointed to the presence of a volatilization effect from PM for semi-volatile compounds like ammonium nitrate and 4- or 5-ring PAHs, which affected the measurement of their FINF. We propose the introduction of a new and simple parameter, called volatilization correction, to take account of this effect.
DOE Office of Scientific and Technical Information (OSTI.GOV)
DeRosier, R.; Waterland, L.R.
1987-03-01
The report gives emission results from field tests of a wood-waste-fired industrial firetube boiler. Emission measurements included: continuous monitoring of flue gas emissions: source assessment sampling system (SASS) sampling of the flue-gas with subsequent laboratory analysis of samples to give total flue gas organics in two boiling point ranges, compound category information within these ranges, specific quantitation of the semivolatile organic priority pollutants, and flue gas concentrations of 65 trace elements; Method 5 sampling for particulates; controlled condensation system (CSS) sampling for SO/sub 2/ and SO/sub 3/; and grab sampling of boiler bottom ash for trace element content determinations. Totalmore » organic emissions from the boiler were 5.7 mg/dscm, about 90% of which consisted of volatile compounds.« less
Brasher, A.M.D.; Wolff, R.H.
2004-01-01
Bed-sediment and/or fish samples were collected from 27 sites around the island of Oahu (representing urban, agricultural, mixed, and forested land use) to determine the occurrence and distribution of hydrophobic organic compounds including organochlorine pesticides, polychlorinated biphenyls (PCBs), and semi-volatile organic compounds (SVOCs). Of the 28 organochlorine compounds analyzed in the fish, 14 were detected during this study. Nineteen of the 31 organochlorine compounds and 40 of the 65 SVOCs were detected in the sediment. Urban sites had the highest number of detections and tended to have the highest concentrations of pesticides. Chlordane compounds were the most frequently detected constituents at urban sites, followed by dieldrin, polycyclic aromatic hydrocarbons (PAHs), and DDT compounds. PAHs were the most frequently detected constituents in watersheds with mixed (urban and agricultural) land use. The only pesticides detected at agricultural sites were DDT and its degradation products, DDD and DDE. No pesticides or PCBs were detected at the forested sites, but a few ubiquitous SVOCs were found in sediments at some forested sites. In general, concentrations of the most frequently detected pesticides were higher in fish than in sediment. Following a trend that has been observed elsewhere in the nation, concentrations of most organochlorine pesticides and PCBs are decreasing in Hawaii.
Dynamic behavior of semivolatile organic compounds in indoor air
DOE Office of Scientific and Technical Information (OSTI.GOV)
Loy, Michael David Van
1998-12-09
Exposures to a wide range of air pollutants are often dominated by those occurring in buildings because of three factors: 1) most people spend a large fraction of their time indoors, 2) many pollutants have strong indoor sources, and 3) the dilution volume in buildings is generally several orders of magnitude smaller than that of an urban airshed. Semivolatile organic compounds (SVOCS) are emitted by numerous indoor sources, including tobacco combustion, cooking, carpets, paints, resins, and glues, so indoor gasphase concentrations of these compounds are likely to be elevated relative to ambient levels. The rates of uptake and release ofmore » reversibly sorbing SVOCS by indoor materials directly affect both peak concentrations and persistence of the pollutants indoors after source elimination. Thus, accurate predictions of SVOC dynamics in indoor air require an understanding of contaminant sorption on surface materials such as carpet and wallboard. The dynamic behaviors of gas-phase nicotine and phenanthrene were investigated in a 20 ms stainless steel chamber containing carpet and painted wallboard. Each compound was studied independently, first in the empty chamber, then with each sorbent individually, and finally with both sorbents in the chamber.« less
Li, Xiaojie; Rao, Zhu; Yang, Zhipeng; Guo, Xiaochen; Huang, Yi; Zhang, Jing; Guo, Feng; Liu, Chen
2015-12-18
The status of organic pollution in groundwater in eastern China along the Grand Canal from Hangzhou to Beijing was evaluated. Forty-two semi-volatile organic contaminants were analyzed, including 16 polycyclic aromatic hydrocarbons (PAHs), seven polychlorinated biphenyls (PCBs), 12 organochlorine pesticides (OCPs) and seven organophosphorus pesticides (OPPs). Among the detected contaminants, PAHs were the most widespread compounds. One PCB and six OCPs were detected in the groundwater samples, but none of the target OPPs was detected. The total concentration of the 16 PAHs ranged from 0.21 to 1006 ng/L, among which phenanthrene (271 ng/L) and fluoranthene (233 ng/L) were present at very high concentrations and naphthalene (32 positive detections in 50 samples) and fluorene (28 detections in 50 samples) were the most frequently detected. Benzo[a]pyrene equivalents indicated a high environmental risk related to PAHs in a few groundwater samples. To identify the possible sources of PAHs, three concentration ratios, low molecular weight PAHs/high molecular weight PAHs, anthracene/(anthracene + phenanthrene) and fluoranthene/(fluoranthene + pyrene), were determined, that indicated that the PAHs mainly originated from mixed sources: pyrolytic and petrogenic sources with different ratios at different sites.
Li, Xiaojie; Rao, Zhu; Yang, Zhipeng; Guo, Xiaochen; Huang, Yi; Zhang, Jing; Guo, Feng; Liu, Chen
2015-01-01
The status of organic pollution in groundwater in eastern China along the Grand Canal from Hangzhou to Beijing was evaluated. Forty-two semi-volatile organic contaminants were analyzed, including 16 polycyclic aromatic hydrocarbons (PAHs), seven polychlorinated biphenyls (PCBs), 12 organochlorine pesticides (OCPs) and seven organophosphorus pesticides (OPPs). Among the detected contaminants, PAHs were the most widespread compounds. One PCB and six OCPs were detected in the groundwater samples, but none of the target OPPs was detected. The total concentration of the 16 PAHs ranged from 0.21 to 1006 ng/L, among which phenanthrene (271 ng/L) and fluoranthene (233 ng/L) were present at very high concentrations and naphthalene (32 positive detections in 50 samples) and fluorene (28 detections in 50 samples) were the most frequently detected. Benzo[a]pyrene equivalents indicated a high environmental risk related to PAHs in a few groundwater samples. To identify the possible sources of PAHs, three concentration ratios, low molecular weight PAHs/high molecular weight PAHs, anthracene/(anthracene + phenanthrene) and fluoranthene/(fluoranthene + pyrene), were determined, that indicated that the PAHs mainly originated from mixed sources: pyrolytic and petrogenic sources with different ratios at different sites. PMID:26694442
2011-09-01
of interest. Lack of bias with GC-MS method ........................................................ 12 3.1.1 Data requirements...14 3.2.1 Data ...3.3.1 Data requirements ....................................................................................................... 15 3.3.2 Success
Detection of semi-volatile organic compounds in permeable pavement infiltrate
Abstract The Edison Environmental Center (EEC) has a research and demonstration permeable parking lot comprised of three different permeable systems: permeable asphalt, porous concrete and interlocking concrete permeable pavers. Water quality and quantity analysis has been ongoin...
Physical and Chemical Properties of Anthropogenic Aerosols: An Overview
Aerosol chemical composition is complex. Combustion aerosols can comprise tens of thousands of organic compounds, refractory brown and black carbon, heavy metals, cations, anions, salts, and other inorganic phases. Aerosol organic matter normally contains semivolatile material th...
Using GC×GC-ToF-MS to characterise SVOC from diesel exhaust emissions
NASA Astrophysics Data System (ADS)
Alam, M. S.; Ramadhas, A. S.; Stark, C. P.; Liu, D.; Xu, H.; Harrison, R. M.
2014-12-01
Despite intensive research over the last 20 years, a number of major research questions remain concerning the sources and properties of road traffic-generated particulate matter. There are major knowledge gaps concerning the composition of primary vehicle exhaust aerosol, and its contribution to secondary organic aerosol (SOA) formation. These uncertainties relate especially to the semi-volatile component of the particles. Semi-Volatile Organic Compounds (SVOC) are compounds which partition directly between the gas and aerosol phases under ambient conditions, and include compounds with saturation concentrations roughly between 0.1 and 104 μg m-3. The SVOC in engine exhaust are typically hydrocarbons in the C15-C35 range. They are largely uncharacterised, other than the n-alkanes, because they are unresolved by traditional gas chromatography and form a large hump in the chromatogram referred to as Unresolved Complex Mixture (UCM). In this study, samples were collected from the exhaust of a diesel engine with and without abatement devices fitted. Engine exhaust was diluted with air and collected using both filter and impaction (MOUDI), to resolve total mass and size resolved mass respectively. Particle size distribution was evaluated by sampling simultaneously with a Scanning Mobility Particle Sizer (SMPS). 2D Gas-Chromatography Time-of-Flight Mass-Spectrometry (GC×GC-ToF-MS) was exploited to characterise and quantify the composition of SVOC from the exhaust emission. The SVOC was observed to contain predominantly n-alkanes, alkyl-cyclohexanes and aromatics; similar to both fresh lubricating oil and fuel. Preliminary results indicate that the contribution of diesel fuel to the exhaust SVOC composition is dominant at high speeds, and a more pronounced contribution from lubricating oil is observed at low speeds. Differences were also observed in the SVOC composition when using different fuel types, engine lubricants, starting temperatures and collecting samples with and without abatement devices fitted. The wealth of compounds identified and quantified in the C15-C35 range included PAH, esters, carboxylic acids, alkanes, alkenes, alcohols and hopanes.
In order to provide data to support regulations on municipal wastewater sludge incineration, emissions of metals, hexavalent chromium, nickel subsulfide, polychlorinated dibenzo-dioxins and furans (PCDD/PCDFs), semivolatile and volatile organic compounds, carbon monoxide (CO)...
Detection of semi-volatile organic compounds in permeable pavement infiltrate
Abstract The Edison Environmental Center (EEC) performs research on green infrastructure (GI) treatment options. One such treatment option is the use of permeable pavements. EEC constructed a parking lot comprised of three different permeable systems: permeable asphalt, porous ...
DEMONSTRATION BULLETIN: RAPID OPTICAL SCREEN TOOL (ROST™) - LORAL CORPORATION
The Loral Rapid Optical Screen Tool (ROST™) is a tunable dye laser system used for the detection of petroleum, semi-volatile, and some volatile organic compounds in soils. The technology is used in conjunction with a cone penetrometer (CP).
Vellingiri, Kowsalya; Szulejko, Jan E.; Kumar, Pawan; Kwon, Eilhann E.; Kim, Ki-Hyun; Deep, Akash; Boukhvalov, Danil W.; Brown, Richard J. C.
2016-01-01
In this research, we investigated the sorptive behavior of a mixture of 14 volatile and semi-volatile organic compounds (four aromatic hydrocarbons (benzene, toluene, p-xylene, and styrene), six C2-C5 volatile fatty acids (VFAs), two phenols, and two indoles) against three metal-organic frameworks (MOFs), i.e., MOF-5, Eu-MOF, and MOF-199 at 5 to 10 mPa VOC partial pressures (25 °C). The selected MOFs exhibited the strongest affinity for semi-volatile (polar) VOC molecules (skatole), whereas the weakest affinity toward was volatile (non-polar) VOC molecules (i.e., benzene). Our experimental results were also supported through simulation analysis in which polar molecules were bound most strongly to MOF-199, reflecting the presence of strong interactions of Cu2+ with polar VOCs. In addition, the performance of selected MOFs was compared to three well-known commercial sorbents (Tenax TA, Carbopack X, and Carboxen 1000) under the same conditions. The estimated equilibrium adsorption capacity (mg.g−1) for the all target VOCs was in the order of; MOF-199 (71.7) >Carboxen-1000 (68.4) >Eu-MOF (27.9) >Carbopack X (24.3) >MOF-5 (12.7) >Tenax TA (10.6). Hopefully, outcome of this study are expected to open a new corridor to expand the practical application of MOFs for the treatment diverse VOC mixtures. PMID:27324522
Data is presented on the development of a new automated system combining solid phase extraction (SPE) with GC/MS spectrometry for the single-run analysis of water samples containing a broad range of organic compounds. The system uses commercially available automated in-line 10-m...
Conn, Kathleen E.; Black, Robert W.; Peterson, Norman T.; Senter, Craig A.; Chapman, Elena A.
2018-01-05
From August 2016 to March 2017, the U.S. Geological Survey (USGS) collected representative samples of filtered and unfiltered water and suspended sediment (including the colloidal fraction) at USGS streamgage 12113390 (Duwamish River at Golf Course, at Tukwila, Washington) during 13 periods of differing flow conditions. Samples were analyzed by Washington-State-accredited laboratories for a large suite of compounds, including metals, dioxins/furans, semivolatile compounds including polycyclic aromatic hydrocarbons, butyltins, the 209 polychlorinated biphenyl (PCB) congeners, and total and dissolved organic carbon. Concurrent with the chemistry sampling, water-quality field parameters were measured, and representative water samples were collected and analyzed for river suspended-sediment concentration and particle-size distribution. The results provide new data that can be used to estimate sediment and chemical loads transported by the Green River to the Lower Duwamish Waterway.
Development of a Small Chamber Method to Study SVOCs Sink Effect
The transport mechanisms of semivolatile organic compounds (SVOCs) between sources, air,house dust, and interior surfaces in the residential environment needs to be better understood in order to more accurately estimate indoor SVOC exposure and develop risk management strategies ...
Volatile organic compounds up to C 20 emitted from motor vehicles; measurement methods
NASA Astrophysics Data System (ADS)
Zielinska, Barbara; Sagebiel, John C.; Harshfield, Gregory; Gertler, Alan W.; Pierson, William R.
To understand better the sources of observed differences between on-road vehicle emissions and model estimates, and to evaluate the emission of ozone precursors from motor vehicles, a series of experiments was conducted in the Fort McHenry Tunnel, Baltimore, Maryland (18-24 June 1992), and in the Tuscarora Mountain Tunnel, Pennsylvania (2-8 September 1992). Samples were collected using stainless steel canisters (whole air samples, analyzed for C 2C 12 hydrocarbons), Tenax-TA solid adsorbent cartridges (for semi-volatile hydrocarbons, in the C 8C 20 range), and 2,4-dinitrophenylhydrazine (DNPH) impregnated cartridges (for carbonyl compounds). The samples were analyzed using high resolution gas chromatographic separation with Fourier transform infrared/mass spectrometric detection (GC/IRD/ MSD) for qualitative identification and with flame ionization detection (GC/FID) for quantitation of hydrocarbons, and high performance liquid chromatography (HPLC) for identification and quantitation of carbonyl compounds. A custom-designed database management system was used to handle the large data sets generated by these analyses. From the evaluation of canister and Tenax sample stability upon storage, it was found that hydrocarbons in the C 8C 12 range seemed to be more stable in the Tenax cartridge than in the canister. The effect of the Nafion® dryer (frequently used for moisture removal prior to cryogenic concentration of the canister samples) was also assessed and it was found to lower the measured concentrations of hydrocarbons collected in the canisters. Comparison of hydrocarbon concentrations found in the Tenax and canister samples allows an assessment of the contribution of semi-volatile hydrocarbons (C 10C 20 range derived from Tenax data) to the total non-methane hydrocarbons (C 2C 20, derived from canisters and Tenax data). The results of this study show that hydrocarbons in the range of C 10C 20 are important components of gas-phase hydrocarbons emitted from heavy-duty diesel vehicles (they account for approximately half of the total gas-phase non-methane hydrocarbon emission rates) and hence that solid adsorbent sampling should be used in addition to canister sampling in measurements of motor vehicle emissions.
Bao, Zhongwen; Haberer, Christina; Maier, Uli; Beckingham, Barbara; Amos, Richard T; Grathwohl, Peter
2015-12-15
Soil-atmosphere exchange is important for the environmental fate and atmospheric transport of many semi-volatile organic compounds (SVOCs). This study focuses on modeling the vapor phase exchange of semi-volatile hydrophobic organic pollutants between soil and the atmosphere using the multicomponent reactive transport code MIN3P. MIN3P is typically applied to simulate aqueous and vapor phase transport and reaction processes in the subsurface. We extended the code to also include an atmospheric boundary layer where eddy diffusion takes place. The relevant processes and parameters affecting soil-atmosphere exchange were investigated in several 1-D model scenarios and at various time scales (from years to centuries). Phenanthrene was chosen as a model compound, but results apply for other hydrophobic organic compounds as well. Gaseous phenanthrene was assumed to be constantly supplied to the system during a pollution period and a subsequent regulation period (with a 50% decline in the emission rate). Our results indicate that long-term soil-atmosphere exchange of phenanthrene is controlled by the soil compartment - re-volatilization thus depends on soil properties. A sensitivity analysis showed that accumulation and transport in soils in the short term is dominated by diffusion, whereas in the long term groundwater recharge and biodegradation become relevant. As expected, sorption causes retardation and slows down transport and biodegradation. If atmospheric concentration is reduced (e.g. after environmental regulations), re-volatilization from soil to the atmosphere occurs only for a relatively short time period. Therefore, the model results demonstrate that soils generally are sinks for atmospheric pollutants. The atmospheric boundary layer is only relevant for time scales of less than one month. The extended MIN3P code can also be applied to simulate fluctuating concentrations in the atmosphere, for instance due to temperature changes in the topsoil. Copyright © 2015. Published by Elsevier B.V.
Llompart, M; Li, K; Fingas, M
1998-10-16
In this work we report the use of solid-phase microextraction (SPME) to extract and concentrate water-soluble volatile as well as semi-volatile pollutants. Both methods of exposing the SPME fibre were utilised: immersion in the aqueous solution (SPME) and in the headspace over the solution (HSSPME). The proposed HSSPME procedure was compared to conventional static headspace (HS) analysis for artificially spiked water as well as real water samples, which had been, equilibrated with various oil and petroleum products. Both techniques gave similar results but HSSPME was much more sensitive and exhibited better precision. Detection limits were found to be in the sub-ng/ml level, with precision better than 5% R.S.D. in most cases. To evaluate the suitability of SPME for relatively high contamination level analysis, the proposed HSSPME method was applied to the screening of run-off water samples that had heavy oil suspended in them from a tire fire incident. HSSPME results were compared with liquid--liquid extraction. Library searches were conducted on the resulting GC-MS total ion chromatograms to determine the types of compounds found in such samples. Both techniques found similar composition in the water samples with the exception of alkylnaphthalenes that were detected only by HSSPME. A brief study was carried out to assess using SPME for air monitoring. By sampling and concentrating the volatile organic compounds in the coating of the SPME fibre without any other equipment, this new technique is useful as an alternative to active air monitoring by means of sampling pumps and sorbent tubes.
Nazarenko, Yevgen; Kurien, Uday; Nepotchatykh, Oleg; Rangel-Alvarado, Rodrigo B; Ariya, Parisa A
2016-02-01
Exposure to vehicle exhaust can drive up to 70 % of excess lifetime cancer incidences due to air pollution in urban environments. Little is known about how exhaust-derived particles and organic pollutants, implicated in adverse health effects, are affected by freezing ambient temperatures and the presence of snow. Airborne particles and (semi)volatile organic constituents in dilute exhaust were studied in a novel low-temperature environmental chamber system containing natural urban snow under controlled cold environmental conditions. The presence of snow altered the aerosol size distributions of dilute exhaust in the 10 nm to 10 μm range and decreased the number density of the nanoparticulate (<100 nm) fraction of exhaust aerosols, yet increased the 100-150 nm fraction. Upon 1 hour exhaust exposure, the total organic carbon increased in the natural snow from 0.218 ± 0.014 to 0.539 ± 0.009 mg L(-1), and over 40 additional (semi)volatile organic compounds and a large number of exhaust-derived carbonaceous and likely organic particles were identified. The concentrations of benzene, toluene, ethylbenzene, and xylenes (BTEX) increased from near the detection limit to 52.48, 379.5, 242.7, and 238.1 μg kg(-1) (± 10 %), respectively, indicating the absorption of exhaust-derived toxic organic compounds by snow. The alteration of exhaust aerosol size distributions at freezing temperatures and in the presence of snow, accompanied by changes of the organic pollutant content in snow, has potential to alter health effects of human exposure to vehicle exhaust.
Hydrocarbon emissions speciation in diesel and biodiesel exhausts
NASA Astrophysics Data System (ADS)
Payri, Francisco; Bermúdez, Vicente R.; Tormos, Bernardo; Linares, Waldemar G.
Diesel engine emissions are composed of a long list of organic compounds, ranging from C 2 to C 12+, and coming from the hydrocarbons partially oxidized in combustion or produced by pyrolisis. Many of these are considered as ozone precursors in the atmosphere, since they can interact with nitrogen oxides to produce ozone under atmospheric conditions in the presence of sunlight. In addition to problematic ozone production, Brookes, P., and Duncan, M. [1971. Carcinogenic hydrocarbons and human cells in culture. Nature.] and Heywood, J. [1988. Internal Combustion Engine Fundamentals.Mc Graw-Hill, ISBN 0-07-1000499-8.] determined that the polycyclic aromatic hydrocarbons present in exhaust gases are dangerous to human health, being highly carcinogenic. The aim of this study was to identify by means of gas chromatography the amount of each hydrocarbon species present in the exhaust gases of diesel engines operating with different biodiesel blends. The levels of reactive and non-reactive hydrocarbons present in diesel engine exhaust gases powered by different biodiesel fuel blends were also analyzed. Detailed speciation revealed a drastic change in the nature and quantity of semi-volatile compounds when biodiesel fuels are employed, the most affected being the aromatic compounds. Both aromatic and oxygenated aromatic compounds were found in biodiesel exhaust. Finally, the conservation of species for off-side analysis and the possible influence of engine operating conditions on the chemical characterization of the semi-volatile compound phase are discussed. The use of oxygenated fuel blends shows a reduction in the Engine-Out emissions of total hydrocarbons. But the potential of the hydrocarbon emissions is more dependent on the compositions of these hydrocarbons in the Engine-Out, to the quantity; a large percent of hydrocarbons existing in the exhaust, when biodiesel blends are used, are partially burned hydrocarbons, and are interesting as they have the maximum reactivity, but with the use of pure biodiesel and diesel, the most hydrocarbons are from unburned fuel and they have a less reactivity. The best composition in the fuel, for the control of the hydrocarbon emissions reactivity, needs to be a fuel with high-saturated fatty acid content.
Federal Register 2010, 2011, 2012, 2013, 2014
2012-10-19
.... (2008) found Peck's cave amphipod in gravel, rocks, and organic debris (leaves, roots, wood) immediately..., fertilizer nutrients, petroleum hydrocarbons, and semivolatile compounds such as industrial cleaning agents...; stormwater drainage pollutants including soaps, detergents, pharmaceuticals, heavy metals, fertilizer...
i-SVOC -- A simulation program for indoor SVOCs (Version 1.0)
Program i-SVOC estimates the emissions, transport, and sorption of semivolatile organic compounds (SVOCs) in the indoor environment as functions of time when a series of initial conditions is given. This program implements a framework for dynamic modeling of indoor SVOCs develope...
A Reference Method for Measuring Emissions of SVOCs in Small Chambers
Semivolatile organic compounds (SVOCs) are indoor air pollutants that may may have significant adverse effects on human health, and emission of SVOCs from building materials and consumer products is of growing concern. Few chamber studies have been conducted due to the challenge...
LABORATORY MICROCOSM EXPERIMENTS OF OXIDATION PROCESSES AFTER STEAM INJECTION
Aggressive thermal methods such as steam injection or resistive heating are known to be effective for the recovery of many types of volatile and semivolatile compounds. It has been suggested that oxidation or other chemical reactions that occur at remediation temperatures can ai...
The report goes results of (1) a comparison the hood and chamber techniques for quantifying pollutant emission rates from unvented combustion appliances, and (2) an assessment of the semivolatile and nonvolatile organic-compound emissions from unvented kerosene space heaters. In ...
Development of a Small Chamber for SVOCs Sink Effect Study
Semi-volatile organic compounds (SVOCs) have low emissions over a long period of time due to their low vapor pressure. Understanding the transport mechanisms of SVOCs between sources, air, house dust, and interior surfaces in the residential environment will help to characterize ...
IMPACTS OF HISTORIC AND CURRENT-USE CHEMICALS IN WESTERN NATIONAL PARKS
The Western Airborne Contaminants Assessment Project (WACAP) is an interagency effort to determine if airborne contaminants such as semi-volatile organic compounds (sacs) and metals
(e.g. mercury) are impacting National Parks in the western United States. Remote, high elev...
The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
Simulation Program i-SVOC User’s Guide
This document is the User’s Guide for computer program i-SVOC, which estimates the emissions, transport, and sorption of semivolatile organic compounds (SVOCs) in the indoor environment as a function of time when a series of initial conditions is given. This program implements a ...
SVOC emissions from diesel trucks operating on biodiesel fuels
This study measured semivolatile organic compounds (SVOCs) in particle matter (PM) emitted from three heavy-duty trucks equipped with modern after-treatment technologies. Emissions testing was conducted as described by the George et al. VOC study also presented as part of this se...
Liao, Wenta; Draper, William M
2013-02-21
The mass-to-structure or MTS Search Engine is an Access 2010 database containing theoretical molecular mass information for 19,438 compounds assembled from common sources such as the Merck Index, pesticide and pharmaceutical compilations, and chemical catalogues. This database, which contains no experimental mass spectral data, was developed as an aid to identification of compounds in atmospheric pressure ionization (API)-LC-MS. This paper describes a powerful upgrade to this database, a fully integrated utility for filtering or ranking candidates based on isotope ratios and patterns. The new MTS Search Engine is applied here to the identification of volatile and semivolatile compounds including pesticides, nitrosoamines and other pollutants. Methane and isobutane chemical ionization (CI) GC-MS spectra were obtained from unit mass resolution mass spectrometers to determine MH(+) masses and isotope ratios. Isotopes were measured accurately with errors of <4% and <6%, respectively, for A + 1 and A + 2 peaks. Deconvolution of interfering isotope clusters (e.g., M(+) and [M - H](+)) was required for accurate determination of the A + 1 isotope in halogenated compounds. Integrating the isotope data greatly improved the speed and accuracy of the database identifications. The database accurately identified unknowns from isobutane CI spectra in 100% of cases where as many as 40 candidates satisfied the mass tolerance. The paper describes the development and basic operation of the new MTS Search Engine and details performance testing with over 50 model compounds.
Semivolatile Particulate Organic Material Southern Africa during SAFARI 2000
NASA Technical Reports Server (NTRS)
Eatough, D. J.; Eatough, N. L.; Pang, Y.; Sizemore, S.; Kirchstetter, T. W.; Novakov, T.
2005-01-01
During August and September 2000, the University of Washington's Cloud and Aerosol Research Group (CARG) with its Convair-580 research aircraft participated in the Southern African Fire-Atmosphere Research Initiative (SAFARI) 2000 field study in southern Africa. Aboard this aircraft was a Particle Concentrator-Brigham Young University Organic Sampling System (PC-BOSS), which was used to determine semivolatile particulate material with a diffusion denuder sampler. Denuded quartz filters and sorbent beds in series were used to measure nonvolatile and semivolatile materials, respectively. Results obtained with the PC-BOSS are compared to those obtained with conventional quartz-quartz and Teflon-quartz filter pack samplers. Various 10-120 min integrated samples were collected during flights through the h e troposphere, in the atmospheric boundary layer, and in plumes from savanna fires. Significant fine particulate semivolatile organic compounds (SVOC) were found in all samples. The SVOC was not collected by conventional filter pack samplers and therefore would not have been determined in previous studies that used only filter pack samplers. The SVOC averaged 24% of the fine particulate mass in emissions from the fires and 36% of the fine particulate mass in boundary layer samples heavily impacted by aged emissions from savanna fires. Concentrations of fine particulate material in the atmospheric mixed layer heavily impacted by aged savanna frre emissions averaged 130 micrograms per cubic meter. This aerosol was 85% carbonaceous mated.
In November 1990, the Silicate Technology Corporation`s (STC) proprietary process for treating soil contaminated with toxic semivolatile organic and inorganic contaminants was evaluated in a Superfund Innovative Technology Evaluation (SITE) field demonstration at the Selma Pressu...
GAS- AND SOLID-PHASE PARTITIONING OF PCDDS/FS ON MSWI FLY ASH AND THE EFFECTS OF SAMPLING
Semi-volatile organic compounds (SOCs), including polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDDs/Fs), are partitioned as gas-phase and particle-bound products of many industrial combustion processes. This gas/particle partitioning of SOCs has severe implications on both ...
Semivolatile and Volatile Organic Compound Emissions from Wood-Fired Hydronic Heaters
Four commercially available HH technologies were studied: a single-stage combustor with natural updraft, a three-stage downdraft combustion system, a bottom-fed pellet burner, and a two-stage heater with both a combustion and gasification chamber. The fuel consisted of three wood...
NASA Astrophysics Data System (ADS)
Murphy, Benjamin N.; Woody, Matthew C.; Jimenez, Jose L.; Carlton, Ann Marie G.; Hayes, Patrick L.; Liu, Shang; Ng, Nga L.; Russell, Lynn M.; Setyan, Ari; Xu, Lu; Young, Jeff; Zaveri, Rahul A.; Zhang, Qi; Pye, Havala O. T.
2017-09-01
Mounting evidence from field and laboratory observations coupled with atmospheric model analyses shows that primary combustion emissions of organic compounds dynamically partition between the vapor and particulate phases, especially as near-source emissions dilute and cool to ambient conditions. The most recent version of the Community Multiscale Air Quality model version 5.2 (CMAQv5.2) accounts for the semivolatile partitioning and gas-phase aging of these primary organic aerosol (POA) compounds consistent with experimentally derived parameterizations. We also include a new surrogate species, potential secondary organic aerosol from combustion emissions (pcSOA), which provides a representation of the secondary organic aerosol (SOA) from anthropogenic combustion sources that could be missing from current chemical transport model predictions. The reasons for this missing mass likely include the following: (1) unspeciated semivolatile and intermediate volatility organic compound (SVOC and IVOC, respectively) emissions missing from current inventories, (2) multigenerational aging of organic vapor products from known SOA precursors (e.g., toluene, alkanes), (3) underestimation of SOA yields due to vapor wall losses in smog chamber experiments, and (4) reversible organic compounds-water interactions and/or aqueous-phase processing of known organic vapor emissions. CMAQ predicts the spatially averaged contribution of pcSOA to OA surface concentrations in the continental United States to be 38.6 and 23.6 % in the 2011 winter and summer, respectively. Whereas many past modeling studies focused on a particular measurement campaign, season, location, or model configuration, we endeavor to evaluate the model and important uncertain parameters with a comprehensive set of United States-based model runs using multiple horizontal scales (4 and 12 km), gas-phase chemical mechanisms, and seasons and years. The model with representation of semivolatile POA improves predictions of hourly OA observations over the traditional nonvolatile model at sites during field campaigns in southern California (CalNex, May-June 2010), northern California (CARES, June 2010), the southeast US (SOAS, June 2013; SEARCH, January and July, 2011). Model improvements manifest better correlations (e.g., the correlation coefficient at Pasadena at night increases from 0.38 to 0.62) and reductions in underprediction during the photochemically active afternoon period (e.g., bias at Pasadena from -5.62 to -2.42 µg m-3). Daily averaged predictions of observations at routine-monitoring networks from simulations over the continental US (CONUS) in 2011 show modest improvement during winter, with mean biases reducing from 1.14 to 0.73 µg m-3, but less change in the summer when the decreases from POA evaporation were similar to the magnitude of added SOA mass. Because the model-performance improvement realized by including the relatively simple pcSOA approach is similar to that of more-complicated parameterizations of OA formation and aging, we recommend caution when applying these more-complicated approaches as they currently rely on numerous uncertain parameters. The pcSOA parameters optimized for performance at the southern and northern California sites lead to higher OA formation than is observed in the CONUS evaluation. This may be due to any of the following: variations in real pcSOA in different regions or time periods, too-high concentrations of other OA sources in the model that are important over the larger domain, or other model issues such as loss processes. This discrepancy is likely regionally and temporally dependent and driven by interferences from factors like varying emissions and chemical regimes.
Zhang, Meihua; Bi, Jinhu; Yang, Cui; Li, Donghao; Piao, Xiangfan
2012-01-01
In order to achieve rapid, automatic, and efficient extraction for trace chemicals from samples, a system of gas-purged headspace liquid phase microextraction (GP-HS-LPME) has been researched and developed based on the original HS-LPME technique. In this system, semiconductor condenser and heater, whose refrigerating and heating temperatures were controlled by microcontroller, were designed to cool the extraction solvent and to heat the sample, respectively. Besides, inert gas, whose gas flow rate was adjusted by mass flow controller, was continuously introduced into and discharged from the system. Under optimized parameters, extraction experiments were performed, respectively, using GP-HS-LPME system and original HS-LPME technique for enriching volatile and semivolatile target compounds from the same kind of sample of 15 PAHs standard mixture. GC-MS analysis results for the two experiments indicated that a higher enrichment factor was obtained from GP-HS-LPME. The enrichment results demonstrate that GP-HS-LPME system is potential in determination of volatile and semivolatile analytes from various kinds of samples. PMID:22448341
Data is presented showing the progress made towards the development of a new automated system combining solid phase extraction (SPE) with gas chromatography/mass spectrometry for the single run analysis of water samples containing a broad range of acid, base and neutral compounds...
Huang, Yu; Ho, Kin Fai; Ho, Steven Sai Hang; Lee, Shun Cheng; Yau, P S; Cheng, Yan
2011-09-15
The effect of air exchange rate (ACH), temperature (T), and relative humidity (RH) on the formation of indoor secondary organic aerosols (SOAs) through ozonolysis of biogenic organic compounds (BVOCs) emitted from floor cleaner was investigated in this study. The total particle count (with D(p) of 6-225 nm) was up to 1.2 × 10(3)#cm(-3) with ACH of 1.08 h(-1), and it became much more significant with ACH of 0.36 h(-1) (1.1 × 10(4)#cm(-3)). This suggests that a higher ventilation rate can effectively dilute indoor BVOCs, resulting in a less ultrafine particle formation. The total particle count increased when temperature changed from 15 to 23 °C but it decreased when the temperature further increased to 30 °C. It could be explained that high temperature restrained the condensation of formed semi-volatile compounds resulting in low yields of SOAs. When the RH was at 50% and 80%, SOA formation (1.1-1.2 × 10(4)#cm(-3)) was the more efficient compared with that at RH of 30% (5.9 × 10(3)#cm(-3)), suggesting higher RH facilitating the initial nucleation processes. Oxidation generated secondary carbonyl compounds were also quantified. Acetone was the most abundant carbonyl compound. The formation mechanisms of formaldehyde and acetone were proposed. Copyright © 2011 Elsevier B.V. All rights reserved.
Vilaplana, Francisco; Martínez-Sanz, Marta; Ribes-Greus, Amparo; Karlsson, Sigbritt
2010-01-15
The emission of low molecular weight compounds from recycled high-impact polystyrene (HIPS) has been investigated using headspace solid-phase microextraction (HS-SPME) and gas chromatography-mass spectrometry (GC-MS). Four released target analytes (styrene, benzaldehyde, acetophenone, and 2-phenylpropanal) were selected for the optimisation of the HS-SPME sampling procedure, by analysing operating parameters such as type of SPME fibre (polarity and operating mechanism), particle size, extraction temperature and time. 26 different compounds were identified to be released at different temperatures from recycled HIPS, including residues of polymerisation, oxidated derivates of styrene, and additives. The type of SPME fibre employed in the sampling procedure affected the detection of emitted components. An adsorptive fibre such as carbowax/polydimethylsiloxane (CAR/PDMS fibre) offered good selectivity for both non-polar and polar volatile compounds at lower temperatures; higher temperatures result in interferences from less-volatile released compounds. An absorptive fibre as polydimethylsiloxane (PDMS) fibre is suitable for the detection of less-volatile non-polar molecules at higher temperatures. The nature and relative amount of the emitted compounds increased with higher exposure temperature and smaller polymeric particle size. HS-SPME proves to be a suitable technique for screening the emission of semi-volatile organic compounds (SVOCs) from polymeric materials; reliable quantification of the content of target analytes in recycled HIPS is however difficult due to the complex mass-transfer processes involved, matrix effects, and the difficulties in equilibrating the analytical system. 2009 Elsevier B.V. All rights reserved.
Predicting SVOC Emissions into Air and Foods in Support of High-Throughput Exposure Assessment
The release of semi-volatile organic compounds (SVOCs) from consumer articles may be a critical human exposure pathway. In addition, the migration of SVOCs from food packaging materials into foods may also be a dominant source of exposure for some chemicals. Here we describe re...
VALIDATION OF STANDARD ANALYTICAL PROTOCOL FOR SEMI-VOLATILE ORGANIC COMPOUNDS
There is a growing concern with the potential for terrorist use of chemical weapons to cause civilian harm. In the event of an actual or suspected outdoor release of chemically hazardous material in a large area, the extent of contamination must be determined. This requires a s...
This study evaluates the treatment of gas-phase atmospheric deposition in a screening level model of the multimedia environmental distribution of toxics (MEND-TOX). Recent algorithmic additions to MEND-TOX for the estimation of gas-phase deposition velocity over vegetated surf...
The addition of brominated organic compounds to the feed of a pilot-scale incinerator burning chlorinated waste has been found previously, under some circumstances, to enhance emissions of volatile and semivolatile organic chlorinated products of incomplete combustion (PiCs) incl...
USDA-ARS?s Scientific Manuscript database
Southern and southeastern US production of blueberries has increased markedly in recent years. Gas chromatography-olfactometry (GC-O) and volatile and semi-volatile compounds are seldom reported in rabbiteye blueberry (RAB). Few comparisons have been made between the organoleptic differences betwe...
The solid-phase diffusion coefficient (Dm) and material-air partition coefficient (Kma) are key parameters for characterizing the sources and transport of semivolatile organic compounds (SVOCs) in the indoor environment. In this work, a new experimental method was developed to es...
BIOMARKERS OF PM EXPOSURE TO COMBUSTION SOURCE EMISSIONS & ORGANIC (TOXIC) COMPONENTS
Fine particles (PM2.5) and associated semivolatile organic compounds (SVOC) contain a very complex mixture of both organic and inorganic chemicals that may contribute to toxicity of the particles. The health effects of PM2.5 exposures in humans result from both acute and chronic...
Methods have been developed for screening and assessing the level of volatile, semi-volatile and non-volatile organic pollutants in human blood. The specific methodology is developed for measuring the presence of "native" compounds rather than their metabolites. Spe...
The U.S. produces roughly 5 billion liters of biodiesel per year currently. Use of biodiesel is projected to increase owing to the potential economic, energy, and environmental benefits. Despite these benefits, there is public health concern about the possible direct and indirect...
A laboratory chamber was used to determine transport of a suspected anti-androgenic dicarboximide fungicide, vinclozolin (3,5-dichlorophenyl)-5-methyl-5-vinyl-oxzoli-dine-2,4-dione) and three degradation products from a North Carolina Piedmont aquic hapludult soil following a s...
INTEGRATED AND REAL-TIME DIFFUSION DENUDER SAMPLE FOR PM2.5. (R825367)
Particulate matter (PM) is a complex mixture of stable condensed phases, adsorbed or dissolved gases, and semi-volatile materials, i.e. compounds that transfer between the gas and condensed phases. Fine particles in both rural and urban environments contain su...
A method for measuring the atmospheric flux of the antiandrogenic dicarboxirnide, vinclozolin, and its degradation products was investigated. A nitric oxide laboratory chamber was modified to measure the flux of semi-volatile compounds. Pesticide application systems and soil in...
AUTOMATED SOLID PHASE EXTRACTION GC/MS FOR ANALYSIS OF SEMIVOLATILES IN WATER AND SEDIMENTS
Data is presented on the development of a new automated system combining solid phase extraction (SPE) with GC/MS spectrometry for the single-run analysis of water samples containing a broad range of organic compounds. The system uses commercially available automated in-line sampl...
Conn, Kathleen E.; Black, Robert W.
2014-01-01
Between February and June 2013, the U.S. Geological Survey collected representative samples of whole water, suspended sediment, and (or) bed sediment from a single strategically located site on the Duwamish River, Washington, during seven periods of different flow conditions. Samples were analyzed by Washington-State-accredited laboratories for a large suite of compounds, including polycyclic aromatic hydrocarbons and other semivolatile compounds, polychlorinated biphenyl Aroclors and the 209 congeners, metals, dioxins/furans, volatile organic compounds, pesticides, butyltins, hexavalent chromium, and total organic carbon. Chemical concentrations associated with bulk bed sediment (<2 mm) and fine bed sediment (<62.5 μm) fractions were compared to chemical concentrations associated with suspended sediment. Bulk bed sediment concentrations generally were lower than fine bed sediment and suspended-sediment concentrations. Concurrent with the chemistry sampling, additional parameters were measured, including instantaneous river discharge, suspended-sediment concentration, sediment particle-size distribution, and general water-quality parameters. From these data, estimates of instantaneous sediment and chemical loads from the Green River to the Lower Duwamish Waterway were calculated.
The characterisation of diesel exhaust particles - composition, size distribution and partitioning.
Alam, Mohammed S; Zeraati-Rezaei, Soheil; Stark, Christopher P; Liang, Zhirong; Xu, Hongming; Harrison, Roy M
2016-07-18
A number of major research questions remain concerning the sources and properties of road traffic generated particulate matter. A full understanding of the composition of primary vehicle exhaust aerosol and its contribution to secondary organic aerosol (SOA) formation still remains elusive, and many uncertainties exist relating to the semi-volatile component of the particles. Semi-Volatile Organic Compounds (SVOCs) are compounds which partition directly between the gas and aerosol phases under ambient conditions. The SVOCs in engine exhaust are typically hydrocarbons in the C15-C35 range, and are largely uncharacterised because they are unresolved by traditional gas chromatography, forming a large hump in the chromatogram referred to as Unresolved Complex Mixture (UCM). In this study, thermal desorption coupled to comprehensive Two Dimensional Gas-Chromatography Time-of-Flight Mass-Spectrometry (TD-GC × GC-ToF-MS) was exploited to characterise and quantify the composition of SVOCs from the exhaust emission. Samples were collected from the exhaust of a diesel engine, sampling before and after a diesel oxidation catalyst (DOC), while testing at steady state conditions. Engine exhaust was diluted with air and collected using both filter and impaction (nano-MOUDI), to resolve total mass and size resolved mass respectively. Adsorption tubes were utilised to collect SVOCs in the gas phase and they were then analysed using thermal desorption, while particle size distribution was evaluated by sampling with a DMS500. The SVOCs were observed to contain predominantly n-alkanes, branched alkanes, alkyl-cycloalkanes, alkyl-benzenes, PAHs and various cyclic aromatics. Particle phase compounds identified were similar to those observed in engine lubricants, while vapour phase constituents were similar to those measured in fuels. Preliminary results are presented illustrating differences in the particle size distribution and SVOCs composition when collecting samples with and without a DOC. The results indicate that the DOC tested is of very limited efficiency, under the studied engine operating conditions, for removal of SVOCs, especially at the upper end of the molecular weight range.
Uncertainty in aerosol hygroscopicity resulting from semi-volatile organic compounds
NASA Astrophysics Data System (ADS)
Goulden, Olivia; Crooks, Matthew; Connolly, Paul
2018-01-01
We present a novel method of exploring the effect of uncertainties in aerosol properties on cloud droplet number using existing cloud droplet activation parameterisations. Aerosol properties of a single involatile particle mode are randomly sampled within an uncertainty range and resulting maximum supersaturations and critical diameters calculated using the cloud droplet activation scheme. Hygroscopicity parameters are subsequently derived and the values of the mean and uncertainty are found to be comparable to experimental observations. A recently proposed cloud droplet activation scheme that includes the effects of co-condensation of semi-volatile organic compounds (SVOCs) onto a single lognormal mode of involatile particles is also considered. In addition to the uncertainties associated with the involatile particles, concentrations, volatility distributions and chemical composition of the SVOCs are randomly sampled and hygroscopicity parameters are derived using the cloud droplet activation scheme. The inclusion of SVOCs is found to have a significant effect on the hygroscopicity and contributes a large uncertainty. For non-volatile particles that are effective cloud condensation nuclei, the co-condensation of SVOCs reduces their actual hygroscopicity by approximately 25 %. A new concept of an effective hygroscopicity parameter is introduced that can computationally efficiently simulate the effect of SVOCs on cloud droplet number concentration without direct modelling of the organic compounds. These effective hygroscopicities can be as much as a factor of 2 higher than those of the non-volatile particles onto which the volatile organic compounds condense.
DOE Office of Scientific and Technical Information (OSTI.GOV)
ITLV.
1999-03-01
The Corrective Action Investigation Plan for Corrective Action Unit 428, Area 3 Septic Waste Systems 1 and 5, has been developed in accordance with the Federal Facility Agreement and Consent Order that was agreed to by the U. S. Department of Energy, Nevada Operations Office; the State of Nevada Division of Environmental Protection; and the U. S. Department of Defense. Corrective Action Unit 428 consists of Corrective Action Sites 03- 05- 002- SW01 and 03- 05- 002- SW05, respectively known as Area 3 Septic Waste System 1 and Septic Waste System 5. This Corrective Action Investigation Plan is used inmore » combination with the Work Plan for Leachfield Corrective Action Units: Nevada Test Site and Tonopah Test Range, Nevada , Rev. 1 (DOE/ NV, 1998c). The Leachfield Work Plan was developed to streamline investigations at leachfield Corrective Action Units by incorporating management, technical, quality assurance, health and safety, public involvement, field sampling, and waste management information common to a set of Corrective Action Units with similar site histories and characteristics into a single document that can be referenced. This Corrective Action Investigation Plan provides investigative details specific to Corrective Action Unit 428. A system of leachfields and associated collection systems was used for wastewater disposal at Area 3 of the Tonopah Test Range until a consolidated sewer system was installed in 1990 to replace the discrete septic waste systems. Operations within various buildings at Area 3 generated sanitary and industrial wastewaters potentially contaminated with contaminants of potential concern and disposed of in septic tanks and leachfields. Corrective Action Unit 428 is composed of two leachfield systems in the northern portion of Area 3. Based on site history collected to support the Data Quality Objectives process, contaminants of potential concern for the site include oil/ diesel range total petroleum hydrocarbons, and Resource Conservation and Recovery Act characteristic volatile organic compounds, semivolatile organic compounds, and metals. A limited number of samples will be analyzed for gamma- emitting radionuclides and isotopic uranium from four of the septic tanks and if radiological field screening levels are exceeded. Additional samples will be analyzed for geotechnical and hydrological properties and a bioassessment may be performed. The technical approach for investigating this Corrective Action Unit consists of the following activities: Perform video surveys of the discharge and outfall lines. Collect samples of material in the septic tanks. Conduct exploratory trenching to locate and inspect subsurface components. Collect subsurface soil samples in areas of the collection system including the septic tanks and outfall end of distribution boxes. Collect subsurface soil samples underlying the leachfield distribution pipes via trenching. Collect surface and near- surface samples near potential locations of the Acid Sewer Outfall if Septic Waste System 5 Leachfield cannot be located. Field screen samples for volatile organic compounds, total petroleum hydrocarbons, and radiological activity. Drill boreholes and collect subsurface soil samples if required. Analyze samples for total volatile organic compounds, total semivolatile organic compounds, total Resource Conservation and Recovery Act metals, and total petroleum hydrocarbons (oil/ diesel range organics). Limited number of samples will be analyzed for gamma- emitting radionuclides and isotopic uranium from particular septic tanks and if radiological field screening levels are exceeded. Collect samples from native soils beneath the distribution system and analyze for geotechnical/ hydrologic parameters. Collect and analyze bioassessment samples at the discretion of the Site Supervisor if total petroleum hydrocarbons exceed field- screening levels.« less
2014-01-01
Residential exposure can dominate total exposure for commercial chemicals of health concern; however, despite the importance of consumer exposures, methods for estimating household exposures remain limited. We collected house dust and indoor air samples in 49 California homes and analyzed for 76 semivolatile organic compounds (SVOCs)—phthalates, polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), and pesticides. Sixty chemicals were detected in either dust or air and here we report 58 SVOCs detected in dust for the first time. In dust, phthalates (bis(2-ethylhexyl) phthalate, benzyl butyl phthalate, di-n-butyl phthalate) and flame retardants (PBDE 99, PBDE 47) were detected at the highest concentrations relative to other chemicals at the 95th percentile, while phthalates were highest at the median. Because SVOCs are found in both gas and condensed phases and redistribute from their original source over time, partitioning models can clarify their fate indoors. We use empirical data to validate air-dust partitioning models and use these results, combined with experience in SVOC exposure assessment, to recommend residential exposure measurement strategies. We can predict dust concentrations reasonably well from measured air concentrations (R2 = 0.80). Partitioning models and knowledge of chemical Koa elucidate exposure pathways and suggest priorities for chemical regulation. These findings also inform study design by allowing researchers to select sampling approaches optimized for their chemicals of interest and study goals. While surface wipes are commonly used in epidemiology studies because of ease of implementation, passive air sampling may be more standardized between homes and also relatively simple to deploy. Validation of passive air sampling methods for SVOCs is a priority. PMID:25488487
Peterson, David A.; Boughton, Gregory K.
2000-01-01
A comprehensive water-quality investigation of the Yellowstone River Basin began in 1997, under the National Water-Quality Assessment (NAWQA) Program. Twenty-four sampling sites were selected for sampling of fish tissue and bed sediment during 1998. Organic compounds analyzed included organochlorine insecticides and their metabolites and total polychlorinated biphenyls (PCBs) from fish-tissue and bed-sediment samples, and semivolatile organic compounds from bed-sediment samples. A broad suite of trace elements was analyzed from both fish-tissue and bed-sediment samples, and a special study related to mercury also was conducted. Of the 12 organochlorine insecticides and metabolites detected in the fish-tissue samples, the most compounds per site were detected in samples from integrator sites which represent a mixture of land uses. The presence of DDT, and its metabolites DDD and DDE, in fish collected in the Yellowstone Park area likely reflects long-term residual effects from historical DDT-spraying programs for spruce budworm. Dieldrin, chlordane, and other organic compounds also were detected in the fish-tissue samples. The compound p, p'-DDE was detected at 71 percent of the sampling sites, more than any other compound. The concentrations of total DDT in fish samples were low, however, compared to concentrations from historical data from the study area, other NAWQA studies in the Rocky Mountains, and national baseline concentrations. Only 2 of the 27 organochlorine insecticides and metabolites and total PCBs analyzed in bed sediment were detected. Given that 12 of the compounds were detected in fish-tissue samples, fish appeared to be more sensitive indicators of contamination than bed sediment.Concentrations of some trace elements in fish and bed sediment were higher at sites in mineralized areas than at other sites. Concentrations of selenium in fish tissue from some sites were above background levels. Concentrations of arsenic, chromium, copper, and lead in some of the bed-sediment samples potentially exceeded criteria for the protection of aquatic life.
NASA Astrophysics Data System (ADS)
Roldin, P.; Liao, L.; Mogensen, D.; Dal Maso, M.; Rusanen, A.; Kerminen, V.-M.; Mentel, T. F.; Wildt, J.; Kleist, E.; Kiendler-Scharr, A.; Tillmann, R.; Ehn, M.; Kulmala, M.; Boy, M.
2015-09-01
We used the Aerosol Dynamics gas- and particle-phase chemistry model for laboratory CHAMber studies (ADCHAM) to simulate the contribution of BVOC plant emissions to the observed new particle formation during photooxidation experiments performed in the Jülich Plant-Atmosphere Chamber and to evaluate how well smog chamber experiments can mimic the atmospheric conditions during new particle formation events. ADCHAM couples the detailed gas-phase chemistry from Master Chemical Mechanism with a novel aerosol dynamics and particle phase chemistry module. Our model simulations reveal that the observed particle growth may have either been controlled by the formation rate of semi- and low-volatility organic compounds in the gas phase or by acid catalysed heterogeneous reactions between semi-volatility organic compounds in the particle surface layer (e.g. peroxyhemiacetal dimer formation). The contribution of extremely low-volatility organic gas-phase compounds to the particle formation and growth was suppressed because of their rapid and irreversible wall losses, which decreased their contribution to the nano-CN formation and growth compared to the atmospheric situation. The best agreement between the modelled and measured total particle number concentration (R2 > 0.95) was achieved if the nano-CN was formed by kinetic nucleation involving both sulphuric acid and organic compounds formed from OH oxidation of BVOCs.
The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
Recent studies suggest that semivolatile organic compounds (SVOCs) are important precursors to secondary organic aerosol (SOA) in urban atmospheres. However, knowledge of the chemical composition of SVOCs is limited by current analytical techniques, which are typically unable to...
40 CFR 1065.1109 - Post-test sampler disassembly and sample extraction.
Code of Federal Regulations, 2014 CFR
2014-07-01
... 40 Protection of Environment 33 2014-07-01 2014-07-01 false Post-test sampler disassembly and... Semi-Volatile Organic Compounds § 1065.1109 Post-test sampler disassembly and sample extraction. This... environment as follows after the test: (1) Remove the PM filter, PUF plugs, and all the XAD-2 from the...
SEMIVOLATILE ORGANIC ACIDS AND LEVOGLUCOSAN IN NEW YORK CITY AIR FOLLOWING 9/11/2001
Organic acid compounds and levoglucosan, an important molecular marker of burning cellulose, are detected in New York City air collected between 9/26/01 and 10/24/01 500 m from Ground Zero. Sampling of Ground Zero emissions at our site is commensurate with a southwesterly wind f...
This data was generated from a small chamber bis(2-ethylhexyl) phthalate (DEHP) emission test. It was to participate an interaboratory study of DEHP emissions from vinyl flooring in a SVOC emission chamber organized by Virginia Polytechnic Institute and State University (VT).
An analytical method was developed for the trace analysis of 98 semi-volatile organic compounds (SOCs) in remote, high elevation lake sediment. Sediment cores from Lone Pine Lake (West of the Continental Divide) and Mills Lake (East of the Continental Divide) in Rocky Mountain Na...
Maintaining Acceptable Indoor Air Quality during the Renovation of a School. Technical Bulletin.
ERIC Educational Resources Information Center
Jacobs, Bruce W.
Information that school facility personnel can use concerning the potential impacts of renovation projects on indoor air quality (IAQ), along with details of some effective control strategies, are presented. Various kinds of contaminants may be generated by renovations, including volatile and semivolatile organic compounds, dusts and fibers (e.g.,…
This study will result in the development of a new method for the rapid measurement of SVOCs. The characterization of VOC and SVOC emissions of vehicles with different fuel types will improve our understanding of the processes leading to secondary organic aerosol pollution and...
The present study examines the effects of fuel (an ultra-low sulfur diesel [ULSD] versus a 20% v/v soy-based biodiesel—80% v/v petroleum blend [B20]), temperature, load, vehicle, driving cycle, and active regeneration technology on gas- and particle-phase carbon emissions f...
MacCoy, Dorene E.; Domagalski, Joseph L.
1999-01-01
Elevated levels of trace elements and hydrophobic organic compounds were detected in streambed sediments and aquatic biota [Asiatic clam (Corbicula fluminea) or bottom-feeding fish] of the Sacramento River Basin, California, during October and November 1995. Trace elements detected included cadmium, copper, mercury, lead, and zinc. Elevated levels of cadmium, copper, and zinc in the upper Sacramento River are attributed to a mining land use, and elevated levels of zinc and lead in an urban stream, and possibly in the lower Sacramento River, are attributed to urban runoff processes. Elevated levels of mercury in streambed sediment are attributed to either past mercury mining or to the use of mercury in past gold mining operations. Mercury mining was an important land use within the Coast Ranges in the past and gold mining was an important land use of the Sierra Nevada in the past. Mercury was the only trace element found in elevated levels in the tissue of aquatic biota, and those levels also could be attributed to either mining or urban runoff. Hydrophobic organic compounds also were detected in streambed sediments and aquatic biota. The most frequently detected compounds were DDT and its breakdown products, dieldrin, oxychlordane, and toxaphene. Differences were found in the types of compounds detected at agricultural sites and the urban site. Although both types of sites had measurable concentrations of DDT or its breakdown products, the urban site also had measurable concentrations of pesticides used for household pest control. Few semivolatile compounds were detected in the streambed sediments of any site. The semivolatile compound p-cresol, a coal-tar derivative associated with road maintenance, was found in the highest concentration.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Weiss, P.
The concentrations (C) of several semivolatile organic compounds (SOCs) in Norway spruce needles (N) and in the local humus horizon (O) of 25 remote Austrian forest sites were used to calculate an ecosystem-oriented partition coefficient needles/humus horizon (C{sub N}/C{sub O}). Between 66 and 78% of the compounds' variation of this quotient could be explained by each of the following physicochemical parameters: vapor pressure (p{sub s}) and the partition coefficients n-octanol/water (K{sub OW}), n-octanol/air (K{sub OA}), and adsorbed/ dissolved in soil (K{sub OC}) of the compounds. This result further underlines the usefulness of these parameters for predicting the behavior of SOCsmore » in terrestrial ecosystems. Compounds with low p{sub s} and high K{sub OW}, K{sub OA}, and K{sub OC} show a very low C{sub N}/C{sub O} quotient, which implies a higher accumulation of these compounds in the O horizon than in the needles. The role of forest soils as sink for these SOCs is demonstrated. Alternatively, C{sub N}/C{sub O} > 1, due to higher concentrations in the needles than in the O horizon, have been shown for SOCs with comparably high p{sub s} and low K{sub OW}, K{sub OA}, and K{sub OC}. In this respect, the possible role of revolatilization of the more volatile SOCs from soils to needles is discussed. In the mineral soil layers below the O horizon, SOCs with lower K{sub OC} and better water solubility tend to be less accumulated. However, if all investigated compounds are taken into consideration, accumulation in the mineral soil layers showed no general trend in relation to the selected physicochemical parameters.« less
NASA Astrophysics Data System (ADS)
Cai, C.; Zhao, C.
2017-12-01
Quantifying the gas/particle partitioning of organic compounds is of great significance to the understanding of atmospheric aerosol indirect effect. Accurate determination of the hygroscopicities and vapor pressures of semi-volatile organic compounds (SVOC) is of crucial importance in studying their partitioning behavior into atmospheric aerosol, as current published vapor pressures results of compounds of interest (usually with vapor pressures smaller than 0.01 Pa) vary by several orders of magnitude. On the other hand, influences on SVOCs evaporation from participation of inorganic species remains ambiguous. In this study we present quantitative investigation of hygroscopicities and volatilities of single aerosol droplets in an aerosol optical tweezers. The trapped droplet (3-7 µm radii) in the aerosol optical tweezers acts as a micro cavity, which stimulates the cavity enhanced Raman spectroscopy (CERS) signal. Size and composition of the particle are calculated from Mie fit to the positions of the "whispering gallery modes" in the CERS fingerprint. Hygroscopic behaviors and SVOC pure component vapor pressure can then be extracted from the correlation between the changing droplet radius and solute concentration (derived from experimentally determined RI real part). We will further present the influences between mass transfer on the gas-particle interface and within the droplet.
The effect of ventilation on indoor exposure to semivolatile organic compounds.
Liu, C; Zhang, Y; Benning, J L; Little, J C
2015-06-01
A mechanistic model was developed to examine how natural ventilation influences residential indoor exposure to semivolatile organic compounds (SVOCs) via inhalation, dermal sorption, and dust ingestion. The effect of ventilation on indoor particle mass concentration and mass transfer at source/sink surfaces, and the enhancing effect of particles on mass transfer at source/sink surfaces are included. When air exchange rate increases from 0.6/h to 1.8/h, the steady-state SVOC (gas-phase plus particle phase with log KOA varying from 9 to 13) concentration in the idealized model decreases by about 60%. In contrast, for the same change in ventilation, the simulated indoor formaldehyde (representing volatile organic compounds) gas-phase concentration decreases by about 70%. The effect of ventilation on exposure via each pathway has a relatively insignificant association with the KOA of the SVOCs: a change of KOA from 10(9) to 10(13) results in a change of only 2-30%. Sensitivity analysis identifies the deposition rate of PM2.5 as a primary factor influencing the relationship between ventilation and exposure for SVOCs with log KOA = 13. The relationship between ventilation rate and air speed near surfaces needs to be further substantiated. © 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.
Xu, Y; Liang, Y; Urquidi, J R; Siegel, J A
2015-02-01
Retail stores contain a wide range of products that can emit a variety of indoor pollutants. Among these chemicals, phthalate esters and polybrominated diphenyl ethers (PBDEs) are two important categories of semi-volatile organic compounds (SVOCs). Filters in heating, ventilation, and air-conditioning (HVAC) system collect particles from large volumes of air and thus potentially provide spatially and temporally integrated SVOC concentrations. This study measured six phthalate and 14 PBDE compounds in HVAC filter dust in 14 retail stores in Texas and Pennsylvania, United States. Phthalates and PBDEs were widely found in the HVAC filter dust in retail environment, indicating that they are ubiquitous indoor pollutants. The potential co-occurrence of phthalates and PBDEs was not strong, suggesting that their indoor sources are diverse. The levels of phthalates and PBDEs measured in HVAC filter dust are comparable to concentrations found in previous investigations of settled dust in residential buildings. Significant correlations between indoor air and filter dust concentrations were found for diethyl phthalate, di-n-butyl phthalate, and benzyl butyl phthalate. Reasonable agreement between measurements and an equilibrium model to describe SVOC partitioning between dust and gas-phase is achieved. © 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.
MATRIX-VBS Condensing Organic Aerosols in an Aerosol Microphysics Model
NASA Technical Reports Server (NTRS)
Gao, Chloe Y.; Tsigaridis, Konstas; Bauer, Susanne E.
2015-01-01
The condensation of organic aerosols is represented in a newly developed box-model scheme, where its effect on the growth and composition of particles are examined. We implemented the volatility-basis set (VBS) framework into the aerosol mixing state resolving microphysical scheme Multiconfiguration Aerosol TRacker of mIXing state (MATRIX). This new scheme is unique and advances the representation of organic aerosols in models in that, contrary to the traditional treatment of organic aerosols as non-volatile in most climate models and in the original version of MATRIX, this new scheme treats them as semi-volatile. Such treatment is important because low-volatility organics contribute significantly to the growth of particles. The new scheme includes several classes of semi-volatile organic compounds from the VBS framework that can partition among aerosol populations in MATRIX, thus representing the growth of particles via condensation of low volatility organic vapors. Results from test cases representing Mexico City and a Finish forrest condistions show good representation of the time evolutions of concentration for VBS species in the gas phase and in the condensed particulate phase. Emitted semi-volatile primary organic aerosols evaporate almost completely in the high volatile range, and they condense more efficiently in the low volatility range.
Cheng, Yuan; Li, Shao-Meng; Liggio, John; Hayden, Katherine; Han, Yuemei; Stroud, Craig; Chan, Tak; Poitras, Marie-Josée
2017-11-01
Semivolatile organic compounds (SVOCs) represent a dominant category of secondary organic aerosol precursors that are increasingly included in air quality models. In the present study, an experimental system was developed and applied to a light-duty diesel engine to determine the emission factors of particulate SVOCs (pSVOCs) and nonvolatile particulate matter (PM) components at dilution ratios representative of ambient conditions. The engine was tested under three steady-state operation modes, using ultra-low-sulfur diesel (ULSD), three types of pure biodiesels and their blends with ULSD. For ULSD, the contribution of pSVOCs to total particulate organic matter (POM) mass in the engine exhaust ranged between 21 and 85%. Evaporation of pSVOCs from the diesel particles during dilution led to decreases in the hydrogen to carbon ratio of POM and the PM number emission factor of the particles. Substituting biodiesels for ULSD could increase pSVOCs emissions but brought on large reductions in black carbon (BC) emissions. Among the biodiesels tested, tallow/used cooking oil (UCO) biodiesel showed advantages over soybean and canola biodiesels in terms of both pSVOCs and nonvolatile PM emissions. It is noteworthy that PM properties, such as particle size and BC mass fraction, differed substantially between emissions from conventional diesel and biodiesels. Copyright © 2017 Elsevier Ltd. All rights reserved.
Foreman, William T.; Connor, Brooke F.; Furlong, Edward T.; Vaught, Deborah G.; Merten, Leslie M.
1995-01-01
A method for the determination of 30 individual organochlorine pesticides, total toxaphene, and total polychlorinated biphenyls (PCBs) in bottom sediment is described. The method isolates the pesticides and PCBs by solvent extraction with dichlorobenzene, removes inorganic sulfur, large naturally occurring molecules, and other unwanted interferences by gel permeation chromatography, and further cleans up and class fractionates the extract using adsorption chromatography. The com- pounds then are instrumentally determined using dual capillary-column gas chromatography with electron-capture detection. Reporting limits range from 1 to 5 micrograms per kilogram for 30 individual pesticides, 50 micrograms per kilogram for total PCBs, and 200 micrograms per kilogram for total toxaphene. The method also is designed to allow the simultaneous isolation of 79 other semivolatile organic compounds from the sediment, which are separately quantified using gas chromatography with mass spectrometric detection. The method was developed in support of the U.S. Geological Survey's National Water-Quality Assessment program.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Goldstein, A. H.; Yee, L. D.; Issacman-VanWertz, G.
In areas where biogenic emissions are oxidized in the presence of anthropogenic pollutants such as SO2, NOx, and black carbon, it has become increasingly apparent that secondary organic aerosol (SOA) formation from biogenic volatile organic compounds (VOCs) is substantially enhanced. Research is urgently needed to elucidate fundamental processes of natural and anthropogenically influenced VOC oxidation and the contribution of these processes to SOA formation. GoAmazon 2014/15 afforded study of the chemical transformations in the region downwind of Manaus, Brazil, where local biogenic VOC emissions are high, and their chemical oxidation can be studied both inside and outside of the urbanmore » plume to differentiate the role of anthropogenic influence on secondary aerosol formation during oxidation of these natural VOC emissions. To understand the connection between primary biogenic VOC emissions and their secondary products that form aerosols, we made time-resolved molecular level measurements by deploying a Semi-Volatile Thermal Desorption Aerosol Gas Chromatograph (SV-TAG) and a sequential filter sampler during two intensive operational periods (IOPs) of the GoAmazon 2014/15 field campaign. The SV-TAG measured semi-volatile organic compounds in both the gas and particle phases and the sequential filter sampler collected aerosols on quartz fiber filters in four-hour increments used for offline analysis. SV-TAG employed novel online derivatization that provided chemical speciation of highly oxygenated or functionalized compounds that comprise a substantial fraction of secondary organic aerosols, yet are poorly characterized. It also provided partitioning of these compounds between the vapor and particle phases at sufficient time resolution to define the importance of competing atmospheric processes. These measurements were supported by offline analysis of the filters using two-dimensional gas chromatography (GC x GC) with high-resolution time-of-flight mass spectrometry (HR-TOF-MS) using both electron impact (EI) and soft vacuum ultraviolet (VUV) ionization with derivatization. Speciated chemical data from SV-TAG and filter measurements were used to elucidate the relative importance of potential oxidation pathways by providing detailed information on the product distribution from atmospheric reactions and the quantification of known tracers for various oxidation pathways. Together, these techniques provided unequivocal molecular identification of a wide range of atmospheric organic compounds spanning the volatile, semi-volatile, and non-volatile phases. This level of chemical characterization provided insight into the chemical and physical processes that control the atmospheric oxidation of biogenic VOC and subsequent formation of SOA.« less
[Research on source profile of aerosol organic compounds in leather plant].
Wang, Bo-Guang; Zhou, Yan; Feng, Zhi-Cheng; Liu, Hui-Xuan
2009-04-15
Through investigating current air pollution condition for PM10 in every factories of different style leather plants in Pearl River Delta, characteristic profile of semi-volatile organic compounds in PM10 emitted from leather factories and their contents were researched by using ultrasonic and gas chromatography and mass spectrum technology. The 6 types of organic compounds containing 46 species in total were found in the collected samples, including phenyl compounds, alcohols, PAHs, acids, esters and amides. The concentrations of PM10 in leather tanning plant, leather dying plant and man-made leather plant were 678.5, 454.5, 498.6 microgm x m(-3) respectively, and concentration of organic compounds in PM10 were 10.04, 6.89, 14.21 microg x m(-3) in sequence. The more important type of pollutants in each leather plants had higher contribution to total organic mass as follows, esters and amides in tanning plants profile account for 43.47% and 36.51% respectively; esters and alcohols in dying plants profiles account for 52.52% and 16.16% respectively; esters and amide in man-made leather plant have the highest content and account for 57.07% and 24.17% respectively. In the aerosol organic source profiles of tested leather plants, 9-octadecenamide was the abundant important species with the weight of 26.15% in tanning plant, and Bis(2-ethylhexyl) phthalate was up to 44.19% in the dying plant, and Bis(2-ethylhexyl) maleate and 1-hydroxy-piperidine had obviously higher weight in man-made plant than the other two plants.
Development of a continuous monitoring system for PM10 and components of PM2.5.
Lippmann, M; Xiong, J Q; Li, W
2000-01-01
While particulate matter with aerodynamic diameters below 10 and 2.5 microns (PM10 and PM2.5) correlate with excess mortality and morbidity, there is evidence for still closer epidemiological associations with sulfate ion, and experimental exposure-response studies suggest that the hydrogen ion and ultrafine (PM0.15) concentrations may be important risk factors. Also, there are measurement artifacts in current methods used to measure ambient PM10 and PM2.5, including negative artifacts because of losses of sampled semivolatile components (ammonium nitrate and some organics) and positive artifacts due to particle-bound water. To study such issues, we are developing a semi-continuous monitoring system for PM10, PM2.5, semivolatiles (organic compounds and NH4NO3), particle-bound water, and other PM2.5 constituents that may be causal factors. PM10 is aerodynamically sorted into three size-fractions: (1) coarse (PM10-PM2.5); (2) accumulation mode (PM2.5-PM0.15); and (3) ultrafine (PM0.15). The mass concentration of each fraction is measured in terms of the linear relation between accumulated mass and pressure drop on polycarbonate pore filters. The PM0.15 mass, being highly correlated with the ultrafine number concentration, provides a good index of the total number concentration in ambient air. For the accumulation mode (PM2.5-PM0.15), which contains nearly all of the semivolatiles and particle-bound water by mass, aliquots of the aerosol stream flow into system components that continuously monitor sulfur (by flame photometry), ammonium and nitrate (by chemiluminescence following catalytic transformations to NO), organics (by thermal-optical analysis) and particle-bound water (by electrolytic hygrometer after vacuum evaporation of sampled particles). The concentration of H+ can be calculated (by ion balance using the monitoring data on NO3-, NH4+, and SO4=).
The impact of add-on catalytic devices on pollutant emissions from unvented kerosene heaters
DOE Office of Scientific and Technical Information (OSTI.GOV)
Apte, M.G.; Traynor, G.W.; Froehlich, D.A.
1989-09-01
Many studies have documented pollutant emission rates from kerosene heaters. Carbon monoxide (CO), carbon dioxide (CO{sub 2}), nitric oxide (NO), nitrogen dioxide (NO{sub 2}), formaldehyde (HCHO), suspended particles, and semivolatile and nonvolatile organic compounds, including some nitrated and non-nitrated polycyclic aromatic hydrocarbons, can be emitted by kerosene heaters. Recently, several add-on catalytic devices designed to reduce some pollutant emissions have become commercially available. The tests described here were designed to measure the impact of these devices on pollutant emissions from unvented kerosene heaters. Emissions of CO, NO, NO{sub 2}, HCHO, and total suspended particles were investigated in this study. Inmore » addition, analyses of particulate sulfur and chromium were conducted for some tests.« less
The United States (U.S.) National Park Service has initiated research on the atmospheric deposition and fate of semi-volatile organic compounds in its alpine, sub-Arctic, and Arctic ecosystems in the Western U.S. Results for the analysis of pesticides in seasonal snowpack samples...
The impact of extensively used arsenic-containing herbicides on groundwater beneath golf courses has become a topic of interest. Although currently used organoarsenicals are less toxic, their application into the environment may produce the more toxic inorganic arsenicals. The ob...
Penetration of n-hexadecane and water into wood under conditions simulating catastrophic floods
Ganna Baglayeva; Wayne S. Seames; Charles R. Frihart; Jane O' Dell; Evguenii I. Kozliak
2017-01-01
To simulate fuel oil spills occurring during catastrophic floods, short-term absorption of two chemicals, n-hexadecane (representative of semivolatile organic compounds in fuel oil) and water, into southern yellow pine was gravimetrically monitored as a function of time at ambient conditions. Different scenarios were run on the basis of (1) the...
NASA Astrophysics Data System (ADS)
Moreau-Guigon, Elodie; Alliot, Fabrice; Gaspéri, Johnny; Blanchard, Martine; Teil, Marie-Jeanne; Mandin, Corinne; Chevreuil, Marc
2016-12-01
Fifty-eight semi-volatile organic compounds (SVOCs) were investigated simultaneously in three indoor (apartment, nursery and office building) and one outdoor environment in the centre of Paris (France). All of these compounds except tetrabromobisphenol A were quantified in the gaseous and particulate phases in all three environments, and at a frequency of 100% for the predominant compounds of each SVOC class. Phthalic acid esters (PAEs) were the most abundant group (di-iso-butyl phthalate: 29-661 ng m-3, diethyl phthalate: 15-542 ng m-3), followed by 4-nonylphenol (1.4-81 ng m-3), parabens (methylparaben: 0.03-2.5 ng m-3), hexachlorobenzene (HCB) (0.002-0.26 ng m-3) and pentachlorobenzene (PeCB) (0.001-0.23 ng m-3). Polycyclic aromatic hydrocarbons (as ∑8PAHs) ranged from 0.17 to 5.40 ng m-3, polychlorinated biphenyls (as ∑7PCBi) from 0.06 to 4.70 ng.m3 and polybromodiphenyl ethers (as ∑8PBDEs) from 0.002 to 0.40 ng m-3. For most pollutants, significantly higher concentrations were observed in the nursery compared to the apartment and office. Overall, the indoor air concentrations were up to ten times higher than outdoor air concentrations. Seasonal variations were observed for PAEs, PCBs and PAHs. SVOCs were predominantly identified in the gaseous phase (>90%), except for some high-molecular-weight PAEs, PAHs and PCBs.
Advanced Characterization of Semivolatile Organic Compounds Emitted from Biomass Burning
NASA Astrophysics Data System (ADS)
Hatch, L. E.; Liu, Y.; Rivas-Ubach, A.; Shaw, J. B.; Lipton, M. S.; Barsanti, K. C.
2016-12-01
Biomass burning (BB) emits large amounts of non-methane organic gases (NMOGs) and primary (directly emitted) particulate matter (PM). NMOGs also react in plume to form secondary PM (i.e., SOA) and ozone. BB-PM has been difficult to represent accurately in models used for chemistry and climate predictions, including for air quality and fire management purposes. Much recent research supports that many previously unconsidered SOA precursors exist, including oxidation of semivolatile compounds (SVOCs). Although many recent studies have characterized relatively volatile BB-derived NMOGs and relatively non-volatile particle-phase organic species, comparatively few studies have performed detailed characterization of SVOCs emitted from BB. Here we present efforts to expand the volatility and compositional ranges of compounds measured in BB smoke. In this work, samples of SVOCs in gas and particle phases were collected from 18 fires representing a range of fuel types during the 2016 FIREX fire laboratory campaign; samples were analyzed by two-dimensional gas chromatography with time-of-flight mass spectrometry (GCxGC-TOFMS) and Fourier-transform ion cyclotron resonance mass spectrometry (FTICR-MS). Hundreds of compounds were detectable in both gas and particle phases by GCxGC-TOFMS whereas thousands of peaks were present in the FTICR mass spectra. Data from both approaches highlight that chemical fingerprints of smoke are fuel/burn-dependent. These efforts support our continued research in building the understanding and model representation of BB emissions and BB-derived SOA.
Advanced Characterization of Semivolatile Organic Compounds Emitted from Biomass Burning
NASA Astrophysics Data System (ADS)
Hatch, L. E.; Liu, Y.; Rivas-Ubach, A.; Shaw, J. B.; Lipton, M. S.; Barsanti, K. C.
2017-12-01
Biomass burning (BB) emits large amounts of non-methane organic gases (NMOGs) and primary (directly emitted) particulate matter (PM). NMOGs also react in plume to form secondary PM (i.e., SOA) and ozone. BB-PM has been difficult to represent accurately in models used for chemistry and climate predictions, including for air quality and fire management purposes. Much recent research supports that many previously unconsidered SOA precursors exist, including oxidation of semivolatile compounds (SVOCs). Although many recent studies have characterized relatively volatile BB-derived NMOGs and relatively non-volatile particle-phase organic species, comparatively few studies have performed detailed characterization of SVOCs emitted from BB. Here we present efforts to expand the volatility and compositional ranges of compounds measured in BB smoke. In this work, samples of SVOCs in gas and particle phases were collected from 18 fires representing a range of fuel types during the 2016 FIREX fire laboratory campaign; samples were analyzed by two-dimensional gas chromatography with time-of-flight mass spectrometry (GCxGC-TOFMS) and Fourier-transform ion cyclotron resonance mass spectrometry (FTICR-MS). Hundreds of compounds were detectable in both gas and particle phases by GCxGC-TOFMS whereas thousands of peaks were present in the FTICR mass spectra. Data from both approaches highlight that chemical fingerprints of smoke are fuel/burn-dependent. These efforts support our continued research in building the understanding and model representation of BB emissions and BB-derived SOA.
Tight coupling of particle size and composition in atmospheric cloud droplet activation
NASA Astrophysics Data System (ADS)
Topping, D.; McFiggans, G.
2011-09-01
The substantial uncertainty in the indirect effect on radiative forcing in large part arises from the influences of atmospheric aerosol particles on (i) the brightness of clouds, exerting significant shortwave cooling with no appreciable compensation in the longwave, and on (ii) their ability to precipitate, with implications for cloud cover and lifetime. Predicting the ambient conditions at which aerosol particles may become cloud droplets is largely reliant on an equilibrium relationship derived in 1936. However, the theoretical basis of the relationship restricts its application to particles solely comprising involatile compounds and water, whereas a substantial fraction of particles in the real atmosphere will contain potentially thousands of semi-volatile organic compounds in addition to containing semi-volatile inorganic components such as ammonium nitrate. We show that equilibration of atmospherically reasonable concentrations of organic compounds with a growing particle as the ambient humidity increases has larger implications on cloud droplet formation than any other equilibrium compositional dependence, owing to inextricable linkage between the aerosol composition and a particles size under ambient conditions. Whilst previous attempts to account for co-condensation of gases other than water vapour have been restricted to one inorganic condensate, our method demonstrates that accounting for the co-condensation of any number of organic compounds substantially decreases the saturation ratio of water vapour required for droplet activation. This effect is far greater than any other compositional dependence; moreso even than the unphysical effect of surface tension reduction in aqueous organic mixtures, ignoring differences in bulk and surface surfactant concentrations.
Fontana, Ariel; Rodríguez, Isaac; Cela, Rafael
2018-04-20
The suitability of dispersive liquid-liquid microextraction (DLLME) and gas chromatography accurate mass spectrometry (GC-MS), based on a time-of-flight (TOF) MS analyzer and using electron ionization (EI), for the characterization of volatile and semi-volatile profiles of grape marc distillates (grappa) are evaluated. DLLME conditions are optimized with a selection of compounds, from different chemical families, present in the distillate spirit. Under final working conditions, 2.5 mL of sample and 0.5 mL of organic solvents are consumed in the sample preparation process. The absolute extraction efficiencies ranged from 30 to 100%, depending on the compound. For the same sample volume, DLLME provided higher responses than solid-phase microextraction (SPME) for most of the model compounds. The GC-EI-TOF-MS records of grappa samples were processed using a data mining non-targeted search algorithm. In this way, chromatographic peaks and accurate EI-MS spectra of sample components were linked. The identities of more than 140 of these components are proposed from comparison of their accurate spectra with those in a low resolution EI-MS database, accurate masses of most intense fragment ions of known structure, and available chromatographic retention index. The use of chromatographic and spectral data, associated to the set of components mined from different grappa samples, for multivariate analysis purposes is also illustrated in the study. Copyright © 2018 Elsevier B.V. All rights reserved.
Guimaraes, Wladmir B.; Falls, W. Fred; Caldwell, Andral W.; Ratliff, W. Hagan; Wellborn, John B.; Landmeyer, James E.
2011-01-01
The U.S. Geological Survey, in cooperation with the U.S. Department of the Army Environmental and Natural Resources Management Office of the U.S. Army Signal Center and Fort Gordon, Georgia, assessed the hyporheic zone, flood plain, soil gas, soil, and surface-water for contaminants at the Old Incinerator Area at Fort Gordon, from October 2009 to September 2010. The assessment included the detection of organic contaminants in the hyporheic zone, flood plain, soil gas, and surface water. In addition, the organic contaminant assessment included the analysis of explosives and chemical agents in selected areas. Inorganic contaminants were assessed in soil and surface-water samples. The assessment was conducted to provide environmental contamination data to the U.S. Army at Fort Gordon pursuant to requirements of the Resource Conservation and Recovery Act Part B Hazardous Waste Permit process. Total petroleum hydrocarbons were detected above the method detection level in all 13 samplers deployed in the hyporheic zone and flood plain of an unnamed tributary to Spirit Creek. The combined concentrations of benzene, toluene, ethylbenzene, and total xylene were detected at 3 of the 13 samplers. Other organic compounds detected in one sampler included octane and trichloroethylene. In the passive soil-gas survey, 28 of the 60 samplers detected total petroleum hydrocarbons above the method detection level. Additionally, 11 of the 60 samplers detected the combined masses of benzene, toluene, ethylbenzene, and total xylene above the method detection level. Other compounds detected above the method detection level in the passive soil-gas survey included octane, trimethylbenzene, perchlorethylene, and chloroform. Subsequent to the passive soil-gas survey, six areas determined to have relatively high contaminant mass were selected, and soil-gas samplers were deployed, collected, and analyzed for explosives and chemical agents. No explosives or chemical agents were detected above their method detection levels, but those that were detected were above the nondetection level. The same six locations that were sampled for explosives and chemical agents were selected for the collection of soil samples. No metals that exceeded the Regional Screening Levels for Industrial Soils as classified by the U.S. Environmental Protection Agency were detected at any of the six Old Incinerator Area locations. The soil samples also were compared to values from the ambient, uncontaminated (background) levels for soils in South Carolina. Because South Carolina is adjacent to Georgia and the soils in the coastal plain are similar, these comparisons are valid. No similar values are available for Georgia to use for comparison purposes. The only metal detected above the ambient background levels for South Carolina was barium. A surface-water sample collected from a tributary west and north of the Old Incinerator Area was analyzed for volatile organic compounds, semivolatile organic compounds, and inorganic compounds (metals). The only volatile organic and (or) semivolatile organic compound that was detected above the laboratory reporting level was toluene. The compounds 4-isopropyl-1-methylbenzene and isophorone were detected above the nondetection level but below the laboratory reporting level and were estimated. These compounds were detected at levels below the maximum contaminant levels set by the U.S. Environmental Protection Agency National Primary Drinking Water Standard. Iron was the only inorganic compound detected in the surface-water sample that exceeded the maximum contaminant level set by the U.S. Environmental Protection Agency National Secondary Drinking Water Standard. No other inorganic compounds exceeded the maximum contaminant levels for the U.S. Environmental Protection Agency National Primary Drinking Water Standard, National Secondary Drinking Water Standard, or the Georgia In-Stream Water Quality Standard.
Murphy, Benjamin N.; Woody, Matthew C.; Jimenez, Jose L.; ...
2017-09-20
Mounting evidence from field and laboratory observations coupled with atmospheric model analyses shows that primary combustion emissions of organic compounds dynamically partition between the vapor and particulate phases, especially as near-source emissions dilute and cool to ambient conditions. The most recent version of the Community Multiscale Air Quality model version 5.2 (CMAQv5.2) accounts for the semivolatile partitioning and gas-phase aging of these primary organic aerosol (POA) compounds consistent with experimentally derived parameterizations. We also include a new surrogate species, potential secondary organic aerosol from combustion emissions (pcSOA), which provides a representation of the secondary organic aerosol (SOA) from anthropogenic combustionmore » sources that could be missing from current chemical transport model predictions. The reasons for this missing mass likely include the following: (1) unspeciated semivolatile and intermediate volatility organic compound (SVOC and IVOC, respectively) emissions missing from current inventories, (2) multigenerational aging of organic vapor products from known SOA precursors (e.g., toluene, alkanes), (3) underestimation of SOA yields due to vapor wall losses in smog chamber experiments, and (4) reversible organic compounds–water interactions and/or aqueous-phase processing of known organic vapor emissions. CMAQ predicts the spatially averaged contribution of pcSOA to OA surface concentrations in the continental United States to be 38.6 and 23.6 % in the 2011 winter and summer, respectively. Whereas many past modeling studies focused on a particular measurement campaign, season, location, or model configuration, we endeavor to evaluate the model and important uncertain parameters with a comprehensive set of United States-based model runs using multiple horizontal scales (4 and 12 km), gas-phase chemical mechanisms, and seasons and years. The model with representation of semivolatile POA improves predictions of hourly OA observations over the traditional nonvolatile model at sites during field campaigns in southern California (CalNex, May–June 2010), northern California (CARES, June 2010), the southeast US (SOAS, June 2013; SEARCH, January and July, 2011). Model improvements manifest better correlations (e.g., the correlation coefficient at Pasadena at night increases from 0.38 to 0.62) and reductions in underprediction during the photochemically active afternoon period (e.g., bias at Pasadena from -5.62 to -2.42 µg m -3). Daily averaged predictions of observations at routine-monitoring networks from simulations over the continental US (CONUS) in 2011 show modest improvement during winter, with mean biases reducing from 1.14 to 0.73 µg m -3, but less change in the summer when the decreases from POA evaporation were similar to the magnitude of added SOA mass. Because the model-performance improvement realized by including the relatively simple pcSOA approach is similar to that of more-complicated parameterizations of OA formation and aging, we recommend caution when applying these more-complicated approaches as they currently rely on numerous uncertain parameters. The pcSOA parameters optimized for performance at the southern and northern California sites lead to higher OA formation than is observed in the CONUS evaluation. This may be due to any of the following: variations in real pcSOA in different regions or time periods, too-high concentrations of other OA sources in the model that are important over the larger domain, or other model issues such as loss processes. This discrepancy is likely regionally and temporally dependent and driven by interferences from factors like varying emissions and chemical regimes.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Murphy, Benjamin N.; Woody, Matthew C.; Jimenez, Jose L.
Mounting evidence from field and laboratory observations coupled with atmospheric model analyses shows that primary combustion emissions of organic compounds dynamically partition between the vapor and particulate phases, especially as near-source emissions dilute and cool to ambient conditions. The most recent version of the Community Multiscale Air Quality model version 5.2 (CMAQv5.2) accounts for the semivolatile partitioning and gas-phase aging of these primary organic aerosol (POA) compounds consistent with experimentally derived parameterizations. We also include a new surrogate species, potential secondary organic aerosol from combustion emissions (pcSOA), which provides a representation of the secondary organic aerosol (SOA) from anthropogenic combustionmore » sources that could be missing from current chemical transport model predictions. The reasons for this missing mass likely include the following: (1) unspeciated semivolatile and intermediate volatility organic compound (SVOC and IVOC, respectively) emissions missing from current inventories, (2) multigenerational aging of organic vapor products from known SOA precursors (e.g., toluene, alkanes), (3) underestimation of SOA yields due to vapor wall losses in smog chamber experiments, and (4) reversible organic compounds–water interactions and/or aqueous-phase processing of known organic vapor emissions. CMAQ predicts the spatially averaged contribution of pcSOA to OA surface concentrations in the continental United States to be 38.6 and 23.6 % in the 2011 winter and summer, respectively. Whereas many past modeling studies focused on a particular measurement campaign, season, location, or model configuration, we endeavor to evaluate the model and important uncertain parameters with a comprehensive set of United States-based model runs using multiple horizontal scales (4 and 12 km), gas-phase chemical mechanisms, and seasons and years. The model with representation of semivolatile POA improves predictions of hourly OA observations over the traditional nonvolatile model at sites during field campaigns in southern California (CalNex, May–June 2010), northern California (CARES, June 2010), the southeast US (SOAS, June 2013; SEARCH, January and July, 2011). Model improvements manifest better correlations (e.g., the correlation coefficient at Pasadena at night increases from 0.38 to 0.62) and reductions in underprediction during the photochemically active afternoon period (e.g., bias at Pasadena from -5.62 to -2.42 µg m -3). Daily averaged predictions of observations at routine-monitoring networks from simulations over the continental US (CONUS) in 2011 show modest improvement during winter, with mean biases reducing from 1.14 to 0.73 µg m -3, but less change in the summer when the decreases from POA evaporation were similar to the magnitude of added SOA mass. Because the model-performance improvement realized by including the relatively simple pcSOA approach is similar to that of more-complicated parameterizations of OA formation and aging, we recommend caution when applying these more-complicated approaches as they currently rely on numerous uncertain parameters. The pcSOA parameters optimized for performance at the southern and northern California sites lead to higher OA formation than is observed in the CONUS evaluation. This may be due to any of the following: variations in real pcSOA in different regions or time periods, too-high concentrations of other OA sources in the model that are important over the larger domain, or other model issues such as loss processes. This discrepancy is likely regionally and temporally dependent and driven by interferences from factors like varying emissions and chemical regimes.« less
Volatile and semivolatile organic compounds in laboratory ...
Speciated volatile organic compounds (VOCs) and organic fine particulate matter (PM2.5) mass emission factors were determined from laboratory peat fire experiments. Peat samples originated from two wildlife reserves located near the coast of North Carolina, U.S. Gas and particulate organics were quantified by gas chromatography/mass spectrometry and by high pressure liquid chromatography. Hazardous air pollutants (HAPs) accounted for a large fraction (~60 %) of the speciated VOC emissions from peat burning, including large contributions of acetaldehyde, formaldehyde, benzene, toluene, and chloromethane. Speciated organic PM2.5 mass was dominated by the following compound classes: organic acids, levoglucosan, n-alkanes, and n-alkenes. Emission factors for PM2.5 organic acids including n-alkanoic acids, n-alkenoic acids, n-alkanedioic acids, and aromatic acids were reported for the first time for peat burning, representing the largest fraction of organic carbon (OC) mass (11-12 %) of all speciated compound classes measured in this work. Levoglucosan contributed 2-3 % of the OC mass, while methoxyphenols represented 0.2-0.3 % of the OC mass on a carbon mass basis. Retene was the most abundant particulate phase polycyclic aromatic hydrocarbon. Total HAP VOC and particulate polycyclic aromatic hydrocarbon emissions from a 2008 peat wildfire in North Carolina were estimated, suggesting that peat fires can contribute a large fraction of state-wide HAP emissions. This p
Seagrave, JeanClare; McDonald, Jacob D; Gigliotti, Andrew P; Nikula, Kristen J; Seilkop, Steven K; Gurevich, Michael; Mauderly, Joe L
2002-12-01
Exposure to engine emissions is associated with adverse health effects. However, little is known about the relative effects of emissions produced by different operating conditions, fuels, or technologies. Rapid screening techniques are needed to compare the biological effects of emissions with different characteristics. Here, we examined a set of engine emission samples using conventional bioassays. The samples included combined particulate material and semivolatile organic compound fractions of emissions collected from normal- and high-emitter gasoline and diesel vehicles collected at 72 degrees F, and from normal-emitter groups collected at 30 degrees F. The relative potency of the samples was determined by statistical analysis of the dose-response curves. All samples induced bacterial mutagenicity, with a 10-fold range of potency among the samples. Responses to intratracheal instillation in rats indicated generally parallel rankings of the samples by multiple endpoints reflecting cytotoxic, inflammatory, and lung parenchymal changes, allowing selection of a more limited set of parameters for future studies. The parameters selected to assess oxidative stress and macrophage function yielded little useful information. Responses to instillation indicated little difference in potency per unit of combined particulate material and semivolatile organic compound mass between normal-emitter gasoline and diesel vehicles, or between emissions collected at different temperatures. However, equivalent masses of emissions from high-emitter vehicles of both types were more potent than those from normal-emitters. While preliminary in terms of assessing contributions of different emissions to health hazards, the results indicate that a subset of this panel of assays will be useful in providing rapid, cost-effective feedback on the biological impact of modified technology.
Zaugg, Steven D.; Burkhardt, Mark R.; Burbank, Teresa L.; Olson, Mary C.; Iverson, Jana L.; Schroeder, Michael P.
2006-01-01
A method for the determination of 38 polycyclic aromatic hydrocarbons (PAHs) and semivolatile organic compounds in solid samples is described. Samples are extracted using a pressurized solvent extraction system. The compounds of interest are extracted from the solid sample twice at 13,800 kilopascals; first at 120 degrees Celsius using a water/isopropyl alcohol mixture (50:50, volume-to-volume ratio), and then the sample is extracted at 200 degrees Celsius using a water/isopropyl alcohol mixture (80:20, volume-to-volume ratio). The compounds are isolated using disposable solid-phase extraction (SPE) cartridges containing divinylbenzene-vinylpyrrolidone copolymer resin. The cartridges are dried with nitrogen gas, and then sorbed compounds are eluted from the SPE material using a dichloromethane/diethyl ether mixture (80:20, volume-to-volume ratio) and passed through a sodium sulfate/Florisil SPE cartridge to remove residual water and to further clean up the extract. The concentrated extract is solvent exchanged into ethyl acetate and the solvent volume reduced to 0.5 milliliter. Internal standard compounds are added prior to analysis by capillary-column gas chromatography/mass spectrometry. Comparisons of PAH data for 28 sediment samples extracted by Soxhlet and the accelerated solvent extraction (ASE) method described in this report produced similar results. Extraction of PAH compounds from standard reference material using this method also compared favorably with Soxhlet extraction. The recoveries of PAHs less than molecular weight 202 (pyrene or fluoranthene) are higher by up to 20 percent using this ASE method, whereas the recoveries of PAHs greater than or equal to molecular weight 202 are equivalent. This ASE method of sample extraction of solids has advantages over conventional Soxhlet extraction by increasing automation of the extraction process, reducing extraction time, and using less solvent. Extract cleanup also is greatly simplified because SPE replaces commonly used gel permeation chromatography. The performance of the method (as expressed by mean recoveries and mean precision) was determined using Ottawa sand, a commercially available topsoil, and an environmental stream sediment, fortified at 1.5 and 15 micrograms per compound. Recoveries of PAH and semivolatile compounds in Ottawa sand samples fortified at 1.5 micrograms averaged 88 percent ? 9.4 percent relative standard deviation, and calculated initial method detection limits per compound averaged 14 micrograms per kilogram, assuming a 25-gram sample size. The recovery for 1,2,4-trichlorobenzene is less than 60 percent; thus, the concentration of this compound will always be reported as estimated with the E remark code. The analysis of 25 alkylated PAH homolog groups also can be determined with this method with extra data analysis and review, but because of the lack of authentic reference standard compounds, these results are considered to be semiquantitative. The PAH homolog groups are quantitated using the response factor of a parent PAH method compound, if available. Precision data for the alkylated PAH homologs detected in a marine sediment standard reference material (SRM 1944) also are presented to document and demonstrate method capability.
Moniruzzaman, M; Rodríguez, I; Rodríguez-Cabo, T; Cela, R; Sulaiman, S A; Gan, S H
2014-11-14
The suitability of the dispersive liquid-liquid microextraction (DLLME) technique for gas chromatography (GC) characterization of minor organic compounds in honey samples is evaluated. Under optimized conditions, samples were pre-treated by liquid-liquid extraction with acetonitrile followed by DLLME using carbon tetrachloride (CCl4, 0.075 mL) as extractant. The yielded settled phase was analyzed by GC using high resolution time-of-flight (TOF) mass spectrometry (MS). The whole sample preparation process is completed in approximately 10 min, with a total consumption of organic solvents below 4 mL, relative standard deviations lower than 12% and with more than 70 organic compounds, displaying linear retention index in the range from 990 to 2900, identified in the obtained extracts. In comparison with HS SPME extraction, higher peak intensities were attained for most volatile and semi-volatile compounds amenable to both extraction techniques. Furthermore, other species such as highly polar and water soluble benzene acids, long chain fatty acids, esters and flavonoids, which are difficult to concentrate by HS SPME, could be identified in DLLME extracts. Some of the compounds identified in DLLME extracts have been proposed as useful for samples classification and/or they are recognized as markers of honeys from certain geographic areas. Copyright © 2014 Elsevier B.V. All rights reserved.
Kay, Robert T.; Greeman, Theodore K.; Duwelius, Richard F.; King, Robin B.; Nazimek, John E.; Petrovski, David M.
1997-01-01
Industrial wastes, municipal solid wastes, steel-industry wastes, and, perhaps, dredging spoil can be associated with increased concentrations of volatile and semivolatile organic compounds, pesticides, cyanide, metals, or major ions in ground water in this area. Construction debris, ash, cinders, and natural fill may be associated with increased concentrations of major ions in ground water.
USDA-ARS?s Scientific Manuscript database
Secondary metabolites are major constituents of plant defense against herbivore attack. Relatively little is known about the cell type-specific formation and anti-herbivore activities of secondary compounds in roots despite the substantial impact of root herbivory on plant performance and fitness. ...
Liu, Xinyu; Pawliszyn, Janusz
2007-04-01
In this paper, we present results for the on-line determination of semivolatile organic compounds (SVOCs) in air using membrane extraction with a sorbent interface-ion mobility spectrometry (MESI-IMS) system with a preheated carrier (stripping) gas. The mechanism of the mass transfer of SVOCs across a membrane was initially studied. In comparison with the extraction of volatile analytes, the mass transfer resistance that originated from the slow desorption from the internal membrane surface during the SVOC extraction processes should be taken into account. A preheated carrier gas system was therefore built to facilitate desorption of analytes from the internal membrane surface. With the benefit of a temperature gradient existing between the internal and external membrane surfaces, an increase in the desorption rate of a specific analyte at the internal surface and the diffusion coefficient within the membrane could be achieved while avoiding a decrease of the distribution constant on the external membrane interface. This technique improved both the extraction rate and response times of the MESI-IMS system for the analysis of SVOCs. Finally, the MESI-IMS system was shown to be capable of on-site measurement by monitoring selected polynuclear aromatic hydrocarbons emitted from cigarette smoke.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Castaldini, C.; Waterland, L.R.
1987-03-01
The two-volume report gives results from field tests of a wood-waste-fired industrial watertube boiler. Two series of tests were performed: one firing dry (11% moisture) wood waste, and the other firing green (34% moisture) wood waste. Emission measurements included: continuous monitoring of flue-gas emissions; source-assessment sampling system (SASS) sampling of the flue gas with subsequent laboratory analysis of samples to give total flue-gas organics in two boiling-point ranges, compound category information within these ranges, specific quantitation of the semi-volatile organic priority pollutants, and flue-gas concentrations of 73 trace elements; Method 5 sampling for particulate; controlled condensation system sampling for SO/submore » 2/ and SO/sub 3/; and grab sampling of boiler mechanical collector hopper ash for inorganic composition determinations. Total organic emissions decreased from 60-135 mg/dscm firing dry wood to 2-65 mg/dscm firing green wood, in parallel with corresponding boiler CO emissions.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Castaldini, C.; Waterland, L.R.
1987-03-01
The two-volume report gives results from field tests of a wood-waste-fired industrial watertube boiler. Two series of tests were performed: one firing dry (11% moisture) wood waste, and the other firing green (34% moisture) wood waste. Emission measurements included: continuous monitoring of flue-gas emissions; source-assessment sampling system (SASS) sampling of the flue-gas with subsequent laboratory analysis of samples to give total flue-gas organics in two boiling-point ranges, compound category information within these ranges, specific quantitation of the semi-volatile organic priority pollutants, and flue gas concentrations of 73 trace elements; Method 5 sampling for particulate; controlled condensation system sampling for SO/submore » 2/ and SO/sub 3/; and grab sampling of boiler mechanical collector hopper ash for inorganic and organic composition determinations. Total organic emissions decreased from 60-135 mg/dscm firing dry wood to 2-65 mg/dscm firing green wood, in parallel with corresponding boiler CO emissions.« less
Simulating the Effects of Semivolatile Compounds on Cloud Processing of Aerosol
NASA Astrophysics Data System (ADS)
Kokkola, H.; Kudzotsa, I.; Tonttila, J.; Raatikainen, T.; Romakkaniemi, S.
2017-12-01
Aerosol removal processes largely dictate how well aerosol is transported in the atmosphere and thus the aerosol load over remote regions depends on how effectively aerosol is removed during its transport from the source regions. This means that in order to model the global distribution aerosol, both in vertical and horizontal, wet deposition processes have to be properly modelled. However, in large scale models, the description of wet removal and the vertical redistribution of aerosol by cloud processes is often extremely simplified.Here we present a novel aerosol-cloud model SALSA, where the aerosol properties are tracked through different cloud processes. These processes include: cloud droplet activation, precipitation formation, ice nucleation, melting, and evaporation. It is a sectional model that includes separate size sections for non-activated aerosol, cloud droplets, precipitation droplets, and ice crystals. The aerosol-cloud model was coupled to a large eddy model UCLALES which simulates the boundary-layer dynamics. In this study, the model has been applied in studying the wet removal as well as interactions between aerosol, clouds, and semi-volatile compounds, ammonia and nitric acid. These semi-volative compounds are special in the sense that they co-condense together with water during cloud activation and have been suggested to form droplets that can be considered cloud-droplet-like already in subsaturated conditions. In our model, we calculate the kinetic partitioning of ammonia and sulfate thus explicitly taking into account the effect of ammonia and nitric acid in the cloud formation. Our simulations indicate that especially in polluted conditions, these compounds significantly affect the properties of cloud droplets thus significantly affecting the lifecycle of different aerosol compounds.
Valentão, Patrícia; Gonçalves, Rui F; Belo, Cristóvão; de Pinho, Paula Guedes; Andrade, Paula B; Ferreres, Federico
2010-10-01
Piper betle is a species growing in South East Asia, where its leaves are economically and medicinally important. To screen the highest possible number of volatile and semivolatile components, the leaves were subjected to headspace solid-phase microextraction, hydrodistillation and Soxhlet extraction, prior to analysis by GC/MS. Fifty compounds (identified by comparison with standard compounds or tentatively by National Institute of Standards and Technology database) were determined, 23 being described for the first time in this matrix. An aqueous extract was also analysed, in which only seven compounds were characterized. The organic acids' composition of this extract was determined by HPLC/UV and eight compounds are reported for the first time in P. betle. This extract also displayed acetylcholinesterase inhibitory capacity.
Chemical sensing of plant stress at the ecosystem scale
NASA Astrophysics Data System (ADS)
Karl, T.; Guenther, A.; Turnipseed, A.; Patton, E. G.; Jardine, K.
2008-09-01
Significant ecosystem-scale emissions of methylsalicylate (MeSA), a semivolatile plant hormone thought to act as the mobile signal for systemic acquired resistance (SAR), were observed in an agroforest. Our measurements show that plant internal defence mechanisms can be activated in response to temperature stress and are modulated by water availability on large scales. Highest MeSA fluxes (up to 0.25 mg/m2/h) were observed after plants experienced ambient night-time temperatures of ~7.5°C followed by a large daytime temperature increase (e.g. up to 22°C). Under these conditions estimated night-time leaf temperatures were as low as ~4.6°C, likely inducing a response to prevent chilling injury. Our observations imply that plant hormones can be a significant component of ecosystem scale volatile organic compound (VOC) fluxes (e.g. as high as the total monoterpene (MT) flux) and therefore contribute to the missing VOC budget. If generalized to other ecosystems and different types of stresses these findings suggest that semivolatile plant hormones have been overlooked by investigations of the impact of biogenic VOCs on aerosol formation events in forested regions. Our observations show that the presence of MeSA in canopy air serves as an early chemical warning signal indicating ecosystem-scale stresses before visible damage becomes apparent. As a chemical metric, ecosystem emission measurements of MeSA in ambient air could therefore support field studies investigating factors that adversely affect plant growth.
NASA Astrophysics Data System (ADS)
Alliot, Fabrice; Moreau-Guigon, Elodie; Bourges, Catherine; Desportes, Annie; Teil, Marie-Jeanne; Blanchard, Martine; Chevreuil, Marc
2014-08-01
A number of semi-volatile compounds occur in indoor air most of them being considered as potent endocrine disruptors and thus, exerting a possible impact upon health. To assess their concentration levels in indoor air, we developed and validated a method for sampling and multi-residue analysis of 58 compounds including phthalates, polycyclic aromatic hydrocarbons (PAHs), polybromodiphenylethers (PBDEs), polychlorobiphenyls (PCBs), parabens, bisphenol A (BPA) and tetrabromobisphenol A (TBBPA) in gaseous and particulate phases of air. We validated each step of procedures from extraction until analysis. Matrice spiking were performed at extraction, fractionation and purification stages. The more volatile compounds were analyzed with a gas chromatography system coupled with a mass spectrometer (GC/MS) or with a tandem mass spectrometer (GC/MS/MS). The less volatile compounds were analyzed with a liquid chromatography system coupled with a tandem mass spectrometer (LC/MS/MS). Labeled internal standard method was used ensuring high quantification accuracy. The instrumental detection limits were under 1 pg for all compounds and therefore, a limit of quantification averaging 1 pg m-3 for the gaseous and the particulate phases and a volume of 150 m3, except for phthalates, phenol compounds and BDE-209. Satisfactory recoveries were found except for phenol compounds. That method was successfully applied to several indoor air samples (office, apartment and day nursery) and most of the targeted compounds were quantified, mainly occurring in the gaseous phase. The most abundant were phthalates (up to 918 ng m-3 in total air), followed by PCBs > parabens > BPA > PAHs > PBDEs.
NASA Astrophysics Data System (ADS)
Octaviani, Mega; Tost, Holger; Lammel, Gerhard
2017-04-01
Polycyclic aromatic hydrocarbons (PAHs) are emitted by incomplete combustion from fossil fuel, vehicles, and biomass burning. They may persist in environmental compartments, pose a health hazard and may bio accumulate along food chains. The ECHAM/MESSy Atmospheric Chemistry (EMAC) model had been used to simulate global tropospheric, stratospheric chemistry and climate. In this study, we improve the model to include simulations of the transport and fate of semi-volatile organic compounds (SVOC). The EMAC-SVOC model takes into account essential environmental processes including gas-particle partitioning, dry and wet deposition, chemical and bio-degradation, and volatilization from sea surface, soils, vegetation, and snow. The model was evaluated against observational data in the Arctic, mid-latitudes, and tropics, and further applied to study total environmental lifetime and long-range transport potential (LRTP) of PAHs. We selected four compounds for study, spanning a wide range of volatility, i.e., phenanthrene, fluoranthene, pyrene, and benzo[a]pyrene. Several LRTP indicators were investigated, including the Arctic contamination potential, meridional spreading, and zonal and meridional fluxes to remote regions.
Comprehensive characterization of atmospheric organic carbon at a forested site
NASA Astrophysics Data System (ADS)
Hunter, James F.; Day, Douglas A.; Palm, Brett B.; Yatavelli, Reddy L. N.; Chan, Arthur W. H.; Kaser, Lisa; Cappellin, Luca; Hayes, Patrick L.; Cross, Eben S.; Carrasquillo, Anthony J.; Campuzano-Jost, Pedro; Stark, Harald; Zhao, Yunliang; Hohaus, Thorsten; Smith, James N.; Hansel, Armin; Karl, Thomas; Goldstein, Allen H.; Guenther, Alex; Worsnop, Douglas R.; Thornton, Joel A.; Heald, Colette L.; Jimenez, Jose L.; Kroll, Jesse H.
2017-10-01
Atmospheric organic compounds are central to key chemical processes that influence air quality, ecological health, and climate. However, longstanding difficulties in predicting important quantities such as organic aerosol formation and oxidant lifetimes indicate that our understanding of atmospheric organic chemistry is fundamentally incomplete, probably due in part to the presence of organic species that are unmeasured using standard analytical techniques. Here we present measurements of a wide range of atmospheric organic compounds--including previously unmeasured species--taken concurrently at a single site (a ponderosa pine forest during summertime) by five state-of-the-art mass spectrometric instruments. The combined data set provides a comprehensive characterization of atmospheric organic carbon, covering a wide range in chemical properties (volatility, oxidation state, and molecular size), and exhibiting no obvious measurement gaps. This enables the first construction of a measurement-based local organic budget, highlighting the high emission, deposition, and oxidation fluxes in this environment. Moreover, previously unmeasured species, including semivolatile and intermediate-volatility organic species (S/IVOCs), account for one-third of the total organic carbon, and (within error) provide closure on both OH reactivity and potential secondary organic aerosol formation.
Role of the microbial population on the flavor of the soft-bodied cheese Torta del Casar.
Ordiales, Elena; Martín, Alberto; Benito, María José; Hernández, Alejandro; Ruiz-Moyano, Santiago; Córdoba, María de Guía
2013-09-01
The purpose of this work was to investigate the influence of the spontaneous microbial population on the flavor of Torta del Casar cheese. A total of 16 batches of cheeses with different microbial qualities were used. Their physicochemical and microbial characteristics were evaluated during ripening and then related with the volatile compounds, taste, and flavor properties of the finished cheeses. Acids were the most abundant volatile compounds, followed by alcohols and carbonyls. The amount of acetic acid and several alcohols were linked to cheeses with higher counts of lactic acid bacteria (LAB), whereas Enterobacteriaceae counts were associated with semivolatile fatty acids. The gram-positive catalase-positive cocci counts were correlated with esters and methyl ketones. Although the role of the LAB in the flavor development of Torta del Casar is the most relevant, other microbial groups are necessary to impart the flavor of the cheese and to minimize the possible off-flavor derived from excessive concentrations of LAB metabolites, such as acetic acid. Copyright © 2013 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.
Sullivan, Daniel J.; Stinson, Troy W.; Crawford, J. Kent; Schmidt, Arthur R.; Colman, John A.
1998-01-01
The distribution of pesticides and other synthetic organic compounds in water, sediment, and biota in the upper Illinois River Basin in Illinois, Indiana, and Wisconsin was examined from 1987 through 1990 as part of the pilot National Water-Quality Assesssment Program conducted by the U.S. Geological Survey. Historical data for water and sediment collected from 1975 through 1986 were similar to data collected from 1987 through 1990. Some compounds were detected in concentrations that exceed U.S. Environmental Protection Agency water-quality criteria. Results from pesticide sampling at four stations in 1988 and 1989 identified several agricultural pesticides that were detected more frequently and at higher concentrations in urban areas than in agricultural areas. Results from herbicide sampling at 17 stations in the Kankakee and Iroquois River Basins in 1990 indicated that atrazine concentrations exceeded the U.S. Environmental Protection Agency's maximum contaminant level for drinking water during runoff periods. Results from sampling for volatile and semivolatile organic compounds in water indicate that, with one exception, all stations at which more than one compound was detected were within 2 miles downstream from the nearest point source. Detections at two stations in the Chicago urban area accounted for 37 percent of the total number of detections. Concentrations of tetrachloroethylene, trichloroethylene, and 1,2-dichlorethane from stations in the Des Plaines River Basin exceeded the U.S. Environmental Protection Agency's maximum contaminant level for drinking water in one and two samples from the two stations in the Chicago area. Phenols and pentachlorophenols were detected most frequently in the Des Plaines River Basin where point-source discharges were common. Phenol concentrations were significantly different among the Des Plaines, Kankakee, and Fox River Basins. Phenols and pentachlorophenols never exceeded the general use and secondary contact standards. Results from a 1989 synoptic survey of semivolatile organic compounds in sediment indicate that these compounds were detected most frequently at sites in the Chicago urban area. Of the 17 stations at which 10 or more compounds were detected, 14 were located in the Des Plaines River subbasin, and 1 was on the Illinois River mainstem. As was the case with organic compounds in water, each of these sites was located within 2 miles downstream from point sources. Biota samples were collected and analyzed for organochlorines and polynuclear aromatic hydrocarbons in 1989 and 1990. The most commonly detected compound in both years was p,p'-DDE. National Academy of Science recommendations for chlordane and dieldrin for protection of predators were exceeded in 19 and 10 samples, respectively, when the 1989 and 1990 data were combined. In the nine fish-fillet samples collected in 1989, concentrations exceeded U.S. Environmental Protection Agency fish-tissue criteria in nine fillets for p,p'-DDE and five fillets for dieldrin.
Chalmers, Ann
2002-01-01
Streambed sediment and fish tissue were collected at 14 river sites in eastern New England during low-flow conditions in 1998 and 1999 as part of the New England Coastal Basins (NECB) study of the U.S. Geological Survey National Water-Quality Assessment (NAWQA) Program. Sampling sites were selected over a range of urban settings. Population densities at selected sites ranged from 26 to 3,585 people per square mile, and urban land use ranged from 1 to 68 percent. The streambed sediment samples were analyzed for a total of 141 contaminants, including 45 trace elements, 32 organochlorine compounds, and 64 semi-volatile organic compounds. The fish tissue samples were analyzed for 22 trace elements and 28 organochlorine compounds. Concentrations of selected contaminants in both streambed sediment and fish tissue correlated more strongly with population density than with other watershed characteristics. Cadmium, copper, lead, mercury, zinc, total polycyclic aromatic hydrocarbons (PAHs), total polychlorinated biphenyls (PCBs), dichloro diphenyl trichloroethane and metabolites (DDTM), and total chlordane in streambed sediment all showed strong positive correlations with population density (rho = 0.71 to 0.85, p value = 0.005 to <0.001). Correlations between population density and selected contaminants in fish tissue were less significant than with streambed sediment (rho = 0.62 to 0.72, p value = 0.03 to 0.008). Organic carbon concentrations were correlated with concentrations of arsenic, selenium, total PAHs, total PCBs, and DDTM in streambed sediment. The relation between concentrations of contaminants in streambed sediment and fish tissue was stronger for organochlorine compounds (rho = 0.75 to 0.55, p = 0.005 to 0.065) than for trace elements (rho = 0.63 to 0.53, p = 0.029 to 0.069). The NECB study area had the highest median concentrations of lead, mercury, total PAHs, total PCBs, and DDTM in streambed sediment and the highest median concentration of PCBs in fish tissue compared to 45 other NAWQA study units across the Nation. Concentrations of many of these constituents in streambed sediment also were frequently above the consensus-based Sediment-Quality Guidelines for the protection of wildlife, suggesting they are a threat to the health of aquatic biota in New England.
Illicit psychotropic substance contents in the air of Italy
NASA Astrophysics Data System (ADS)
Cecinato, Angelo; Balducci, Catia; Budetta, Valentina; Pasini, Antonello
2010-06-01
Two in-field campaigns were performed in 2009 to elucidate the contents of illicit psychotropic substances in airborne particulates of Italian cities. Twenty-eight localities of eight Italian regions were investigated in winter, and further eleven sites in June (14 regions in total), thanks to contribution of Regional Environmental Agencies. Cocaine was found almost everywhere, although some sites were rural or suburban. The maximum was recorded in Milan in winter (˜0.39 ng m -3), and "high" values (up to ˜0.16 ng m -3) in other Northern cities and in Rome. Besides cocaine, three cannabinoids will be monitored, namely Δ 9-tetrahydrocannabinol, cannabidiol and cannabinol. The three compounds often affected the air at lower extents than cocaine, and sometimes resulted absent. Cannabinol accounted for up to 90% of the total. The concentrations of illicit compounds were up to six times lower in June than in winter. This decrease was probably induced by the lowering of boundary layer height typical of winter, and by the oxidizing capacity of atmosphere, which is stronger in the warm season. Compared to n-alkanes, polynuclear aromatic compounds, nicotine, caffeine and airborne particulate, cocaine seemed to follow a peculiar behaviour; in fact, meaningful (≥0.80) Pearson (linear) regression coefficients were calculated from the corresponding concentrations only at local scale (e.g. Rome), and within just one season. Improvements of the method are needed to monitor illicit drug metabolites (e.g. benzoylecgonine, ecgonine methyl ester, 9-carboxy-11-nor-Δ 9-tetrahydrocannabinol), heroin and semi-volatile amphetamines.
A Novel Inlet System for On-line Chemical Analysis of Semi-Volatile Submicron Particulate Matter
NASA Astrophysics Data System (ADS)
Wisthaler, A.; Eichler, P.; Müller, M.
2015-12-01
Semi-volatile organic molecules bound to particles are difficult to measure, especially if they are reactive in nature. Any technique based on aerosol collection onto a substrate generates sampling artifacts due to surface reactions and ad- and desorption of semi-volatile analytes. On-line sampling without sample pre-collection, as for example implemented in the AMS, has greatly reduced many sampling artifacts. AMS measurements of organics do, however, suffer from the drawback that molecular-level information is, in most cases, lost during hard ionization events. As a consequence, only little speciated and thus mechanistically informative data on organic matter is obtained. PTR-ToF-MS is a well-established on-line measurement technique for gas-phase organics. Soft ionization via gas-phase hydronium ions preserves, to a large extent, molecular-level information and thus allows identifying organic compounds at an elemental composition level. We have recently developed a particle inlet system for PTR-ToF-MS instruments (doi:10.5194/amt-8-1353-2015). The CHARON ("Chemical Analysis of Aerosol On-line") inlet consists of a gas-phase denuder, an aerodynamic lens and a thermodesorption unit. In its latest version, it includes a heatable tube upstream of the denuder to form a thermodenuder. Over the last year, the CHARON PTR-ToF-MS system has been successfully used in a series of measurement campaigns to characterize i) POA emitted from a marine diesel engine, ii) SOA generated from the photo-oxidation of toluene, iii) SOA generated from the photo-oxidation of selected amines, iv) ambient aerosol in two major European cities and v) SOA generated from the photo-oxidation of biogenic VOCs. These measurements have demonstrated that the CHARON PTR-ToF-MS system i) generates on-line and real-time elemental composition information of semi-volatile organics in submicron particles (both POA and SOA), ii) detects 80-100 % of the organic mass as measured by the AMS and iii) generates volatility information of semi-volatile organics at an elemental composition level. Selected application examples will be shown.
Review of the fate and transformation of per- and polyfluoroalkyl substances (PFASs) in landfills.
Hamid, Hanna; Li, Loretta Y; Grace, John R
2018-04-01
A critical review of existing publications is presented i) to summarize the occurrence of various classes of per- and polyfluoroalkyl substances (PFASs) and their sources in landfills, ii) to identify temporal and geographical trends of PFASs in landfills; iii) to delineate the factors affecting PFASs in landfills; and iv) to identify research gaps and future research directions. Studies have shown that perfluoroalkyl acids (PFAAs) are routinely detected in landfill leachate, with short chain (C4-C7) PFAAs being most abundant, possibly indicating their greater mobility, and reflecting the industrial shift towards shorter-chain compounds. Despite its restricted use, perfluorooctanoic acid (PFOA) remains one of the most abundant PFAAs in landfill leachates. Recent studies have also documented the presence of PFAA-precursors (e.g., saturated and unsaturated fluorotelomer carboxylic acids) in landfill leachates at concentrations comparable to, or higher than, the most frequently detected PFAAs. Landfill ambient air also contains elevated concentrations of PFASs, primarily semi-volatile precursors (e.g., fluorotelomer alcohols) compared to upwind control sites, suggesting that landfills are potential sources of atmospheric PFASs. The fate of PFASs inside landfills is controlled by a combination of biological and abiotic processes, with biodegradation releasing most of the PFASs from landfilled waste to leachate. Biodegradation in simulated anaerobic reactors has been found to be closely related to the methanogenic phase. The methane-yielding stage also results in higher pH (>7) of leachates, correlated with higher mobility of PFAAs. Little information exists regarding PFAA-precursors in landfills. To avoid significant underestimation of the total PFAS released from landfills, PFAA-precursors and their degradation products should be determined in future studies. Owing to the semi-volatile nature of some precursor compounds and their degradation products, future studies also need to include landfill gas to clarify degradation pathways and the overall fate of PFASs. Copyright © 2017 Elsevier Ltd. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Not Available
1993-08-10
The Skinner Landfill is a former landfill in West Chester, Butler County, Ohio. On-site soil, groundwater, and surface water are contaminated with volatile organic compounds (VOCs), semivolatile organic compounds, pesticides, arsenic, and lead. Off-site contamination is minimal. The Skinner Landfill site poses an indeterminate public health hazard. Potential exposure pathways of concern are the ingestion of surface soils containing lead and the ingestion of VOCs in groundwater. Groundwater is a potential exposure pathway because there are uncertainties concerning the potential for contaminated groundwater to move off site.
DOE Office of Scientific and Technical Information (OSTI.GOV)
DOE /NV
1999-03-26
The Corrective Action Investigation Plan for Corrective Action Unit 428, Area 3 Septic Waste Systems 1 and 5, has been developed in accordance with the Federal Facility Agreement and Consent Order that was agreed to by the U. S. Department of Energy, Nevada Operations Office; the State of Nevada Division of Environmental Protection; and the U. S. Department of Defense. Corrective Action Unit 428 consists of Corrective Action Sites 03- 05- 002- SW01 and 03- 05- 002- SW05, respectively known as Area 3 Septic Waste System 1 and Septic Waste System 5. This Corrective Action Investigation Plan is used inmore » combination with the Work Plan for Leachfield Corrective Action Units: Nevada Test Site and Tonopah Test Range, Nevada , Rev. 1 (DOE/ NV, 1998c). The Leachfield Work Plan was developed to streamline investigations at leachfield Corrective Action Units by incorporating management, technical, quality assurance, health and safety, public involvement, field sampling, and waste management information common to a set of Corrective Action Units with similar site histories and characteristics into a single document that can be referenced. This Corrective Action Investigation Plan provides investigative details specific to Corrective Action Unit 428. A system of leachfields and associated collection systems was used for wastewater disposal at Area 3 of the Tonopah Test Range until a consolidated sewer system was installed in 1990 to replace the discrete septic waste systems. Operations within various buildings at Area 3 generated sanitary and industrial wastewaters potentially contaminated with contaminants of potential concern and disposed of in septic tanks and leachfields. Corrective Action Unit 428 is composed of two leachfield systems in the northern portion of Area 3. Based on site history collected to support the Data Quality Objectives process, contaminants of potential concern for the site include oil/ diesel range total petroleum hydrocarbons, and Resource Conservation and Recovery Act characteristic volatile organic compounds, semivolatile organic compounds, and metals. A limited number of samples will be analyzed for gamma- emitting radionuclides and isotopic uranium from four of the septic tanks and if radiological field screening levels are exceeded. Additional samples will be analyzed for geotechnical and hydrological properties and a bioassessment may be performed. The technical approach for investigating this Corrective Action Unit consists of the following activities: (1) Perform video surveys of the discharge and outfall lines. (2) Collect samples of material in the septic tanks. (3) Conduct exploratory trenching to locate and inspect subsurface components. (4) Collect subsurface soil samples in areas of the collection system including the septic tanks and outfall end of distribution boxes. (5) Collect subsurface soil samples underlying the leachfield distribution pipes via trenching. (6) Collect surface and near- surface samples near potential locations of the Acid Sewer Outfall if Septic Waste System 5 Leachfield cannot be located. (7) Field screen samples for volatile organic compounds, total petroleum hydrocarbons, and radiological activity. (8) Drill boreholes and collect subsurface soil samples if required. (9) Analyze samples for total volatile organic compounds, total semivolatile organic compounds, total Resource Conservation and Recovery Act metals, and total petroleum hydrocarbons (oil/ diesel range organics). Limited number of samples will be analyzed for gamma- emitting radionuclides and isotopic uranium from particular septic tanks and if radiological field screening levels are exceeded. (10) Collect samples from native soils beneath the distribution system and analyze for geotechnical/ hydrologic parameters. (11) Collect and analyze bioassessment samples at the discretion of the Site Supervisor if total petroleum hydrocarbons exceed field- screening levels.« less
Semivolatile compounds in schools and their influence on cognitive performance of children.
Hutter, Hans-Peter; Haluza, Daniela; Piegler, Kathrin; Hohenblum, Philipp; Fröhlich, Marina; Scharf, Sigrid; Uhl, Maria; Damberger, Bernhard; Tappler, Peter; Kundi, Michael; Wallner, Peter; Moshammer, Hanns
2013-08-01
WHO's Children's Environment and Health Action Plan for Europe (CEHAPE) focuses on improvements of indoor environments where children spend most of their time. To investigate the relationship between school indoor air pollutants and cognitive performance in elementary school children, a multidisciplinary study was planned in all-day schools in Austria. In a cross-sectional study (LuKi study: Air and Children) indoor air pollutants were monitored in nine elementary all-day schools in urban and rural regions of Austria. In addition, school dust and suspended particulates (PM10, PM2.5) were measured, focusing on semivolatile compounds (e.g. phthalates, phosphororganic compounds [POC]). Health status and environmental conditions were determined by parents' questionnaire, cognitive function was measured by Standard Progressive Matrices (SPM). Overall, 596 children (6-8 years of age) were eligible for the study. Cognitive tests were performed in 436 children. Analysis showed significant correlations of tris(2-chlorethyl)-phosphate (TCEP) in PM10 and PM2.5 and school dust samples with cognitive performance. Cognitive performance decreased with increasing concentrations of TCEP. Furthermore, cognitive function decreased significantly with increasing CO2 levels. POC are widely used as plasticizers, flame retardants and floor sealing. This is the first report of a correlation between TCEP in indoor air samples and impairment of cognitive performance in school children. As a precautionary measure, it is recommended to prohibit the use of toxic chemicals and those suspected of a toxic potential in children's environments such as schools.
Stocker, Judith; Scheringer, Martin; Wegmann, Fabio; Hungerbuhler, Konrad
2007-09-01
Snow and ice have been implemented in a global multimedia box model to investigate the influence of these media on the environmental fate and long-range transport (LRT) of semivolatile organic compounds (SOCs). Investigated compounds include HCB, PCB28, PCB180, PBDE47, PBDE209, alpha-HCH, and dacthal. In low latitudes, snow acts as a transfer medium taking up chemicals from air and releasing them to water or soil during snowmelt. In high latitudes, snow and ice shield water, soil, and vegetation from chemical deposition. In the model version including snow and ice (scenario 2), the mass of chemicals in soil in high latitudes is between 27% (HCB) and 97% (alpha-HCH) of the mass calculated with the model version without snow and ice (scenario 1). Amounts in Arctic seawater in scenario 2 are 8% (alpha-HCH) to 21% (dacthal) of the amounts obtained in scenario 1. For all investigated chemicals except alpha-HCH, presence of snow and ice in the model increases the concentration in air by a factor of 2 (HCB)to 10 (PBDE209). Because of reduced net deposition to snow-covered surfaces in high latitudes, LRT to the Arctic is reduced for most chemicals whereas transport to the south is more pronounced than in scenario 1 ("southward shift"). The presence of snow and ice thus considerably changes the environmental fate of SOCs.
Hertz-Schünemann, Romy; Streibel, Thorsten; Ehlert, Sven; Zimmermann, Ralf
2013-09-01
A micro-probe (μ-probe) gas sampling device for on-line analysis of gases evolving in confined, small objects by single-photon ionisation time-of-flight mass spectrometry (SPI-TOFMS) was developed. The technique is applied for the first time in a feasibility study to record the formation of volatile and flavour compounds during the roasting process within (inside) or in the direct vicinity (outside) of individual coffee beans. A real-time on-line analysis of evolving volatile and semi-volatile organic compounds (VOC and SVOC) as they are formed under the mild pyrolytic conditions of the roasting process was performed. The soft-ionisation mass spectra depict a molecular ion signature, which is well corresponding with the existing knowledge of coffee roasting and evolving compounds. Additionally, thereby it is possible to discriminate between Coffea arabica (Arabica) and Coffea canephora (Robusta). The recognized differences in the roasting gas profiles reflect the differences in the precursor composition of the coffee cultivars very well. Furthermore, a well-known set of marker compounds for Arabica and Robusta, namely the lipids kahweol and cafestol (detected in their dehydrated form at m/z 296 and m/z 298, respectively) were observed. If the variation in time of different compounds is observed, distinctly different evolution behaviours were detected. Here, phenol (m/z 94) and caffeine (m/z 194) are exemplary chosen, whereas phenol shows very sharp emission peaks, caffeine do not have this highly transient behaviour. Finally, the changes of the chemical signature as a function of the roasting time, the influence of sampling position (inside, outside) and cultivar (Arabica, Robusta) is investigated by multivariate statistics (PCA). In summary, this pilot study demonstrates the high potential of the measurement technique to enhance the fundamental knowledge of the formation processes of volatile and semi-volatile flavour compounds inside the individual coffee bean.
Demonstration of the Gore Module for Passive Ground Water Sampling
2014-06-01
ix ACRONYMS AND ABBREVIATIONS % RSD percent relative standard deviation 12DCA 1,2-dichloroethane 112TCA 1,1,2-trichloroethane 1122TetCA...Analysis of Variance ROD Record of Decision RSD relative standard deviation SBR Southern Bush River SVOC semi-volatile organic compound...replicate samples had a relative standard deviation ( RSD ) that was 20% or less. For the remaining analytes (PCE, cDCE, and chloroform), at least 70
Davie-Martin, Cleo L; Hageman, Kimberly J; Chin, Yu-Ping; Rougé, Valentin; Fujita, Yuki
2015-09-01
Soil-air partition coefficient (Ksoil-air) values are often employed to investigate the fate of organic contaminants in soils; however, these values have not been measured for many compounds of interest, including semivolatile current-use pesticides. Moreover, predictive equations for estimating Ksoil-air values for pesticides (other than the organochlorine pesticides) have not been robustly developed, due to a lack of measured data. In this work, a solid-phase fugacity meter was used to measure the Ksoil-air values of 22 semivolatile current- and historic-use pesticides and their degradation products. Ksoil-air values were determined for two soils (semiarid and volcanic) under a range of environmentally relevant temperature (10-30 °C) and relative humidity (30-100%) conditions, such that 943 Ksoil-air measurements were made. Measured values were used to derive a predictive equation for pesticide Ksoil-air values based on temperature, relative humidity, soil organic carbon content, and pesticide-specific octanol-air partition coefficients. Pesticide volatilization losses from soil, calculated with the newly derived Ksoil-air predictive equation and a previously described pesticide volatilization model, were compared to previous results and showed that the choice of Ksoil-air predictive equation mainly affected the more-volatile pesticides and that the way in which relative humidity was accounted for was the most critical difference.
Ghidotti, Michele; Fabbri, Daniele; Mašek, Ondřej; Mackay, Colin Logan; Montalti, Marco; Hornung, Andreas
2017-06-06
Water-soluble organic compounds (WSOCs) were extracted from corn stalk biochar produced at increasing pyrolysis temperatures (350-650 °C) and from the corresponding vapors, collected as bio-oil. WSOCs were characterized by gas chromatography (semivolatile fraction), negative electron spray ionization high resolution mass spectrometry (hydrophilic fraction) and fluorescence spectroscopy. The pattern of semivolatile WSOCs in bio-oil was dominated by aromatic products from lignocellulose, while in biochar was featured by saturated carboxylic acids from hemi/cellulose and lipids with concentrations decreasing with decreasing H/C ratios. Hydrophilic species in poorly carbonized biochar resembled those in bio-oil, but the increasing charring intensity caused a marked reduction in the molecular complexity and degree of aromaticity. Differences in the fluorescence spectra were attributed to the predominance of fulvic acid-like structures in biochar and lignin-like moieties in bio-oil. The divergence between pyrolysis vapors and biochar in the distribution of WSOCs with increasing carbonization was explained by the hydrophobic carbonaceous matrix acting like a filter favoring the release into water of carboxylic and fulvic acid-like components. The formation of these structures was confirmed in biochar produced by pilot plant pyrolysis units. Biochar affected differently shoot and root length of cress seedlings in germination tests highlighting its complex role on plant growth.
Detection of semi-volatile organic compounds in permeable ...
Abstract The Edison Environmental Center (EEC) has a research and demonstration permeable parking lot comprised of three different permeable systems: permeable asphalt, porous concrete and interlocking concrete permeable pavers. Water quality and quantity analysis has been ongoing since January, 2010. This paper describes a subset of the water quality analysis, analysis of semivolatile organic compounds (SVOCs) to determine if hydrocarbons were in water infiltrated through the permeable surfaces. SVOCs were analyzed in samples collected from 11 dates over a 3 year period, from 2/8/2010 to 4/1/2013.Results are broadly divided into three categories: 42 chemicals were never detected; 12 chemicals (11 chemical test) were detected at a rate of less than 10% or less; and 22 chemicals were detected at a frequency of 10% or greater (ranging from 10% to 66.5% detections). Fundamental and exploratory statistical analyses were performed on these latter analyses results by grouping results by surface type. The statistical analyses were limited due to low frequency of detections and dilutions of samples which impacted detection limits. The infiltrate data through three permeable surfaces were analyzed as non-parametric data by the Kaplan-Meier estimation method for fundamental statistics; there were some statistically observable difference in concentration between pavement types when using Tarone-Ware Comparison Hypothesis Test. Additionally Spearman Rank order non-parame
Modeling study of secondary organic aerosol in winter in China using NAQPMS
NASA Astrophysics Data System (ADS)
Yang, W.; Li, J.
2017-12-01
The concentration of organic aerosol (OA) in the central and eastern China is much higher than that in Europe and America. Compared with the observation, the current numerical modeling studies largely underestimated the concentration of OA, especially the secondary component. Based on the volatility basis set framework, a secondary organic aerosol (SOA) module was developed, which considering the multi-generation oxidation of volatile organic compounds (VOCs), semi-volatile POA and intermediate volatility organic compounds (IVOCs). The newly developed SOA module was coupled into the NAQPMS, and the performance of the simulation was validated by the observation with high temporal resolution. In wintertime, the OA concentration in the central and eastern China was maintained above 15-20 μg·m-3, and SOA accounted for 50-65% of OA concentration. The OA concentration even reached 40 μg·m-3 in the provinces emitting most pollutants (such as Hunan, Hubei, Henan, Anhui, Jiangsu, Shandong and Hubei province). IVOCs were important precursors of SOA in China, and could reduce the great discrepancy between simulation and observation. In wintertime, the contribution from IVOCs accounted for 60-80% of SOA formation. The aging of semi-volatile POA had less impact on the SOA formation, which maintained only 2-8% over central and eastern China.
Stashenko, Elena E; Andrés Ordóñez, Sergio; Marín, Néstor Armando; Martínez, Jairo René
2009-10-01
Volatile and semi-volatile secondary metabolites, as well as aristolochic acids (AA), present in leaves, stems, and flowers of Aristolochia ringens were determined by gas chromatography (GC)-mass spectrometry (MS) and high-performance liquid chromatography (HPLC) methods, respectively. Metabolite isolation was performed using different extraction techniques: microwave-assisted hydrodistillation (MWHD), supercritical fluid extraction, and headspace solid-phase microextraction (HS-SPME). The chemical composition of the extracts and oils was established by GC-MS. The determinations of AAI and AAII were conducted by methanolic extraction of different plant parts followed by HPLC analysis. Essential oil yields from leaves and stems were 0.008 +/- 0.0022% and 0.047 +/- 0.0026%, respectively. Aristolochia ringens flowers did not yield essential oil under MWHD. Sesquiterpene hydrocarbons (66%) were the main compounds in the essential oil isolated from leaves whereas monoterpene hydrocarbons (73%) predominated in the stems essential oil. Yields of extracts isolated by SFE from leaves, stems, and flowers were 4 +/- 1.8%, 1.2 +/- 0.25%, and 4 +/- 1.8%, respectively. In vivo HS-SPME of flowers isolated compounds with known unpleasant smells such as volatile aldehydes and short-chain carboxylic acids. HPLC analysis detected the presence of AAII in the flowers of Aristolochia ringens at a concentration of 610 +/- 47 mg/kg of dried flower.
Beaulieu, John C; Lea, Jeanne M
2006-10-04
Seedless triploid watermelons have increased in popularity since the early 1990s, and the demand for seedless fruit is on the rise. Sweetness and sugars are crucial breeding focuses for fruit quality. Volatiles also play an important role; yet, we found no literature for seedless varieties and no reports using solid-phase microextraction (SPME) in watermelon. The objective of this experiment was to identify volatile and semivolatile compounds in five seedless watermelon varieties using carboxen divinylbenzene polydimethylsiloxane solid-phase microextraction (SPME) with gas chromatography-mass spectrometry (GC-MS). Fully ripe watermelon was squeezed through miracloth to produce rapid juice extracts for immediate headspace SPME GC-MS. Aldehydes, alcohols, ketones, and one furan (2-pentyl furan, a lipid oxidation product) were recovered. On the basis of total ion count peak area, the most abundant compounds in five varieties were 3-nonen-1-ol/(E,Z)-2,6-nonadienal (16.5-28.2%), (E)-2-nonenal (10.6-22.5%), and (Z)-6-nonenal (2.0-11.3%). Hexanal was most abundant (37.7%) in one variety (Petite Perfection) [corrected] The most abundant ketone was 6-methyl-5-hepten-2-one (2.7-7.7%). Some sensory attributes reported for these compounds are melon, citrus, cucumber, orange, rose, floral, guava, violet, vegetable, green, grassy, herbaceous, pungent, fatty, sweet, and waxy. Identifying and relating these compounds to sensory attributes will allow for future monitoring of the critical flavor compounds in seedless watermelon after processing and throughout fresh-cut storage.
DOE Office of Scientific and Technical Information (OSTI.GOV)
DeRosier, R.; Waterland, L.R.
1987-03-01
The report gives emission results from field tests of a wood-waste-fired industrial firetube boiler. Emission measurements included: continuous monitoring of flue-gas emissions; source assessment sampling system (SASS) sampling of the flue gas with subsequent laboratory analysis of samples to give total flue-gas organics in two boiling-point ranges, compound category information within these ranges, specific quantitation of the semivolatile organic priority pollutants, and flue-gas concentrations of 65 trace elements; Method 5 sampling for particulates; controlled condensation system (CSS) sampling for SO/sub 2/ and SO/sub 3/; and grab sampling of boiler bottom ash for trace-element-content determinations. Emission levels of five polycyclic organicmore » matter species and phenol were quantitated: except for naphthalene, all were emitted at less than 0.4 microgram/dscm.« less
NASA Astrophysics Data System (ADS)
Liu, J.; Chen, Z.; Horowitz, L. W.; Carlton, A. M. G.; Fan, S.; Cheng, Y.; Ervens, B.; Fu, T. M.; He, C.; Tao, S.
2014-12-01
Secondary organic aerosols (SOA) have a profound influence on air quality and climate, but large uncertainties exist in modeling SOA on the global scale. In this study, five SOA parameterization schemes, including a two-product model (TPM), volatility basis-set (VBS) and three cloud SOA schemes (Ervens et al. (2008, 2014), Fu et al. (2008) , and He et al. (2013)), are implemented into the global chemical transport model (MOZART-4). For each scheme, model simulations are conducted with identical boundary and initial conditions. The VBS scheme produces the highest global annual SOA production (close to 35 Tg·y-1), followed by three cloud schemes (26-30 Tg·y-1) and TPM (23 Tg·y-1). Though sharing a similar partitioning theory to the TPM scheme, the VBS approach simulates the chemical aging of multiple generations of VOCs oxidation products, resulting in a much larger SOA source, particularly from aromatic species, over Europe, the Middle East and Eastern America. The formation of SOA in VBS, which represents the net partitioning of semi-volatile organic compounds from vapor to condensed phase, is highly sensitivity to the aging and wet removal processes of vapor-phase organic compounds. The production of SOA from cloud processes (SOAcld) is constrained by the coincidence of liquid cloud water and water-soluble organic compounds. Therefore, all cloud schemes resolve a fairly similar spatial pattern over the tropical and the mid-latitude continents. The spatiotemporal diversity among SOA parameterizations is largely driven by differences in precursor inputs. Therefore, a deeper understanding of the evolution, wet removal, and phase partitioning of semi-volatile organic compounds, particularly above remote land and oceanic areas, is critical to better constrain the global-scale distribution and related climate forcing of secondary organic aerosols.
Ayala-Cabrera, Juan F; Javier Santos, F; Moyano, Encarnación
2018-05-24
In this work, the feasibility of negative-ion atmospheric pressure chemical ionisation (APCI) and atmospheric pressure photoionisation (APPI) for ultra-high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) determination of fluorotelomer alcohols (FTOHs), fluorinated octanesulfonamides (FOSAs) and fluorinated octanesulfonamido-ethanols (FOSEs) was evaluated. The study of the effect of mobile phase composition on the atmospheric pressure ionisation of these compounds indicated that methanol/water mixtures provided the best responses in APCI, while acetonitrile/water with a post-column addition of toluene as dopant was the most appropriated mixture in APPI. Under the optimal working conditions, most of the target compounds produced the ion [M-H] - as base peak, although in-source collision-induced dissociation fragment ions in APCI and APPI and superoxide adduct ions [M+O 2 ] -• in APPI were also present. These ions proved to be more useful as precursor ions for MS/MS determination than the adduct ions generated in electrospray. Although the UHPLC-APCI-MS/MS method allowed the determination of these semi-volatile compounds at low concentration levels, the analysis by UHPLC-APPI-MS/MS provided the lowest limits of detection and it was applied to the analysis of water samples in combination with solid-phase extraction. Quality parameters demonstrated the good performance of the proposed method, providing low method limits of detection (0.3-6 ng L -1 ), good precision (RSD % < 5%) and an accurate quantification (relative error % < 14%). Among the river water samples analysed by the developed method, 4:2 FTOH and N-EtFOSA were determined at 30 and 780 ng L -1 , respectively.
Groenewold, Gary S; Scott, Jill R; Rae, Catherine
2011-07-04
Recovery of chemical contaminants from fixed surfaces for analysis can be challenging, particularly if it is not possible to acquire a solid sample to be taken to the laboratory. A simple device is described that collects semi-volatile organic compounds from fixed surfaces by creating an enclosed volume over the surface, then generating a modest vacuum. A solid-phase microextraction (SPME) fiber is then inserted into the evacuated volume where it functions to sorb volatilized organic contaminants. The device is based on a syringe modified with a seal that is used to create the vacuum, with a perforable plunger through which the SPME fiber is inserted. The reduced pressure speeds partitioning of the semi-volatile compounds into the gas phase and reduces the boundary layer around the SPME fiber, which enables a fraction of the volatilized organics to partition into the SPME fiber. After sample collection, the SPME fiber is analyzed using conventional gas chromatography/mass spectrometry. The methodology has been used to collect organophosphorus compounds from glass surfaces, to provide a simple test for the functionality of the devices. Thirty minute sampling times (ΔT(vac)) resulted in fractional recovery efficiencies that ranged from 10(-3) to >10(-2), and in absolute terms, collection of low nanograms was demonstrated. Fractional recovery values were positively correlated to the vapor pressure of the compounds being sampled. Fractional recovery also increased with increasing ΔT(vac) and displayed a roughly logarithmic profile, indicating that an operational equilibrium is being approached. Fractional recovery decreased with increasing time between exposure and sampling; however, recordable quantities of the phosphonates could be collected three weeks after exposure. Copyright © 2011 Elsevier B.V. All rights reserved.
Overview of air pollution and endocrine disorders
Darbre, Philippa D
2018-01-01
Over recent years, many environmental pollutant chemicals have been shown to possess the ability to interfere in the functioning of the endocrine system and have been termed endocrine disrupting chemicals (EDCs). These compounds exist in air as volatile or semi-volatile compounds in the gas phase or attached to particulate matter. They include components of plastics (phthalates, bisphenol A), components of consumer goods (parabens, triclosan, alkylphenols, fragrance compounds, organobromine flame retardants, fluorosurfactants), industrial chemicals (polychlorinated biphenyls), products of combustion (polychlorinated dibenzodioxins/furans, polyaromatic hydrocarbons), pesticides, herbicides, and some metals. This review summarizes current knowledge concerning the sources of EDCs in air, measurements of levels of EDCs in air, and the potential for adverse effects of EDCs in air on human endocrine health. PMID:29872334
Chemical sensing of plant stress at the ecosystem scale
NASA Astrophysics Data System (ADS)
Karl, T.; Guenther, A.; Turnipseed, A.; Patton, E. G.; Jardine, K.
2008-06-01
Significant ecosystem-scale emissions of methylsalicylate (MeSA), a semivolatile plant hormone thought to act as the mobile signal for systemic acquired resistance (SAR) (Park et al., 2006), were observed in an agroforest. Our measurements show that plant internal defence mechanisms can be activated in response to temperature stress and are modulated by water availability on large scales. Highest MeSA fluxes (up to 0.25 mg/m2/h) were observed after plants experienced ambient night-time temperatures of ~7.5°C followed by a large daytime temperature increase (e.g. up to 22°C). Under these conditions estimated night-time leaf temperatures were as low as ~4.6°C, likely inducing a response to prevent chilling injury (Ding et al., 2002). Our observations imply that plant hormones can be a significant component of ecosystem scale volatile organic compound (VOC) fluxes (e.g. as high as the total monoterpene (MT) flux) and therefore contribute to the missing VOC budget (de Carlo et al., 2004; Goldstein and Galbally, 2007). If generalized to other ecosystems and different types of stresses these findings suggest that semivolatile plant hormones have been overlooked by investigations of the impact of biogenic VOCs on aerosol formation events in forested regions (Kulmala et al., 2001; Boy et al., 2000). Our observations show that the presence of MeSA in canopy air serves as an early chemical warning signal indicating ecosystem-scale stresses before visible damage becomes apparent. As a chemical metric, ecosystem emission measurements of MeSA in ambient air could therefore support field studies investigating factors that adversely affect plant growth.
Field Portable GC-MS Unit for Semi-Volatile Compound Analysis in Groundwater
2011-06-01
for the collection of information is estimated to average 1 hour per response, including the time for reviewing instructions, searching existing data ...sources, gathering and maintaining the data needed, and completing and reviewing the collection of information. Send comments regarding this burden...notwithstanding any other provision of law, no person shall be subject to a penalty for failing to comply with a collection of information if it does
Ashley, Nicholas A; Valsaraj, Kalliat T; Thibodeaux, Louis J
2008-01-01
Sediment samples were collected from two homes which were flooded in the wake of Hurricane Katrina in August 2005. The samples were analyzed for trace metals and semi-volatile organic compounds using techniques based on established EPA methods. The data showed higher concentrations of some metals and semi-volatile organic pollutants than reported in previous outdoor sampling events of soils and sediments. The Lake Pontchartrain sediments became resuspended during the hurricane, and this material subsequently was found in the residential areas of New Orleans following levee breaches. The clay and silt particles appear to be selectively deposited inside homes, and sediment contaminant concentrations are usually greatest within this fraction. Re-entry advisories based on outdoor sample concentration results may have under-predicted the exposure levels to homeowners and first responders. All contaminants found in the sediment sampled in this study have their origin in the sediments of Lake Pontchartrain and other localized sources.
DOE Office of Scientific and Technical Information (OSTI.GOV)
NONE
1998-10-01
The Lincoln Creosote Site (Site) is located in Bossier City, Louisiana, and consists of a 20-acre industrial area that includes the former location of a wood treatment plant. Wood products such as railroad ties and utility poles were pressure treated at the plant, using creosote, chromated copper-arsenate (CCA) and pentachlorophenol (PCP) as wood preservatives. The compounds used for wood treatment contained metals, a number of semi-volatile organic base-neutral extractable compounds such as polynuclear aromatic hydrocarbon (PAHs). EPA`s selected removal action called for excavation of residential soils containing concentrations of wood treatment product residuals.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Harrison, W.; Nashold, B.; Meshkov, N.K.
1990-07-01
The proposed eight-acre building site for the Walter Reed Army Institute of Research (WRAIR) facility is a former uncontrolled landfill. As a prerequisite to foundation design and to formulation of an excavation plan, it was necessary to characterize the landfill materials and to conduct a qualitative human risk assessment. Chemical analysis of surface-water, groundwater, and landfill soils followed the analytical protocol promulgated under the US Environmental Protection Agency's (EPA's) Contract Laboratory Program for its Target Compound List of contaminants. This protocol was used to determine concentrations of volatile organic compounds (VOCs), semivolatile organic compounds (SVOCs) polychlorinated biphenyls (PCBs)/pesticides, inorganic compounds,more » radioactive materials, asbestos, and many of the metals analyzed. 49 refs., 19 figs., 24 tabs.« less
PAHs, NITRO-PAHs, HOPANES, AND STERANES IN LAKE TROUT FROM LAKE MICHIGAN
Huang, Lei; Chernyak, Sergei M.; Batterman, Stuart A.
2015-01-01
The present study examines concentrations and risks of polycyclic aromatic hydrocarbons (PAHs), nitro-PAHs (NPAHs), steranes, and hopanes in lake trout collected in Lake Michigan. A total of 74 fish were collected in 2 seasons at 3 offshore sites. The total PAH concentration (Σ9PAH) in whole fish ranged from 223 pg/g to 1704 pg/g wet weight, and PAH concentrations and profiles were similar across season, site, and sex. The total NPAH (Σ9NPAH) concentrations ranged from 0.2 pg/g to 31 pg/g wet weight, and carcinogenic compounds, including 1-nitropyrene and 6-nitrochrysene, were detected. In the fall, NPAH concentrations were low at the Illinois site (0.2–0.5 pg/g wet wt), and site profiles differed considerably; in the spring, concentrations and profiles were similar across sites, possibly reflecting changes in fish behavior. In the fall, the total sterane (Σ5Sterane) and total hopane (Σ2Hopane) levels reached 808 pg/g and 141 pg/g wet weight, respectively, but concentrations in the spring were 10 times lower. Concentrations in eggs (fall only) were on the same order of magnitude as those in whole fish. These results demonstrate the presence of target semivolatile organic compounds in a top predator fish, and are consistent with PAH biodilution observed previously. Using the available toxicity information for PAHs and NPAHs, the expected cancer risk from consumption of lake trout sampled are low. However, NPAHs contributed a significant portion of the toxic equivalencies in some samples. The present study provides the first measurements of NPAHs in freshwater fish, and results suggest that additional assessment is warranted. PMID:24764175
Characterization of kerosene-heater emissions inside two mobile homes
DOE Office of Scientific and Technical Information (OSTI.GOV)
Burton, R.M.; Seila, R.A.; Wilson, W.E.
1990-03-01
In an effort to determine the impact of kerosene heater emissions on indoor air quality, measurements were made in and around two mobile homes at a rural mobile home park near Apex, NC. The sampling was performed at two single-wide mobile homes equipped with kerosene heaters. The concentrations of acidic aerosols and gases, fine and coarse particulate aerosol mass, carbon monoxide, nitrogen oxides, volatile organic compounds and semivolatiles, were determined for periods of heater operation and for periods in which heaters were not operated. Simultaneous outdoor measurements of acid aerosols and gases, fine and coarse aerosol mass, and volatile organicmore » compounds were conducted to determine the contribution of outdoor pollutants to the indoor concentrations. Comparisons between the concentrations obtained from the analysis of outdoor, heater-on, and heater-off samples allowed the authors to examine the impacts of the kerosene emissions on indoor concentrations. Concentrations of sulfates, aerosol strong acidity, fine and coarse aerosol mass, carbon monoxide, and sulfur dioxide were found to be higher when the heater was operated; however, these heater-on concentrations were comparable to those observed in moderately polluted atmospheres. Indoor concentrations of nitrous acid and nitrogen oxides during heater operation were found to be considerably higher than those observed in polluted atmospheres. Finally, use of kerosene heaters was found to be responsible for increased concentrations of non-methane volatile and semi-volatile organic compounds indoors. Acid aerosol indoor concentrations were quite variable during the study and were found to exist in the presence of excess ammonia.« less
Semi-volatile organic compounds in the particulate phase in dwellings: A nationwide survey in France
NASA Astrophysics Data System (ADS)
Mandin, Corinne; Mercier, Fabien; Ramalho, Olivier; Lucas, Jean-Paul; Gilles, Erwann; Blanchard, Olivier; Bonvallot, Nathalie; Glorennec, Philippe; Le Bot, Barbara
2016-07-01
Sixty-six semi-volatile organic compounds (SVOCs)-phthalates, polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), one pyrethroid, organochlorine and organophosphorous pesticides, alkylphenols, synthetic musks, tri-n-butylphosphate and triclosan-were measured on PM10 filters collected over 7 days during a nationwide survey of 285 French dwellings, representative of nearly 25 million housing units. Thirty-five compounds were detected in more than half of the dwellings. PAHs, phthalates and triclosan were the major particle-bound SVOCs, with a median concentration greater than 1 ng m-3 for butylbenzyl phthalate (BBP) (median: 1.6 ng m-3), di(2-ethylhexyl) phthalate (DEHP) (46 ng m-3) and di-iso-nonyl phthalate (DiNP) (7.9 ng m-3), and greater than 0.1 ng m-3 for triclosan (114 pg m-3), benzo(a)pyrene (138 pg m-3), benzo(b)fluoranthene (306 pg m-3), benzo(g,h,i)perylene (229 pg m-3), and indeno(1,2,3-c,d)pyrene (178 pg m-3). For most of the SVOCs, higher concentrations were found in the dwellings of smokers and during the heating season. The concentrations of banned SVOCs-namely, PCBs and organochlorine pesticides-were correlated. Permethrin, 4-tert-butylphenol and bisphenol-A showed no correlation with the other SVOCs and seemed to have their own specific sources. Most SVOCs were positively associated with PM10 concentration, suggesting that any factor that raises the mass of indoor airborne particles also increases the exposure to SVOCs through inhalation.
Koziel, Jacek A; Spinhirne, Jarett P; Lloyd, Jenny D; Parker, David B; Wright, Donald W; Kuhrt, Fred W
2005-08-01
Odorous gases associated with livestock operations are complex mixtures of hundreds if not thousands of compounds. Research is needed to know how best to sample and analyze these compounds. The main objective of this research was to compare recoveries of a standard gas mixture of 11 odorous compounds from the Carboxen/PDMS 75-microm solid-phase microextraction fibers, polyvinyl fluoride (PVF; Tedlar), fluorinated ethylene propylene copolymer (FEP; Teflon), foil, and polyethylene terephthalate (PET; Melinex) air sampling bags, sorbent 2,b-diphenylene-oxide polymer resin (Tenax TA) tubes, and standard 6-L Stabilizer sampling canisters after sample storage for 0.5, 24, and 120 (for sorbent tubes only) hrs at room temperature. The standard gas mixture consisted of 7 volatile fatty acids (VFAs) from acetic to hexanoic, and 4 semivolatile organic compounds including p-cresol, indole, 4-ethylphenol, and 2'-aminoacetophenone with concentrations ranging from 5.1 ppb for indole to 1270 ppb for acetic acid. On average, SPME had the highest mean recovery for all 11 gases of 106.2%, and 98.3% for 0.5- and 24-hr sample storage time, respectively. This was followed by the Tenax TA sorbent tubes (94.8% and 88.3%) for 24 and 120 hr, respectively; PET bags (71.7% and 47.2%), FEP bags (75.4% and 39.4%), commercial Tedlar bags (67.6% and 22.7%), in-house-made Tedlar bags (47.3% and 37.4%), foil bags (16.4% and 4.3%), and canisters (4.2% and 0.5%), for 0.5 and 24 hr, respectively. VFAs had higher recoveries than semivolatile organic compounds for all of the bags and canisters. New FEP bags and new foil bags had the lowest and the highest amounts of chemical impurities, respectively. New commercial Tedlar bags had measurable concentrations of N,N-dimethyl acetamide and phenol. Foil bags had measurable concentrations of acetic, propionic, butyric, valeric, and hexanoic acids.
Nonvolatile, semivolatile, or volatile: redefining volatile for volatile organic compounds.
Võ, Uyên-Uyén T; Morris, Michael P
2014-06-01
Although widely used in air quality regulatory frameworks, the term "volatile organic compound" (VOC) is poorly defined. Numerous standardized tests are currently used in regulations to determine VOC content (and thus volatility), but in many cases the tests do not agree with each other, nor do they always accurately represent actual evaporation rates under ambient conditions. The parameters (time, temperature, reference material, column polarity, etc.) used in the definitions and the associated test methods were created without a significant evaluation of volatilization characteristics in real world settings. Not only do these differences lead to varying VOC content results, but occasionally they conflict with one another. An ambient evaporation study of selected compounds and a few formulated products was conducted and the results were compared to several current VOC test methodologies: SCAQMD Method 313 (M313), ASTM Standard Test Method E 1868-10 (E1868), and US. EPA Reference Method 24 (M24). The ambient evaporation study showed a definite distinction between nonvolatile, semivolatile, and volatile compounds. Some low vapor pressure (LVP) solvents, currently considered exempt as VOCs by some methods, volatilize at ambient conditions nearly as rapidly as the traditional high-volatility solvents they are meant to replace. Conversely, bio-based and heavy hydrocarbons did not readily volatilize, though they often are calculated as VOCs in some traditional test methods. The study suggests that regulatory standards should be reevaluated to more accurately reflect real-world emission from the use of VOC containing products. The definition of VOC in current test methods may lead to regulations that exclude otherwise viable alternatives or allow substitutions of chemicals that may limit the environmental benefits sought in the regulation. A study was conducted to examine volatility of several compounds and a few formulated products under several current VOC test methodologies and ambient evaporation. This paper provides ample evidence to warrant a reevaluation of regulatory standards and provides a framework for progressive developments based on reasonable and scientifically justifiable definitions of VOCs.
TOTAL PAH EXPOSURES OF NINE PRESCHOOL CHILDREN
This study evaluates the influence of denuder sampling methods and filter collection media on the measurement of semi-volatile organic carbon (SVOC) associated with PM2.5. Two types of collection media, charcoal (activated carbon) and XAD, were used both in diffusion denuders ...
Estuarine bed-sediment-quality data collected in New Jersey and New York after Hurricane Sandy, 2013
Fischer, Jeffrey M.; Phillips, Patrick J.; Reilly, Timothy J.; Focazio, Michael J.; Loftin, Keith A.; Benzel, William M.; Jones, Daniel K.; Smalling, Kelly L.; Fisher, Shawn C.; Fisher, Irene J.; Iwanowicz, Luke R.; Romanok, Kristin M.; Jenkins, Darkus E.; Bowers, Luke; Boehlke, Adam; Foreman, William T.; Deetz, Anna C.; Carper, Lisa G.; Imbrigiotta, Thomas E.; Birdwell, Justin E.
2015-01-01
Bed-sediment samples were collected from June to October 2013 from 167 estuarine sites extending from Cape May, New Jersey, to the New York Harbor and the eastern end of Long Island. Each sampling location and study region was characterized by using geographic information to identify potential contaminant sources. Characterizations included land cover, locations and types of businesses (industrial, financial, and others), spills (sewage, chemical, and others), bulk storage facilities, effluent discharges within 2 kilometers of the sampling point, and discharges within inundated and non-inundated regions near the sampling location. Samples were analyzed for particle size, total organic carbon, metals and trace elements, semivolatile organic compounds, wastewater compounds, hormones, and sediment toxicity. Samples were also screened using x-ray fluorescence, Fourier transform infrared spectroscopy, and x-ray diffraction. In addition, bioassays for endocrine disruptors and protein phosphatase 2A inhibition were conducted. The study was designed to provide the data needed to understand the extent and sources of contamination resulting from Hurricane Sandy, to compare the chemistry and toxicity of estuarine bed sediments before and after the storm, and to evaluate the usefulness of rapid screening and bioassay approaches in disaster settings.
Jerković, Igor; Tuberoso, Carlo I G; Marijanović, Zvonimir; Kranjac, Marina; Malenica-Staver, M
2015-07-01
The present study is focused on the antioxidant capacity and chemical profiling of eight Croatian Satureja montana L. honey samples. Among the 20 compounds obtained by headspace solid-phase microextraction (HS-SPME) and identified by GC-FID and GC/MS analyses, hotrienol was predominant (75.9-81.7%). The honey matrix volatile/semivolatile profile was investigated by ultrasonic solvent extraction (USE) followed by GC-FID and GC/MS analyses. The major compounds identified by this latter method were the sinapic-acid derivatives methyl syringate (36.2-72.8%) and syringaldehyde (2.2-43.1%). Direct, targeted HPLC-DAD analyses of the native honey samples revealed the presence of methyl syringate (7.10-39.60 mg/kg) and syringic acid (0.10-1.70 mg/kg). In addition, the total phenolic content of the samples was determined by the FolinCiocalteu assay (311.0-465.9 mg GAE/kg), and the antioxidant capacity was evaluated by the DPPH radical-scavenging activity (0.5-1.0 mmol TEAC/kg) and the ferric reducing antioxidant power (2.5-5.1 mmol Fe(2+) /kg). Copyright © 2015 Verlag Helvetica Chimica Acta AG, Zürich.
Fallon, James D.; Yaeger, Christine S.
2009-01-01
Mille Lacs Lake and its tributaries, located in east-central Minnesota, are important resources to the public. In addition, many wetlands and lakes that feed Mille Lacs Lake are of high resource quality and vulnerable to degradation. Construction of a new four-lane expansion of U.S. Highway 169 has been planned along the western part of the drainage area of Mille Lacs Lake in Crow Wing County. Concerns exist that the proposed highway could affect the resource quality of surface waters tributary to Mille Lacs Lake. Baseline water- and bed-sediment quality characteristics of surface waters tributary to Mille Lacs Lake were needed prior to the proposed highway construction. The U.S. Geological Survey, in cooperation with the Minnesota Department of Transportation, characterized the water- and bed-sediment quality at selected locations that the proposed route intersects from October 2003 to October 2006. Locations included Seguchie Creek upstream and downstream from the proposed route and three wetlands draining to Mille Lacs Lake. The mean streamflow of Seguchie Creek increased between the two sites: flow at the downstream streamflow-gaging station of 0.22 cubic meter per second was 5.6 percent greater than the mean streamflow at the upstream streamflow-gaging station of 0.21 cubic meter per second. Because of the large amount of storage immediately upstream from both gaging stations, increases in flow were gradual even during intense precipitation. The ranges of most constituent concentrations in water were nearly identical between the two sampling sites on Seguchie Creek. No concentrations exceeded applicable water-quality standards set by the State of Minnesota. Dissolved-oxygen concentrations at the downstream gaging station were less than the daily minimum standard of 4.0 milligrams per liter for 6 of 26 measurements. Constituent loads in Seguchie Creek were greater at the downstream site than the upstream site for all measured, including dissolved chloride (1.7 percent), ammonia plus organic nitrogen (13 percent), total phosphorus (62 percent), and suspended sediment (11 percent) during the study. All constituents had seasonal peaks in spring and fall. The large loads during the fall resulted from unusually large precipitation and streamflow patterns. This caused the two greatest streamflow peaks at both sites to occur during October (2004 and 2005). In Seguchie Creek, bed-sediment concentrations of five metals and trace elements (arsenic, cadmium, chromium, lead, and zinc) exceeded the Interim Sediment Quality Guidelines (ISQG) set by the Canadian Council of Ministers of the Environment. Bed-sediment samples from the upstream site had more exceedances of ISQGs for metals and trace elements than did samples from the downstream site (seven and two exceedances, respectively). Bed-sediment samples from the downstream site had more exceedances of ISQGs (20 exceedances) for semivolatile organic compounds than did samples from the upstream site (8 exceedances), indicating different sources for organic compounds than for metals and trace elements. Concentrations of 11 semivolatile organic compounds exceeded ISQGs: ancenaphthene, acenaphthylene, anthracene, benzo[a]anthracene, benzo[a]pyrene, chrysene, fluoranthene, fluorene, naphthalene, phenanthrene, and pyrene. In bed-sediment samples collected from three wetlands, concentrations of all six metals exceeded ISQGs: arsenic, cadmium, chromium, copper, lead, and zinc. Concentrations of three semivolatile organic compounds exceeded ISQGs: flouranthene, phenanthrene, and pyrene. Results indicate that areas appearing relatively undisturbed and of high resource value can have degraded quality from previous unknown land use.
NASA Astrophysics Data System (ADS)
Ciarelli, Giancarlo; El Haddad, Imad; Bruns, Emily; Aksoyoglu, Sebnem; Möhler, Ottmar; Baltensperger, Urs; Prévôt, André S. H.
2017-06-01
In this study, novel wood combustion aging experiments performed at different temperatures (263 and 288 K) in a ˜ 7 m3 smog chamber were modelled using a hybrid volatility basis set (VBS) box model, representing the emission partitioning and their oxidation against OH. We combine aerosol-chemistry box-model simulations with unprecedented measurements of non-traditional volatile organic compounds (NTVOCs) from a high-resolution proton transfer reaction mass spectrometer (PTR-MS) and with organic aerosol measurements from an aerosol mass spectrometer (AMS). Due to this, we are able to observationally constrain the amounts of different NTVOC aerosol precursors (in the model) relative to low volatility and semi-volatile primary organic material (OMsv), which is partitioned based on current published volatility distribution data. By comparing the NTVOC / OMsv ratios at different temperatures, we determine the enthalpies of vaporization of primary biomass-burning organic aerosols. Further, the developed model allows for evaluating the evolution of oxidation products of the semi-volatile and volatile precursors with aging. More than 30 000 box-model simulations were performed to retrieve the combination of parameters that best fit the observed organic aerosol mass and O : C ratios. The parameters investigated include the NTVOC reaction rates and yields as well as enthalpies of vaporization and the O : C of secondary organic aerosol surrogates. Our results suggest an average ratio of NTVOCs to the sum of non-volatile and semi-volatile organic compounds of ˜ 4.75. The mass yields of these compounds determined for a wide range of atmospherically relevant temperatures and organic aerosol (OA) concentrations were predicted to vary between 8 and 30 % after 5 h of continuous aging. Based on the reaction scheme used, reaction rates of the NTVOC mixture range from 3.0 × 10-11 to 4. 0 × 10-11 cm3 molec-1 s-1. The average enthalpy of vaporization of secondary organic aerosol (SOA) surrogates was determined to be between 55 000 and 35 000 J mol-1, which implies a yield increase of 0.03-0.06 % K-1 with decreasing temperature. The improved VBS scheme is suitable for implementation into chemical transport models to predict the burden and oxidation state of primary and secondary biomass-burning aerosols.
Parliman, D.J.
2004-01-01
In 2001, the National Guard Bureau and the U.S. Geological Survey began a project to compile hydrogeologic data and determine presence or absence of soil, surface-water, and ground-water contamination at the Idaho Army National Guard Orchard Training Area in southwestern Idaho. Between June 2002 and April 2003, a total of 114 soil, surface-water, ground-water, precipitation, or dust samples were collected from 68 sample sites (65 different locations) in the Orchard Training Area (OTA) or along the vehicle corridor to the OTA. Soil and water samples were analyzed for concentrations of selected total trace metals, major ions, nutrients, explosive compounds, semivolatile organics, and petroleum hydrocarbons. Water samples also were analyzed for concentrations of selected dissolved trace metals and major ions. Distinguishing naturally occurring large concentrations of trace metals, major ions, and nutrients from contamination related to land and water uses at the OTA was difficult. There were no historical analyses for this area to compare with modern data, and although samples were collected from 65 locations in and near the OTA, sampled areas represented only a small part of the complex OTA land-use areas and soil types. For naturally occurring compounds, several assumptions were made?anomalously large concentrations, when tied to known land uses, may indicate presence of contamination; naturally occurring concentrations cannot be separated from contamination concentrations in mid- and lower ranges of data; and smallest concentrations may represent the lowest naturally occurring range of concentrations and (or) the absence of contaminants related to land and water uses. Presence of explosive, semivolatile organic (SVOC), and petroleum hydrocarbon compounds in samples indicates contamination from land and water uses. In areas along the vehicle corridor and major access roads within the OTA, most trace metal, major ion, and nutrient concentrations in soil samples were not in the upper 10th percentile of data, but concentrations of 25 metals, ions, or nutrients were in the upper 10th percentile in a puddle sample near the heavy equipment maneuvering area, MPRC-H. The largest concentrations of tin, ammonia, and nitrite plus nitrate (as nitrogen) in water from the OTA were detected in a sample from this puddle. Petroleum hydrocarbons were the most common contaminant, detected in all soil and surface-water samples. An SVOC, bis (2-ethylhexyl) phthalate, a plasticizer, was detected at a site along the vehicle corridor. In Maneuver Areas within the OTA, many soil samples contained at least one trace metal, major ion, or nutrient in the upper 10th percentile of data, and the largest concentrations of cobalt, iron, mercury, titanium, sodium, ammonia, or total phosphorus were detected in 6 of 13 soil samples outside the Tadpole Lake area. The largest concentrations of aluminum, arsenic, beryllium, nickel, selenium, silver, strontium, thallium, vanadium, chloride, potassium, sulfate, and nitrite plus nitrate were detected in soil samples from the Tadpole Lake area. Water from Tadpole Lake contained the largest total concentrations of 19 trace metals, 4 major ions, and 1 nutrient. Petroleum hydrocarbons were detected in 5 soil samples and water from Tadpole Lake. SVOCs related to combustion of fuel or plasticizers were detected in 1 soil sample. Explosive compounds were detected in 1 precipitation sample.In the Impact Area within the OTA, most soil samples contained at least one trace metal, major ion, or nutrient in the upper 10th percentile of data, and the largest concentrations of barium, chromium, copper, manganese, lead, or orthophosphate were detected in 6 of the 18 soil samples. Petroleum hydrocarbons were detected in 4 soil samples, SVOCs in 6 samples, and explosive compounds in 4 samples. In the mobilization and training equipment site (MATES) compound adjacent to the OTA, all soil and water samples contained at lea
SCHRLAU, JILL E.; GEISER, LINDA; HAGEMAN, KIMBERLY J.; LANDERS, DIXON H.
2011-01-01
A wide range of semi-volatile organic compounds (SOCs), including pesticides and polycyclic aromatic hydrocarbons (PAHs), were measured in lichen, conifer needles, snowpack and XAD-based passive air sampling devices (PASDs) collected from 19 different U.S. national parks in order to compare the magnitude and mechanism of SOC accumulation in the different passive sampling media. Lichen accumulated the highest SOC concentrations, in part because of its long (and unknown) exposure period, while PASDs accumulated the lowest concentrations. However, only the PASD SOC concentrations can be used to calculate an average atmospheric gas-phase SOC concentration because the sampling rates are known and the media is uniform. Only the lichen and snowpack SOC accumulation profiles were statistically significantly correlated (r = 0.552, p-value <0.0001) because they both accumulate SOCs present in the atmospheric particle-phase. This suggests that needles and PASDs represent a different composition of the atmosphere than lichen and snowpack and that the interpretation of atmospheric SOC composition is dependent on the type of passive sampling media used. All four passive sampling media preferentially accumulated SOCs with relatively low air-water partition coefficients, while snowpack accumulated SOCs with higher log KOA values compared to the other media. Lichen accumulated more SOCs with log KOA > 10 relative to needles and showed a greater accumulation of particle-phase PAHs. PMID:22087860
Haefliger, Olivier P; Jeckelmann, Nicolas; Ouali, Lahoussine; León, Géraldine
2010-01-15
An innovative headspace sampling and injection system for gas chromatography was designed using a longitudinally modulating cryogenic system mounted around the sampling loop of a two-position loop injector. The setup was hyphenated to a fast low thermal mass gas chromatograph, allowing transient concentrations of semivolatile analytes to be monitored in real time with a time resolution of 4.5 min. The performance of the instrument, and in particular its cryotrapping efficiency, was characterized using a mixture of long-chain alkanes, methyl esters, ethyl esters, and alcohols of different volatilities. The device was found to be ideally suited to the analysis of semivolatile compounds with boiling points ranging between 190 and 320 degrees C, which are typical for a majority of perfumery raw materials. The new instrument was successfully used to monitor the release of eight odorant compounds from cotton towels to which fabric softener had been applied that alternatively contained the fragrance in free form or in microencapsulated form. The analytical results, unprecedented in their level of precision and time resolution for such an application, evidenced the major impact of microencapsulation technology on the kinetics of fragrance release during the drying of the towels and on the triggering of additional fragrance release by applying mechanical stress to the fabric to rupture the microcapsule walls.
On the implications of aerosol liquid water and phase ...
Organic compounds and liquid water are major aerosol constituents in the southeast United States (SE US). Water associated with inorganic constituents (inorganic water) can contribute to the partitioning medium for organic aerosol when relative humidities or organic matter to organic carbon (OM ∕ OC) ratios are high such that separation relative humidities (SRH) are below the ambient relative humidity (RH). As OM ∕ OC ratios in the SE US are often between 1.8 and 2.2, organic aerosol experiences both mixing with inorganic water and separation from it. Regional chemical transport model simulations including inorganic water (but excluding water uptake by organic compounds) in the partitioning medium for secondary organic aerosol (SOA) when RH > SRH led to increased SOA concentrations, particularly at night. Water uptake to the organic phase resulted in even greater SOA concentrations as a result of a positive feedback in which water uptake increased SOA, which further increased aerosol water and organic aerosol. Aerosol properties, such as the OM ∕ OC and hygroscopicity parameter (κorg), were captured well by the model compared with measurements during the Southern Oxidant and Aerosol Study (SOAS) 2013. Organic nitrates from monoterpene oxidation were predicted to be the least water-soluble semivolatile species in the model, but most biogenically derived semivolatile species in the Community Multiscale Air Quality (CMAQ) model were hig
Raffy, Gaëlle; Mercier, Fabien; Glorennec, Philippe; Mandin, Corinne; Le Bot, Barbara
2018-06-15
Many semi-volatile organic compounds (SVOCs), suspected of reprotoxic, neurotoxic or carcinogenic effects, were measured in indoor settled dust. Dust ingestion is a non-negligible pathway of exposure to some of these SVOCs, and an accurate knowledge of the real exposure is necessary for a better evaluation of health risks. To this end, the bioaccessibility of SVOCs in dust needs to be considered. In the present work, bioaccessibility measurement methods, SVOCs' oral bioaccessibility data and influencing factors were reviewed. SVOC bioaccessibilities (%) ranged from 11 to 94, 8 to 100, 3 to 92, 1 to 81, 6 to 52, and 2 to 17, for brominated flame retardants, organophosphorus flame retardants, polychlorobiphenyls, phthalates, pesticides and polycyclic aromatic hydrocarbons, respectively. Measurements method produced varying results depending on the inclusion of food and/or sink in the model. Characteristics of dust, e.g., organic matter content and particle size, also influenced bioaccessibility data. Last, results were influenced by SVOC properties, such as octanol/water partition coefficient and migration pathway into dust. Factors related to dust and SVOCs could be used in prediction models. To this end, more bioaccessibility studies covering more substances should be performed, using methods that are harmonized and validated by comparison to in-vivo studies. Copyright © 2018 Elsevier B.V. All rights reserved.
MEASUREMENT OF FINE PARTICULATE MATTER (NONVOLATILE AND SEMIVOLATILE FRACTIONS) IN FRESNO, CA
Semi-volatile material, including ammonium nitrate and semi-volatile organic material, is often not measured by traditionally used sampling methods including the FRM and the R&P TEOM Monitor. An intensive sampling campaign was performed at the EPA Fresno, CA Supersite during D...
EPA's recently published draft Risk Burn Guidance recommends that hazardous waste combustion facilities complete a mass balance of the total organics (TOs) that may be emitted from the combustor. TOs, consisting of three distinct fractions (volatile, semivolatile, and nonvolatile...
This study presents the integrated volume method for estimating saturation pressure and enthalpy of vaporization of a whole aerosol distribution. We measure the change of total volume of an aerosol distribution between a reference state and several heated states, with the heating...
MUTAGENICITY OF EMISSIONS FROM THE SIMULATED OPEN BURNING OF SCRAP RUBBER TIRES
The report describes a follow-up to a small-scale combustion study to collect, identify, and quantify products emitted during the simulated open combustion of scrap tires. The initial study found that total estimated emissions of semi-volatile organics ranged from 10 to 50 g/kg o...
Saini, A; Okeme, J O; Mark Parnis, J; McQueen, R H; Diamond, M L
2017-05-01
Uptake kinetics of semi-volatile organic compounds (SVOCs) present indoors, namely phthalates and halogenated flame retardants (HFRs), were characterized for cellulose-based cotton and rayon fabrics. Cotton and rayon showed similar accumulation of gas- and particle-phase SVOCs, when normalized to planar surface area. Accumulation was 3-10 times greater by rayon than cotton, when normalized to Brunauer-Emmett-Teller (BET) specific surface area which suggests that cotton could have a longer linear uptake phase than rayon. Linear uptake rates of eight consistently detected HFRs over 56 days of 0.35-0.92 m 3 /day.dm 2 planar surface area and mass transfer coefficients of 1.5-3.8 m/h were statistically similar for cotton and rayon and similar to those for uptake to passive air sampling media. These results suggest air-side controlled uptake and that, on average, 2 m 2 of clothing typically worn by a person would sequester the equivalent of the chemical content in 100 m 3 of air per day. Distribution coefficients between fabric and air (K') ranged from 6.5 to 7.7 (log K') and were within the range of partition coefficients measured for selected phthalates as reported in the literature. The distribution coefficients were similar for low molecular weight HFRs, and up to two orders of magnitude lower than the equilibrium partition coefficients estimated using the COSMO-RS model. Based on the COSMO-RS model, time to reach 95% of equilibrium for PBDEs between fabric and gas-phase compounds ranged from 0.1 to >10 years for low to high molecular weight HFRs. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.
The Unsolved Mysteries of Atmospheric Chemistry for High School Students and Teachers
NASA Astrophysics Data System (ADS)
Simonich, S. L.
2011-12-01
The grant "CAREER: New Molecular Markers of Asian Air Emissions - Anthropogenic Semi-Volatile Organic Compounds" (ATM-0239823) was funded by NSF from 2003-2008. The CAREER proposal described the integration of research and outreach education activities in the field of atmospheric chemistry, specifically atmospheric measurements and atmospheric transport. The primary objective of the research was to identify anthropogenic semi-volatile organic compounds (SOCs) that could be used as molecular markers for Asian air emissions and trans-Pacific atmospheric transport. The outreach education activity was integrated with the research by developing curriculum to introduce underrepresented minority high school students, and their teachers, to atmospheric chemistry and atmospheric measurements through Oregon State University's National Institute of Environmental Health Sciences funded Hydroville Curriculum Project (http://www.hydroville.org/iaq_resources). A curriculum was developed to allow students to assume the role of "Air Quality Scientist" and measure air temperature, air flow, relative humidity, CO, CO2, O3, and volatile organic compounds in out-door and in-door air. The students gained an understanding of atmospheric transport and compared measured concentrations to recommended guidelines. In addition, the outreach education activities included the development of the "Unsolved Mysteries of Human Health" website (http://www.unsolvedmysteries.oregonstate.edu/), including a specific module on the research conducted under the CAREER grant (http://www.unsolvedmysteries.oregonstate.edu /Gas-Chromatography-Mass-Spectrometry-Overview). The PI of the CAREER proposal, Dr. Staci Massey Simonich, is now a full professor at Oregon State University. To date, she has published over 50 peer-review journal articles, as well as mentored 9 undergraduate students, 20 graduate students, 3 post-doctoral scholars, and 3 international visiting scientists in her laboratory.
Okeme, Joseph O; Parnis, J Mark; Poole, Justen; Diamond, Miriam L; Jantunen, Liisa M
2016-08-01
Polydimethylsiloxane (PDMS) shows promise for use as a passive air sampler (PAS) for semi-volatile organic compounds (SVOCs). To use PDMS as a PAS, knowledge of its chemical-specific partitioning behaviour and time to equilibrium is needed. Here we report on the effectiveness of two approaches for estimating the partitioning properties of polydimethylsiloxane (PDMS), values of PDMS-to-air partition ratios or coefficients (KPDMS-Air), and time to equilibrium of a range of SVOCs. Measured values of KPDMS-Air, Exp' at 25 °C obtained using the gas chromatography retention method (GC-RT) were compared with estimates from a poly-parameter free energy relationship (pp-FLER) and a COSMO-RS oligomer-based model. Target SVOCs included novel flame retardants (NFRs), polybrominated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons (PAHs), organophosphate flame retardants (OPFRs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs). Significant positive relationships were found between log KPDMS-Air, Exp' and estimates made using the pp-FLER model (log KPDMS-Air, pp-LFER) and the COSMOtherm program (log KPDMS-Air, COSMOtherm). The discrepancy and bias between measured and predicted values were much higher for COSMO-RS than the pp-LFER model, indicating the anticipated better performance of the pp-LFER model than COSMO-RS. Calculations made using measured KPDMS-Air, Exp' values show that a PDMS PAS of 0.1 cm thickness will reach 25% of its equilibrium capacity in ∼1 day for alpha-hexachlorocyclohexane (α-HCH) to ∼ 500 years for tris (4-tert-butylphenyl) phosphate (TTBPP), which brackets the volatility range of all compounds tested. The results presented show the utility of GC-RT method for rapid and precise measurements of KPDMS-Air. Copyright © 2016. Published by Elsevier Ltd.
NASA Astrophysics Data System (ADS)
Khan, M. H.; Holzinger, R.
2013-12-01
A Thermal-Desorption Proton-Transfer-Reaction Mass-Spectrometer (TD-PTR-MS) with different sampling systems (multi-stage denuder for gas phase and impact on a collector for aerosol phase) has been deployed in summer 2013 during the Southern Oxidant and Aerosol Study (SOAS) at the SEARCH ground site, Centreville, Alabama for in-situ gas phase and aerosol measurements on an hourly time resolution. A bunch of DB-1 column (0.53 mm x 5.0 μm) is used in the denuder for capturing the bulk of SVOCs and a collection-thermal-desorption (CTD) cell is used for collecting aerosol particles. Several hundreds semivolatile organic compounds (SVOCs) in gas phase and aerosol phases have been detected. The high mass resolution capabilities of ~5000, low detection limit (<0.05 pptv for gas species, <0.01 ng m-3 for aerosol species) and good physical and chemical characterization of SVOCs with the TD-PTR-MS allows constraining both, the quantity and the chemical composition. The SEARCH site was highly impacted by Biogenic Volatile Organic Compounds (BVOCs) and occasionally influenced by anthropogenic pollution. BVOCs and their oxidation products are capable of partitioning into the particle phase, so their simultaneous quantification in both phases has been used to determine the gas/particle-phase partitioning. Our results show the expected diurnal variation based on the changes of air temperature for many species. The results from this study give valuable insights into sources and processing of Secondary Organic Aerosols (SOAs) that can be used to improve parameterization algorithms in regional and global climate models.
Furlong, E.T.; Vaught, D.G.; Merten, L.M.; Foreman, W.T.; Gates, Paul M.
1996-01-01
A method for the determination of 79 semivolatile organic compounds (SOCs) and 4 surrogate compounds in soils and bottom sediment is described. The SOCs are extracted from bottom sediment by solvent extraction, followed by partial isolation using high-performance gel permeation chromatography (GPC). The SOCs then are qualitatively identified and quantitative concentrations determined by capillary-column gas chromatography/mass spectrometry (GC/MS). This method also is designed for an optional simultaneous isolation of polychlorinated biphenyls (PCBs) and organochlorine (OC) insecticides, including toxaphene. When OCs and PCBs are determined, an additional alumina- over-silica column chromatography step follows GPC cleanup, and quantitation is by dual capillary- column gas chromatography with electron-capture detection (GC/ECD). Bottom-sediment samples are centrifuged to remove excess water and extracted overnight with dichloromethane. The extract is concentrated, centrifuged, and then filtered through a 0.2-micrometer polytetrafluoro-ethylene syringe filter. Two aliquots of the sample extract then are quantitatively injected onto two polystyrene- divinylbenzene GPC columns connected in series. The SOCs are eluted with dichloromethane, a fraction containing the SOCs is collected, and some coextracted interferences, including elemental sulfur, are separated and discarded. The SOC-containing GPC fraction then is analyzed by GC/MS. When desired, a second aliquot from GPC is further processed for OCs and PCBs by combined alumina-over-silica column chromatography. The two fractions produced in this cleanup then are analyzed by GC/ECD. This report fully describes and is limited to the determination of SOCs by GC/MS.
NASA Astrophysics Data System (ADS)
Liao, L.; Dal Maso, M.; Mogensen, D.; Roldin, P.; Rusanen, A.; Kerminen, V.-M.; Mentel, T. F.; Wildt, J.; Kleist, E.; Kiendler-Scharr, A.; Tillmann, R.; Ehn, M.; Kulmala, M.; Boy, M.
2014-11-01
We used the MALTE-BOX model including near-explicit air chemistry and detailed aerosol dynamics to study the mechanisms of observed new particle formation events in the Jülich Plant Atmosphere Chamber. The modelled and measured H2SO4 (sulfuric acid) concentrations agreed within a factor of two. The modelled total monoterpene concentration was in line with PTR-MS observations, and we provided the distributions of individual isomers of terpenes, when no measurements were available. The aerosol dynamic results supported the hypothesis that H2SO4 is one of the critical compounds in the nucleation process. However, compared to kinetic H2SO4 nucleation, nucleation involving OH oxidation products of monoterpenes showed a better agreement with the measurements, with R2 up to 0.97 between modelled and measured total particle number concentrations. The nucleation coefficient for kinetic H2SO4 nucleation was 2.1 × 10-11 cm3 s-1, while the organic nucleation coefficient was 9.0 × 10-14 cm3 s-1. We classified the VOC oxidation products into two sub-groups including extremely low-volatility organic compounds (ELVOCs) and semi-volatile organic compounds (SVOCs). These ELVOCs and SVOCs contributed approximately equally to the particle volume production, whereas only ELVOCs made the smallest particles to grow in size. The model simulations revealed that the chamber walls constitute a major net sink of SVOCs on the first experiment day. However, the net wall SVOC uptake was gradually reduced because of SVOC desorption during the following days. Thus, in order to capture the observed temporal evolution of the particle number size distribution, the model needs to consider reversible gas-wall partitioning.
Release of volatile and semi-volatile toxicants during house fires.
Hewitt, Fiona; Christou, Antonis; Dickens, Kathryn; Walker, Richard; Stec, Anna A
2017-04-01
Qualitative results are presented from analysis of volatile and semi-volatile organic compounds (VOCs/SVOCs) obtained through sampling of gaseous effluent and condensed particulates during a series of experimental house fires conducted in a real house. Particular emphasis is given to the 16 polycyclic aromatic hydrocarbons (PAHs) listed by the Environmental Protection Agency due to their potentially carcinogenic effects. The initial fuel packages were either cooking oil or a single sofa; these were burned both alone, and in furnished surroundings. Experiments were performed at different ventilation conditions. Qualitative Gas Chromatography-Mass Spectrometry (GC-MS) analysis found VOC/SVOC releases in the developing stages of the fires, and benzo(a)pyrene - the most carcinogenic PAH - was found in at least one sampling interval in the majority of fires. A number of phosphorus fire retardants were detected, in both the gaseous effluent and particulates, from fires where the initial fuel source was a sofa. Their release during the fire is significant as they pose toxicological concerns separate from those presented by the PAHs. Copyright © 2016. Published by Elsevier Ltd.
Chapman, Melinda J.; Gurley, Laura N.; Fitzgerald, Sharon A.
2014-01-01
Records were obtained for 305 wells and 1 spring in northwestern Lee and southeastern Chatham counties, North Carolina. Well depths ranged from 26 to 720 feet and yields ranged from 0.25 to 100 gallons per minute. A subset of 56 wells and 1 spring were sampled for baseline groundwaterquality constituents including the following: major ions; dissolved metals; nutrients; dissolved gases (including methane); volatile and semivolatile organic compounds; glycols; isotopes of strontium, radium, methane (if sufficient concentration), and water; and dissolved organic and inorganic carbon. Dissolved methane gas concentrations were low, ranging from less than 0.00007 (lowest reporting level) to 0.48 milligrams per liter. Concentrations of nitrate, boron, iron, manganese, sulfate, chloride, total dissolved solids, and measurements of pH exceeded federal and state drinking water standards in a few samples. Iron and manganese concentrations exceeded the secondary (aesthetic) drinking water standard in approximately 35 to 37 percent of the samples.
Environmental evaluations for deepening of Richmond Harbor and Santa Fe Channels
DOE Office of Scientific and Technical Information (OSTI.GOV)
Brown, B.; Kohn, N.P.; Crecelius, E.A.
Richland, California is an important commercial port in San Francisco Bay. The San Francisco District of the US Army Corps of Engineers (USACE) plans to increase the depth of Richmond Harbor and Santa Fe Channels to -38 feet Mean Lower Low Water (MLLW) to accommodate deep-draft commercial vessels. The total volume of dredged material is expected to be approximately 1.4 million cubic yards. The options for disposal of the dredged material are aquatic disposal and upland disposal. The purpose of this study was to develop a database on chemical compounds in the dredged material to assist with determination of disposalmore » methods and the need for additional testing. This purpose was accomplished through an extensive field sampling program followed by chemical analysis of samples. Field sampling involved collection of core samples from Sante Fe and Richmond Harbor Channels. Cores were shipped to Battelle/Marine Sciences Laboratory, where they were subsampled for chemical analysis and/or archived by freezing. All sediment and water samples were analyzed for priority pollutants, including metals, organotins, base/neutral semivolatile organic compounds, chlorinated pesticides and PCBs, herbicide acids, and acidic phenols. Sediment samples were also analyzed for oil and grease and total organic carbon. Organophosphorus pesticides and dioxins and furans were measured in selected sediment samples from Richland Harbor Channel and from both sediment and water samples from Santa Fe Channel. 21 refs., 10 figs., 60 tabs.« less
Estimates of the organic aerosol volatility in a boreal forest using two independent methods
NASA Astrophysics Data System (ADS)
Hong, Juan; Äijälä, Mikko; Häme, Silja A. K.; Hao, Liqing; Duplissy, Jonathan; Heikkinen, Liine M.; Nie, Wei; Mikkilä, Jyri; Kulmala, Markku; Prisle, Nønne L.; Virtanen, Annele; Ehn, Mikael; Paasonen, Pauli; Worsnop, Douglas R.; Riipinen, Ilona; Petäjä, Tuukka; Kerminen, Veli-Matti
2017-03-01
The volatility distribution of secondary organic aerosols that formed and had undergone aging - i.e., the particle mass fractions of semi-volatile, low-volatility and extremely low volatility organic compounds in the particle phase - was characterized in a boreal forest environment of Hyytiälä, southern Finland. This was done by interpreting field measurements using a volatility tandem differential mobility analyzer (VTDMA) with a kinetic evaporation model. The field measurements were performed during April and May 2014. On average, 40 % of the organics in particles were semi-volatile, 34 % were low-volatility organics and 26 % were extremely low volatility organics. The model was, however, very sensitive to the vaporization enthalpies assumed for the organics (ΔHVAP). The best agreement between the observed and modeled temperature dependence of the evaporation was obtained when effective vaporization enthalpy values of 80 kJ mol-1 were assumed. There are several potential reasons for the low effective enthalpy value, including molecular decomposition or dissociation that might occur in the particle phase upon heating, mixture effects and compound-dependent uncertainties in the mass accommodation coefficient. In addition to the VTDMA-based analysis, semi-volatile and low-volatility organic mass fractions were independently determined by applying positive matrix factorization (PMF) to high-resolution aerosol mass spectrometer (HR-AMS) data. The factor separation was based on the oxygenation levels of organics, specifically the relative abundance of mass ions at m/z 43 (f43) and m/z 44 (f44). The mass fractions of these two organic groups were compared against the VTDMA-based results. In general, the best agreement between the VTDMA results and the PMF-derived mass fractions of organics was obtained when ΔHVAP = 80 kJ mol-1 was set for all organic groups in the model, with a linear correlation coefficient of around 0.4. However, this still indicates that only about 16 % (R2) of the variation can be explained by the linear regression between the results from these two methods. The prospect of determining of extremely low volatility organic aerosols (ELVOAs) from AMS data using the PMF analysis should be assessed in future studies.
NASA Astrophysics Data System (ADS)
Liu, X.; Day, D. A.; Ziemann, P. J.; Krechmer, J. E.; Jimenez, J. L.
2017-12-01
The partitioning of semivolatile organic compounds (SVOCs) into and out of particles plays an essential role in secondary organic aerosol (SOA) formation and evolution. Most atmospheric models treat the gas/particle partitioning as an equilibrium between bulk gas and particle phases, despite potential kinetic limitations and differences in thermodynamics as a function of SOA and pre-existing OA composition. This study directly measures the partitioning of oxidized compounds in a Teflon chamber in the presence of single component seeds of different phases and polarities, including oleic acid, squalane, dioctyl sebacate, pentaethylene glycol, dry/wet ammonium sulfate, and dry/wet sucrose. The oxidized compounds are generated by a fast OH oxidation of a series of alkanols under high nitric oxide conditions. The observed SOA mass enhancements are highest with oleic acid, and lowest with wet ammonium sulfate and sucrose. A chemical ionization mass spectrometer (CIMS) was used to measure the decay of gas-phase organic nitrates, which reflects uptake by particles and chamber walls. We observed clear changes in equilibrium timescales with varying seed concentrations and in equilibrium gas-phase concentrations across different seeds. In general, the gas evolution can be reproduced by a kinetic box model that considers partitioning and evaporation with particles and chamber walls, except for the wet sucrose system. The accommodation coefficient and saturation mass concentration of each species in the presence of each seed are derived using the model. The changes in particle size distributions and composition monitored by a scanning mobility particle sizer (SMPS) and a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) are investigated to probe the SOA formation mechanism. Based on these results, the applicability of partitioning theory to these systems and the relevant quantitative parameters, including the dependencies on seed particle composition, will be discussed.
Nizzetto, Luca; Perlinger, Judith A
2012-03-06
An ecophysiological model of a structured broadleaved forest canopy was coupled to a chemical fate model of the air-canopy exchange of gaseous semivolatile chemicals to dynamically assess the short-term (hours) and medium term (days to season) air-canopy exchange and the influence of biological, climatic, and land cover drivers on the dynamics of the air-canopy exchange and on the canopy storage for airborne semivolatile pollutants. The chemical fate model accounts for effects of short-term variations in air temperature, wind speed, stomatal opening, and leaf energy balance, all as a function of layer in the canopy. Simulations showed the potential occurrence of intense short/medium term re-emission of pollutants having log K(OA) up to 10.7 from the canopy as a result of environmental forcing. In addition, relatively small interannual variations in seasonally averaged air temperature, canopy biomass, and precipitation can produce relevant changes in the canopy storage capacity for the chemicals. It was estimated that possible climate change related variability in environmental parameters (e.g., an increase of 2 °C in seasonally averaged air temperature in combination with a 10% reduction in canopy biomass due to, e.g., disturbance or acclimatization) may cause a reduction in canopy storage capacity of up to 15-25%, favoring re-emission and potential for long-range atmospheric transport. On the other hand, an increase of 300% in yearly precipitation can increase canopy sequestration by 2-7% for the less hydrophobic compounds.
Guimaraes, Wladmir B.; Falls, W. Fred; Caldwell, Andral W.; Ratliff, W. Hagan; Wellborn, John B.; Landmeyer, James E.
2011-01-01
The U.S. Geological Survey, in cooperation with the U.S. Department of the Army Environmental and Natural Resources Management Office of the U.S. Army Signal Center and Fort Gordon, Georgia, assessed the hyporheic zone, flood plain, soil gas, soil, and surface water for contaminants at the McCoys Creek Chemical Training Area (MCTA) at Fort Gordon, from October 2009 to September 2010. The assessment included the detection of organic contaminants in the hyporheic zone, flood plain, soil gas, and surface water. In addition, the organic contaminant assessment included the analysis of organic compounds classified as explosives and chemical agents in selected areas. Inorganic contaminants were assessed in soil and surface-water samples. The assessment was conducted to provide environmental contamination data to the U.S. Army at Fort Gordon pursuant to requirements of the Resource Conservation and Recovery Act Part B Hazardous Waste Permit process. Ten passive samplers were deployed in the hyporheic zone and flood plain, and total petroleum hydrocarbons (TPH) and octane were detected above the method detection level in every sampler. Other organic compounds detected above the method detection level in the hyporheic zone and flood-plain samplers were trichloroethylene, and cis- and trans- 1, 2-dichloroethylene. One trip blank detected TPH below the method detection level but above the nondetection level. The concentrations of TPH in the samplers were many times greater than the concentrations detected in the blank; therefore, all other TPH concentrations detected are considered to represent environmental conditions. Seventy-one soil-gas samplers were deployed in a grid pattern across the MCTA. Three trip blanks and three method blanks were used and not deployed, and TPH was detected above the method detection level in two trip blanks and one method blank. Detection of TPH was observed at all 71 samplers, but because TPH was detected in the trip and method blanks, TPH was censored and, therefore, only 7 of the 71 samplers were reported as detecting TPH. In addition, benzene, toluene, ethylbenzene, and total xylene were detected above the method detection level in 22 samplers. Other compounds detected above the method detection level included naphthalene, octane, undecane, tridecane, 1,2,4-trimethylbenzene, trichloroethylene, perchloroethylene, chloroform, and 1,4-dichlorobenzene. Subsequent to the soil-gas survey, five locations with elevated contaminant mass were selected and a passive sampler was deployed at those locations to detect the presence of organic compounds classified as explosives or chemical agents. No explosives or chemical agents were detected above the method detection level, but some compounds were detected below the method detection level but above the nondetection level. Dimethyl disulfide, benzothiazole, chloroacetophenones, and para-chlorophenyl methyl sulfide were all detected below the method detection level but above the nondetection level. The compounds 2,4-dinitrotoluene, and para-chlorophenyl methyl sulfone were detected in samplers but also were detected in trip blanks and are not considered as present in the MCTA. The same five locations that were selected for sampling of explosives and chemical agents were selected for soil sampling. Metal concentrations in composite soil samples collected at five locations from land surface to a depth of 6 inches did not exceed the U.S. Environmental Protection Agency Regional Screening Levels for Industrial Soil. Concentrations in some compounds were higher than the South Carolina Department of Health and Environmental Control background levels for nearby South Carolina, including aluminum, arsenic, barium, beryllium, chromium, copper, iron, lead, manganese, nickel, and potassium. A surface-water sample was collected from McCoys Creek and analyzed for volatile organic compounds, semivolatile organic compounds, and inorganic compounds (metals). No volatile organic compounds and (or) semivolatile organic compounds were detected at levels above the maximum contaminant level of the U.S. Environmental Protection Agency (USEPA) National Primary Drinking Water Standard, and no inorganic compounds exceeded the maximum contaminant level of the USEPA National Primary Drinking Water Standard or the Georgia In-Stream Water-Quality Standard. Iron was the only inorganic compound detected in the surface-water sample (578 micrograms per liter) that exceeded the USEPA National Secondary Drinking Water Standard of 300 micrograms per liter.
Nanoparticle growth by particle-phase chemistry
NASA Astrophysics Data System (ADS)
Apsokardu, Michael J.; Johnston, Murray V.
2018-02-01
The ability of particle-phase chemistry to alter the molecular composition and enhance the growth rate of nanoparticles in the 2-100 nm diameter range is investigated through the use of a kinetic growth model. The molecular components included are sulfuric acid, ammonia, water, a non-volatile organic compound, and a semi-volatile organic compound. Molecular composition and growth rate are compared for particles that grow by partitioning alone vs. those that grow by a combination of partitioning and an accretion reaction in the particle phase between two organic molecules. Particle-phase chemistry causes a change in molecular composition that is particle diameter dependent, and when the reaction involves semi-volatile molecules, the particles grow faster than by partitioning alone. These effects are most pronounced for particles larger than about 20 nm in diameter. The modeling results provide a fundamental basis for understanding recent experimental measurements of the molecular composition of secondary organic aerosol showing that accretion reaction product formation increases linearly with increasing aerosol volume-to-surface-area. They also allow initial estimates of the reaction rate constants for these systems. For secondary aerosol produced by either OH oxidation of the cyclic dimethylsiloxane (D5) or ozonolysis of β-pinene, oligomerization rate constants on the order of 10-3 to 10-1 M-1 s-1 are needed to explain the experimental results. These values are consistent with previously measured rate constants for reactions of hydroperoxides and/or peroxyacids in the condensed phase.
Understanding sources of organic aerosol during CalNex-2010 using the CMAQ-VBS
NASA Astrophysics Data System (ADS)
Woody, M. C.; Baker, K. R.; Hayes, P. L.; Jimenez, J. L.; Koo, B.; Pye, H. O. T.
2015-10-01
Community Multiscale Air Quality (CMAQ) model simulations utilizing the volatility basis set (VBS) treatment for organic aerosols (CMAQ-VBS) were evaluated against measurements collected at routine monitoring networks (Chemical Speciation Network (CSN) and Interagency Monitoring of Protected Visual Environments (IMPROVE)) and those collected during the 2010 California at the Nexus of Air Quality and Climate Change (CalNex) field campaign to examine important sources of organic aerosol (OA) in southern California. CMAQ-VBS (OA lumped by volatility, semivolatile POA) underpredicted total organic carbon (OC) at CSN (-25.5 % Normalized Median Bias (NMdnB)) and IMPROVE (-63.9 % NMdnB) locations and total OC was underpredicted to a greater degree compared to the CMAQ-AE6 (9.9 and -55.7 % NMdnB, respectively; semi-explicit OA treatment, SOA lumped by parent hydrocarbon, nonvolatile POA). However, comparisons to aerosol mass spectrometer (AMS) measurements collected at Pasadena, CA indicated that CMAQ-VBS better represented the diurnal profile and the primary/secondary split of OA. CMAQ-VBS secondary organic aerosol (SOA) underpredicted the average measured AMS oxygenated organic aerosol (OOA, a surrogate of SOA) concentration by a factor of 5.2 (4.7 μg m-3 measured vs. 0.9 μg m-3 modeled), a considerable improvement to CMAQ-AE6 SOA predictions, which were approximately 24× lower than the average AMS OOA concentration. We use two new methods, based on species ratios and on a simplified SOA parameterization from the observations, to apportion the SOA underprediction for CMAQ-VBS to too slow photochemical oxidation (estimated as 1.5× lower than observed at Pasadena using - log (NOx: NOy)), low intrinsic SOA formation efficiency (low by 1.6 to 2× for Pasadena), and too low emissions or too high dispersion for the Pasadena site (estimated to be 1.6 to 2.3× too low/high). The first and third factors will be similar for CMAQ-AE6, while the intrinsic SOA formation efficiency for that model is estimated to be too low by about 7×. For CMAQ-VBS, 90 % of the anthropogenic SOA mass formed was attributed to aged secondary semivolatile vapors (70 % originating from volatile organic compounds (VOCs) and 20 % from intermediate volatility compounds (IVOCs)). From source-apportioned model results, we found most of the CMAQ-VBS modeled POA at the Pasadena CalNex site was attributable to meat cooking emissions (48 %, and consistent with a substantial fraction of cooking OA in the observations), compared to 18 % from gasoline vehicle emissions, 13 % from biomass burning (in the form of residential wood combustion), and 8 % from diesel vehicle emissions. All "other" inventoried emission sources (e.g. industrial/point sources) comprised the final 13 %. The CMAQ-VBS semivolatile POA treatment underpredicted AMS hydrocarbon-like OA (HOA) + cooking-influenced OA (CIOA) at Pasadena by a factor of 1.8 (1.16 μg m-3 modeled vs. 2.05 μg m-3 observed) compared to a factor of 1.4 overprediction of POA in CMAQ-AE6, but did well to capture the AMS diurnal profile of HOA and CIOA, with the exception of the midday peak. We estimated that using the National Emission Inventory (NEI) POA emissions without scaling to represent SVOCs underestimates SVOCs by ~1.7×.
Phenolic compounds in Ross Sea water
NASA Astrophysics Data System (ADS)
Zangrando, Roberta; Barbaro, Elena; Gambaro, Andrea; Barbante, Carlo; Corami, Fabiana; Kehrwald, Natalie; Capodaglio, Gabriele
2016-04-01
Phenolic compounds are semi-volatile organic compounds produced during biomass burning and lignin degradation in water. In atmospheric and paleoclimatic ice cores studies, these compounds are used as biomarkers of wood combustion and supply information on the type of combusted biomass. Phenolic compounds are therefore indicators of paleoclimatic interest. Recent studies of Antarctic aerosols highlighted that phenolic compounds in Antarctica are not exclusively attributable to biomass burning but also derive from marine sources. In order to study the marine contribution to aerosols we developed an analytical method to determine the concentration of vanillic acid, vanillin, p-coumaric acid, syringic acid, isovanillic acid, homovanillic acid, syringaldehyde, acetosyringone and acetovanillone present in dissolved and particle phases in Sea Ross waters using HPLC-MS/MS. The analytical method was validated and used to quantify phenolic compounds in 28 sea water samples collected during a 2012 Ross Sea R/V cruise. The observed compounds were vanillic acid, vanillin, acetovanillone and p-coumaric acid with concentrations in the ng/L range. Higher concentrations of analytes were present in the dissolved phase than in the particle phase. Sample concentrations were greatest in the coastal, surficial and less saline Ross Sea waters near Victoria Land.
Occurrence of priority organic pollutants in the fertilizers, China.
Mo, Ce-Hui; Cai, Quan-Ying; Li, Yun-Hui; Zeng, Qiao-Yun
2008-04-15
The use of large quantities of chemical fertilizers is usually associated with environmental problems. A lot of work has been done on the concentrations of heavy metals and radionuclides in chemical fertilizers, but little work has focused on the occurrence of semi-volatile organic compounds (SVOCs). In this study the occurrence of 43 SVOCs listed as priority pollutants in 22 widely used-fertilizers of China was determined by gas chromatography coupled with mass spectrometry. Twenty-six SVOCs were detected with different detection frequencies and concentrations. The most abundant compounds were phthalic acid esters (PAEs; ranging from 1.17 to 2795 microg kg(-1) dry weight, d.w.) and nitroaromatics (up to 9765 microg kg(-1) d.w.), followed by polycyclic aromatic hydrocarbons (PAHs; <140 microg kg(-1) d.w.) and halogenated hydrocarbons (<900 microg kg(-1) d.w.). Chlorobenzenes and haloethers occurred generally at low concentrations. There are large variations in concentrations of various compounds in different fertilizers, and the total concentrations of each class of contaminants varied widely, too. The highest levels of sum concentration for 16 PAHs, for 6 PAEs and for nitroaromatics were found in organic fertilizer containing pesticide and soil amendments. Concentrations of SVOCs in coated fertilizers (the controlled release fertilizer with coating) were considerably higher than those in the corresponding fertilizers without coating. The occurrence frequencies of SVOCs in the straight fertilizers (containing only one of the major plant nutrients) were lower than in the other fertilizers.
Grimm, Hans; Eatough, Delbert J
2009-01-01
The GRIMM model 1.107 monitor is designed to measure particle size distribution and particulate mass based on a light scattering measurement of individual particles in the sampled air. The design and operation of the instrument are described. Protocols used to convert the measured size number distribution to a mass concentration consistent with U.S. Environmental Protection Agency protocols for measuring particulate matter (PM) less than 10 microm (PM10) and less than 2.5 microm (PM2.5) in aerodynamic diameter are described. The performance of the resulting continuous monitor has been evaluated by comparing GRIMM monitor PM2.5 measurements with results obtained by the Rupprecht and Patashnick Co. (R&P) filter dynamic measurement system (FDMS). Data were obtained during month-long studies in Rubidoux, CA, in July 2003 and in Fresno, CA, in December 2003. The results indicate that the GRIMM monitor does respond to total PM2.5 mass, including the semi-volatile components, giving results comparable to the FDMS. The data also indicate that the monitor can be used to estimate water content of the fine particles. However, if the inlet to the monitor is heated, then the instrument measures only the nonvolatile material, more comparable to results obtained with a conventional heated filter tapered element oscillating microbalance (TEOM) monitor. A recent modification of the model 180, with a Nafion dryer at the inlet, measures total PM2.5 including the nonvolatile and semi-volatile components, but excluding fine particulate water. Model 180 was in agreement with FDMS data obtained in Lindon, UT, during January through February 2007.
An unusual and persistent contamination of drinking water by cutting oil.
Rella, R; Sturaro, A; Parvoli, G; Ferrara, D; Doretti, L
2003-02-01
Drinking water contamination by materials, such as cutting oil, used to set up pipelines is an uncommon but possible event. This paper describes the analytical procedures used to identify the components of that contaminant in drinking water. Volatile and semi-volatile chemical species, responsible for an unpleasant taste and odour, were recognised by solid phase microextraction and GC/MS techniques. Among the volatile compounds, the presence of xylenes, bornyl acetate and diphenyl ether was confirmed by certificate standards and quantified in the most contaminated samples.
Indoor chemistry: research opportunities and challenges.
Nazaroff, W W; Goldstein, A H
2015-08-01
In this editorial, we have highlighted key research opportunities and challenges in four topical themes for indoor chemistry: human occupants as agents influencing indoor chemistry; oxidative chemistry; surface phenomena; and semivolatile organic compounds. In each case, enough prior work has been done to demonstrate the importance of the theme and to create a foundation for future studies. Extensive achievements and ongoing progress in (outdoor) atmospheric chemistry—both in the analytical methods developed and in the scientific knowledge created—also contribute to a strong foundation from which to achieve rapid research progress in this exciting new domain.
Escobar-Arnanz, J; Mekni, S; Blanco, G; Eljarrat, E; Barceló, D; Ramos, L
2018-02-09
Discarded vehicle tires have become an increasing concern worldwide due to the enormous amount of wastes generated and the increasing evidence of health problems associated to their disposal and accidental combustion. Previous studies conducted involving either simulated or open uncontrolled tire fires have identified aromatics belonging to two main classes, volatile organic compounds and polycyclic aromatic compounds (PAHs), as the most relevant chemicals generated in these burning processes. As a consequence, and due to their recognized toxicity, most studies reported up to now have mainly focused on these two categories of compounds being information concerning the possible occurrence of other aromatic classes rather limited. In this study, the enhanced separation power and structural confirmation capabilities provided by comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry (GC×GC-ToF MS) has been used, for the first time, for the non-targeted analysis of soils impacted by a tire fire and an ash collected at the scene of the fire. In total, 118 volatile and semi-volatile aromatic compounds have been differentiated. Among them, 104 compounds have been either positively or tentatively identified. PAHs with 3-5 rings and their alkyl-derivatives were the most numerous and relevant classes in the investigated samples. A significant number of sulfur, oxygen- and nitrogen-containing PAHs were also detected in the samples. The application of a script function to the raw GC×GC-ToF MS data allowed the fast filtering and automatic recognition of compounds containing halogens in their structure. This part of the study evidenced that only a limited number of regulated persistent organic pollutants were present in the investigated samples. However, it also revealed the presence of emerging organophosphorous flame retardants, whose levels in tire fire impacted soils are reported for the first time. Copyright © 2017 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Wentzell, J. J.; Liggio, J.; Li, S.; Brook, J.; Staebler, R. M.; Evans, G. J.; Jeong, C.; Sheppard, A.; Lu, G.; Gordon, M.; Mihele, C.
2010-12-01
The volatility of the organic aerosol fraction has received a great deal of attention recently in light of new volatility-based modelling approaches and due to the inability of current models to fully account for secondary organic aerosol (SOA). In this regard, evaporation of primary organic aerosol species and their subsequent oxidation may contribute significantly to SOA downwind of sources. This implies that moderate ambient temperature fluctuations can significantly increase or decrease the aerosol bound fraction of semi-volatile and intermediate volatility (SVOC + IVOC) compounds. In order to examine the importance of these more volatile organic components, a temperature controlled inlet was developed with the ability to heat and cool the aerosol in 2 C increments to 15 C above or below ambient temperature. The inlet was coupled to an Aerodyne High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and deployed on a mobile platform upwind and downwind of a major Southern Ontario highway as part of the Fast Evolution of Vehicle Emissions near Roadways (FEVER 2010) campaign. Preliminary results suggest that changes in temperature of 5-10 C can alter the partitioning of volatile organic aerosol components by up to 30%. Although the largest affect was observed 10-13 meters downwind of the vehicle emissions, a measurable affect was observed beyond 500 m and in aerosol upwind of the highway. These results suggest that a significant pool of semi-volatile organics exist, which can condense onto particles at slightly lower temperatures or evaporate to the gas phase and be further oxidized. The nature of these organic species at locations upwind and downwind of vehicle emissions will be discussed.
NASA Astrophysics Data System (ADS)
Kim, Youngseob; Sartelet, Karine; Seigneur, Christian; Charron, Aurélie; Besombes, Jean-Luc; Jaffrezo, Jean-Luc; Marchand, Nicolas; Polo, Lucie
2016-09-01
Exhaust emissions of semi-volatile organic compounds (SVOC) from passenger vehicles are usually estimated only for the particle phase via the total particulate matter measurements. However, they also need to be estimated for the gas phase, as they are semi-volatile. To better estimate SVOC emission factors of passenger vehicles, a measurement campaign using a chassis dynamometer was conducted with different instruments: (1) a constant volume sampling (CVS) system in which emissions were diluted with filtered air and sampling was performed on filters and polyurethane foams (PUF) and (2) a Dekati Fine Particle Sampler (FPS) in which emissions were diluted with purified air and sampled with on-line instruments (PTR-ToF-MS, HR-ToF-AMS, MAAP, CPC). Significant differences in the concentrations of organic carbon (OC) measured by the instruments are observed. The differences can be explained by sampling artefacts, differences between (1) the time elapsed during sampling (in the case of filter and PUF sampling) and (2) the time elapsed from emission to measurement (in the case of on-line instruments), which vary from a few seconds to 15 min, and by the different dilution factors. To relate elapsed times and measured concentrations of OC, the condensation of SVOC between the gas and particle phases is simulated with a dynamic aerosol model. The simulation results allow us to understand the relation between elapsed times and concentrations in the gas and particle phases. They indicate that the characteristic times to reach thermodynamic equilibrium between gas and particle phases may be as long as 8 min. Therefore, if the elapsed time is less than this characteristic time to reach equilibrium, gas-phase SVOC are not at equilibrium with the particle phase and a larger fraction of emitted SVOC will be in the gas phase than estimated by equilibrium theory, leading to an underestimation of emitted OC if only the particle phase is considered or if the gas-phase SVOC are estimated by equilibrium theory. Current European emission inventories for passenger cars do not yet estimate gas-phase SVOC emissions, although they may represent 60% of total emitted SVOC (gas + particle phases).
Young, Li-Hao; Liou, Yi-Jyun; Cheng, Man-Ting; Lu, Jau-Huai; Yang, Hsi-Hsien; Tsai, Ying I; Wang, Lin-Chi; Chen, Chung-Bang; Lai, Jim-Shoung
2012-01-15
Diesel engine exhaust contains large numbers of submicrometer particles that degrade air quality and human health. This study examines the number emission characteristics of 10-1000 nm nonvolatile particles from a heavy-duty diesel engine, operating with various waste cooking oil biodiesel blends (B2, B10 and B20), engine loads (0%, 25%, 50% and 75%) and a diesel oxidation catalyst plus diesel particulate filter (DOC+DPF) under steady modes. For a given load, the total particle number concentrations (N(TOT)) decrease slightly, while the mode diameters show negligible changes with increasing biodiesel blends. For a given biodiesel blend, both the N(TOT) and mode diameters increase modestly with increasing load of above 25%. The N(TOT) at idle are highest and their size distributions are strongly affected by condensation and possible nucleation of semivolatile materials. Nonvolatile cores of diameters less than 16 nm are only observed at idle mode. The DOC+DPF shows remarkable filtration efficiency for both the core and soot particles, irrespective of the biodiesel blend and engine load under study. The N(TOT) post the DOC+DPF are comparable to typical ambient levels of ≈ 10(4)cm(-3). This implies that, without concurrent reductions of semivolatile materials, the formation of semivolatile nucleation mode particles post the after treatment is highly favored. Copyright © 2011 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Schnelle-Kreis, Jürgen; Sklorz, Martin; Peters, Anette; Cyrys, Josef; Zimmermann, Ralf
PM 2.5 Particle-associated semi-volatile organic compounds (SVOC) were determined in the city of Augsburg, Germany. Daily samples were collected at a central monitoring station from late summer to late autumn 2002. The concentrations of polycyclic aromatic hydrocarbons (PAH), oxidized PAH (O-PAH), n-alkanes, hopanes and long chain linear alkylbenzenes were determined by direct thermal desorption-gas chromatography-time of flight mass spectrometry (DTD-GC-TOFMS). Additionally, PM 2.5 particle mass and number concentrations were measured. The sampling campaign can be divided into two parts, distinguished by a lower temperature level in the second part of the campaign. The particulate mass concentration showed no significant changes, whereas most of the SVOC had significant higher mean and peak concentrations in the colder period. The analysis of the data showed an increased influence of non-traffic sources in the colder period, reflected by a weak shift in the PAH profile and a significant shift in the hopane pattern. Statistical analysis of the inter-group correlations was carried out. Eight clusters partly representing different sources of the aerosol have been identified.
Wei, Wenjuan; Mandin, Corinne; Ramalho, Olivier
2018-03-01
Semi-volatile organic compounds (SVOCs) in indoor environments can partition among the gas phase, airborne particles, settled dust, and available surfaces. The mass transfer parameters of SVOCs, such as the mass transfer coefficient and the partition coefficient, are influenced by indoor environmental factors. Subsequently, indoor SVOC concentrations and thus occupant exposure can vary depending on environmental factors. In this review, the influence of six environmental factors, i.e., indoor temperature, humidity, ventilation, airborne particle concentration, source loading factor, and reactive chemistry, on the mass transfer parameters and indoor concentrations of SVOCs was analyzed and tentatively quantified. The results show that all mass transfer parameters vary depending on environmental factors. These variations are mostly characterized by empirical equations, particularly for humidity. Theoretical calculations of these parameters based on mass transfer mechanisms are available only for the emission of SVOCs from source surfaces when airborne particles are not present. All mass transfer parameters depend on the temperature. Humidity influences the partition of SVOCs among different phases and is associated with phthalate hydrolysis. Ventilation has a combined effect with the airborne particle concentration on SVOC emission and their mass transfer among different phases. Indoor chemical reactions can produce or eliminate SVOCs slowly. To better model the dynamic SVOC concentration indoors, the present review suggests studying the combined effect of environmental factors in real indoor environments. Moreover, interactions between indoor environmental factors and human activities and their influence on SVOC mass transfer processes should be considered. Copyright © 2017 Elsevier Ltd. All rights reserved.
Lucattini, Luisa; Poma, Giulia; Covaci, Adrian; de Boer, Jacob; Lamoree, Marja H; Leonards, Pim E G
2018-06-01
As many people spend a large part of their life indoors, the quality of the indoor environment is important. Data on contaminants such as flame retardants, pesticides and plasticizers are available for indoor air and dust but are scarce for consumer products such as computers, televisions, furniture, carpets, etc. This review presents information on semi-volatile organic compounds (SVOCs) in consumer products in an attempt to link the information available for chemicals in indoor air and dust with their indoor sources. A number of 256 papers were selected and divided among SVOCs found in consumer products (n = 57), indoor dust (n = 104) and air (n = 95). Concentrations of SVOCs in consumer products, indoor dust and air are reported (e.g. PFASs max: 13.9 μg/g in textiles, 5.8 μg/kg in building materials, 121 ng/g in house dust and 6.4 ng/m 3 in indoor air). Most of the studies show common aims, such as human exposure and risk assessment. The main micro-environments investigated (houses, offices and schools) reflect the relevance of indoor air quality. Most of the studies show a lack of data on concentrations of chemicals in consumer goods and often only the presence of chemicals is reported. At the moment this is the largest obstacle linking chemicals in products to chemicals detected in indoor air and dust. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.
A novel inlet system for online chemical analysis of semi-volatile submicron particulate matter
NASA Astrophysics Data System (ADS)
Eichler, P.; Müller, M.; D'Anna, B.; Wisthaler, A.
2015-03-01
We herein present a novel modular inlet system designed to be coupled to low-pressure gas analyzers for online chemical characterization of semi-volatile submicron particles. The "chemical analysis of aerosol online" (CHARON) inlet consists of a gas-phase denuder for stripping off gas-phase analytes, an aerodynamic lens for particle collimation combined with an inertial sampler for the particle-enriched flow and a thermodesorption unit for particle volatilization prior to chemical analysis. The denuder was measured to remove gas-phase organics with an efficiency > 99.999% and to transmit particles in the 100-750 nm size range with a 75-90% efficiency. The measured average particle enrichment factor in the subsampling flow from the aerodynamic lens was 25.6, which is a factor of 3 lower than the calculated theoretical optimum. We coupled the CHARON inlet to a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) which quantitatively detects most organic analytes and ammonia. The combined CHARON-PTR-ToF-MS setup is thus capable of measuring both the organic and the ammonium fraction in submicron particles in real time. Individual organic compounds can be detected down to levels of 10-20 ng m-3. Two proof-of-principle studies were carried out for demonstrating the analytical power of this new instrumental setup: (i) oxygenated organics and their partitioning between the gas and the particulate phase were observed from the reaction of limonene with ozone and (ii) nicotine was measured in cigarette smoke particles demonstrating that selected organic target compounds can be detected in submicron particles in real time.
Effect of atmospheric ageing on volatility and ROS of biodiesel exhaust nano-particles
NASA Astrophysics Data System (ADS)
Pourkhesalian, A. M.; Stevanovic, S.; Rahman, M. M.; Faghihi, E. M.; Bottle, S. E.; Masri, A. R.; Brown, R. J.; Ristovski, Z. D.
2015-03-01
In the prospect of limited energy resources and climate change, effects of alternative biofuels on primary emissions are being extensively studied. Our two recent studies have shown that biodiesel fuel composition has a~significant impact on primary particulate matter emissions. It was also shown that particulate matter caused by biodiesels was substantially different from the emissions due to petroleum diesel. Emissions appeared to have higher oxidative potential with the increase in oxygen content and decrease of carbon chain length and unsaturation levels of fuel molecules. Overall, both studies concluded that chemical composition of biodiesel is more important than its physical properties in controlling exhaust particle emissions. This suggests that the atmospheric ageing processes, including secondary organic aerosol formation, of emissions from different fuels will be different as well. In this study, measurements were conducted on a modern common-rail diesel engine. To get more information on realistic properties of tested biodiesel particulate matter once they are released into the atmosphere, particulate matter was exposed to atmospheric oxidants, ozone and ultra-violet light; and the change in their properties was monitored for different biodiesel blends. Upon the exposure to oxidative agents, the chemical composition of the exhaust changes. It triggers the cascade of photochemical reactions resulting in the partitioning of semi-volatile compounds between the gas and particulate phase. In most of the cases, aging lead to the increase in volatility and oxidative potential, and the increment of change was mainly dependent on the chemical composition of fuels as the leading cause for the amount and the type of semi-volatile compounds present in the exhaust.
NASA Astrophysics Data System (ADS)
Pereira, K. L.; Hamilton, J. F.; Rickard, A. R.; Bloss, W. J.; Alam, M. S.; Camredon, M.; Muñoz, A.; Vásquez, M.; Borrás, E.; Ródenas, M.
2013-12-01
The increasing demand for palm oil for uses in biofuel and food products is leading to rapid expansion of oil palm agriculture. Methyl chavicol (also known as estragole and 1-allyl-4-methoxybenzene) is an oxygenated biogenic volatile organic compound that was recently identified as the main floral emission from an oil palm plantation in Malaysian Borneo. The emissions of methyl chavicol observed may impact regional atmospheric chemistry, but little is known of its ability to form secondary organic aerosol (SOA). The photo-oxidation of methyl chavicol was investigated at the European Photoreactor chamber as a part of the atmospheric chemistry of methyl chavicol (ATMECH) project. Aerosol samples were collected using a particle into liquid sampler (PILS) and analysed offline using an extensive range of instruments including; high performance liquid chromatography mass spectrometry (HPLC-ITMS), high performance liquid chromatography quadrupole time-of-flight mass spectrometry (HPLC-QTOFMS) and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). The SOA yield was determined as 18-29% depending on initial precursor (VOC : NOx) mixing ratios. In total, 59 SOA compounds were observed and the structures of 10 compounds have been identified using high resolution tandem mass spectrometry. The addition of hydroxyl and/or nitro functional groups to the aromatic ring appears to be an important mechanistic pathway for aerosol formation. This results in the formation of compounds with both low volatility and high O : C ratios, where functionalisation rather than fragmentation is mainly observed as a~result of the stability of the ring. The SOA species observed can be characterized as semi-volatile to low volatile oxygenated organic aerosol (SVOOA and LVOOA) components and therefore may be important in aerosol formation and growth.
Organtini, Kari L; Myers, Anne L; Jobst, Karl J; Reiner, Eric J; Ross, Brian; Ladak, Adam; Mullin, Lauren; Stevens, Douglas; Dorman, Frank L
2015-10-20
Residential and commercial fires generate a complex mixture of volatile, semivolatile, and nonvolatile compounds. This study focused on the semi/nonvolatile components of fire debris to better understand firefighter exposure risks. Using the enhanced sensitivity of gas chromatography coupled to atmospheric pressure ionization-tandem mass spectrometry (APGC-MS/MS), complex fire debris samples collected from simulation fires were analyzed for the presence of potentially toxic polyhalogenated dibenzo-p-dioxins and dibenzofurans (PXDD/Fs and PBDD/Fs). Extensive method development was performed to create multiple reaction monitoring (MRM) methods for a wide range of PXDD/Fs from dihalogenated through hexa-halogenated homologue groups. Higher halogenated compounds were not observed due to difficulty eluting them off the long column used for analysis. This methodology was able to identify both polyhalogenated (mixed bromo-/chloro- and polybromo-) dibenzo-p-dioxins and dibenzofurans in the simulated burn study samples collected, with the dibenzofuran species being the dominant compounds in the samples. Levels of these compounds were quantified as total homologue groups due to the limitations of commercial congener availability. Concentration ranges in household simulation debris were observed at 0.01-5.32 ppb (PXDFs) and 0.18-82.11 ppb (PBDFs). Concentration ranges in electronics simulation debris were observed at 0.10-175.26 ppb (PXDFs) and 0.33-9254.41 ppb (PBDFs). Samples taken from the particulate matter coating the firefighters' helmets contained some of the highest levels of dibenzofurans, ranging from 4.10 ppb to 2.35 ppm. The data suggest that firefighters and first responders at fire scenes are exposed to a complex mixture of potentially hundreds to thousands of different polyhalogenated dibenzo-p-dioxins and dibenzofurans that could negatively impact their health.
Maire, Murielle; Rega, Barbara; Cuvelier, Marie-Elisabeth; Soto, Paola; Giampaoli, Pierre
2013-12-15
This paper investigates the effect of ingredients on the reactions occurring during the making of sponge cake and leading to the generation of volatile compounds related to flavour quality. To obtain systems sensitive to lipid oxidation (LO), a formulation design was applied varying the composition of fatty matter and eggs. Oxidation of polyunsaturated fatty acids (PUFA) and formation of related volatile compounds were followed at the different steps of cake-making. Optimised dynamic Solid Phase Micro Extraction was applied to selectively extract either volatile or semi-volatile compounds directly from the baking vapours. We show for the first time that in the case of alveolar baked products, lipid oxidation occurs very early during the step of dough preparation and to a minor extent during the baking process. The generation of lipid oxidation compounds depends on PUFA content and on the presence of endogenous antioxidants in the raw matter. Egg yolk seemed to play a double role on reactivity: protecting unsaturated lipids from oxidation and being necessary to generate a broad class of compounds of the Maillard reaction during baking and linked to the typical flavour of sponge cake. Copyright © 2013 Elsevier Ltd. All rights reserved.
Pandis, Spyros N; Donahue, Neil M; Murphy, Benjamin N; Riipinen, Ilona; Fountoukis, Christos; Karnezi, Eleni; Patoulias, David; Skyllakou, Ksakousti
2013-01-01
The formation, atmospheric evolution, properties, and removal of organic particulate matter remain some of the least understood aspects of atmospheric chemistry despite the importance of organic aerosol (OA) for both human health and climate change. Here, we summarize our recent efforts to deal with the chemical complexity of the tens of thousands of organic compounds in the atmosphere using the volatility-oxygen content framework (often called the 2D-Volatility Basis Set, 2D-VBS). Our current ability to measure the ambient OA concentration as a function of its volatility and oxygen to carbon (O:C) ratio is evaluated. The combination of a thermodenuder, isothermal dilution and Aerosol Mass Spectrometry (AMS) together with a mathematical aerosol dynamics model is a promising approach. The development of computational modules based on the 2D-VBS that can be used in chemical transport models (CTMs) is described. Approaches of different complexity are tested against ambient observations, showing the challenge of simulating the complex chemical evolution of atmospheric OA. The results of the simplest approach describing the net change due to functionalization and fragmentation are quite encouraging, reproducing both the observed OA levels and O : C in a variety of conditions. The same CTM coupled with source-apportionment algorithms can be used to gain insights into the travel distances and age of atmospheric OA. We estimate that the average age of OA near the ground in continental locations is 1-2 days and most of it was emitted (either as precursor vapors or particles) hundreds of kilometers away. Condensation of organic vapors on fresh particles is critical for the growth of these new particles to larger sizes and eventually to cloud condensation nuclei (CCN) sizes. The semivolatile organics currently simulated by CTMs are too volatile to condense on these tiny particles with high curvature. We show that chemical aging reactions converting these semivolatile compounds to extremely low volatility compounds can explain the observed growth rates of new particles in rural environments.
Volatility of source apportioned wintertime organic aerosol in the city of Athens
NASA Astrophysics Data System (ADS)
Louvaris, Evangelos E.; Florou, Kalliopi; Karnezi, Eleni; Papanastasiou, Dimitrios K.; Gkatzelis, Georgios I.; Pandis, Spyros N.
2017-06-01
The volatility distribution of ambient organic aerosol (OA) and its components was measured during the winter of 2013 in the city of Athens combining a thermodenuder (TD) and a High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS). Positive Matrix Factorization (PMF) analysis of both the ambient and the thermodenuder AMS-spectra resulted in a four-factor solution for the OA, namely: hydrocarbon-like OA (HOA), biomass burning OA (BBOA), cooking OA (COA), and oxygenated OA (OOA). The thermograms of the four factors were analyzed and the corresponding volatility distributions were estimated using the volatility basis set (VBS). All four factors included compounds with a wide range of effective volatilities from 10 to less than 10-4 μg m-3 at 298 K. Almost 40% of the HOA consisted of low-volatility organic compounds (LVOCs) with the semi-volatile compounds (SVOCs) representing roughly 30%, while the remaining 30% consisted of extremely low volatility organic compounds (ELVOCs). BBOA was more volatile than the HOA factor on average, with 10% ELVOCs, 40% LVOCs, and 50% SVOCs. 10% of the COA consisted of ELVOCs, another 65% LVOCs, and 50% SVOCs. Finally, the OOA was the least volatile factor and included 40% ELVOCs, 25% LVOCs, and 35% SVOCs. Combining the volatility distributions and the O:C ratios of the various factors, we placed our results in the 2D-VBS analysis framework of Donahue et al. (2012). HOA and BBOA are in the expected region but also include an ELVOC component. COA is in similar range as HOA, but on average is half an order of magnitude more volatile. The OOA in these wintertime conditions had a moderate O:C ratio and included both semi-volatile and extremely low volatility components. The above results are sensitive to the assumed values of the effective vaporization enthalpy and the accommodation coefficient. A reduction of the accommodation coefficient by an order of magnitude or the reduction of the vaporization enthalpy by 20 kJ mol-1 results in the increase of the average volatility by half an order of magnitude.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Castaldini, C.; Waterland, L.R.; Lips, H.I.
1986-02-01
The report is a compendium of detailed test sampling and analysis data obtained in field tests of an enhanced-oil-recovery steam generator (EOR steamer) equipped with a MHI PM low-NOx crude oil burner. Test data reported include equipment calibration records, steamer operating data, and complete flue-gas emission results. Flue-gas emission measurements included continuous monitoring for criteria pollutants; onsite gas chromatography (GC) for volatile hydrocarbons (Cl-C6); Methods 5/8 sampling for particulate and SO/sub 2/ and SO/sub 3/ emissions; source assessment sampling system (SASS) for total organics in two boiling-point ranges (100 to 300 C and greater than or equal to 300 C),more » organic compound category information using infrared spectrometry (IR), and specific quantitation of the semivolatile organic priority pollutants using gas chromatography/mass spectrometry (GC/MS); Andersen impactor train measurements of emitted particle-size distribution; and N/sub 2/O emissions by gas chromatography/electron-capture detector (GC/ECD).« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
DeRosier, R.; Waterland, L.R.
1986-02-01
This report is a compendium of detailed test sampling and analysis data obtained in field tests of a watertube industrial boiler burning a coal/water slurry (CWS). Test data reported include preliminary stack test data, boiler operating data, and complete flue-gas emission results. Flue-gas emission measurements included continuous monitoring for criteria pollutants; onsite gas chromatography (GC) for volatile hydrocarbons (Cl-C6); Methods 5/8 sampling for particulate, SO/sub 2/, and SO/sub 3/ emissions; source assessment sampling system (SASS) for total organics in two boiling point ranges (100 to 300 C and > 300 C), organic compound category information using infrared spectrometry (IR), liquidmore » column (LC) chromatography separation, and low-resolution mass spectrometry (LRMS), specific quantitation of the semivolatile organic priority pollutants using gas chromatography/mass spectrometry (GC/MS), and trace-element emissions using spark-source mass spectrometry (SSMS) and atomic absorption spectroscopy (AAS); N/sub 2/O emissions by gas chromatography/electron-capture detector (GC/ECD); and biological assay testing of SASS and ash-stream samples.« less
Zhou, Simon Ningsun; Oakes, Ken D; Servos, Mark R; Pawliszyn, Janusz
2008-08-15
Previous field studies utilizing solid-phase microextraction (SPME) predominantly focused on volatile and semivolatile compounds in air or water. Earlier in vivo sampling studies utilizing SPME were limited to the liquid matrix (blood). The present study has expanded the SPME technique to semisolid tissues under laboratory and field conditions through the investigation of both theoretical and applied experimental approaches. Pre-equilibrium extraction and desorption were performed in vivo in two separate animals. Excellent linearity was found between the amounts extracted by SPME from the muscle of living fish and the waterborne concentrations of pharmaceuticals. A simple SPME method is also described to simultaneously determine free and total analyte concentrations in living tissue. The utility of in vivo SPME sampling was evaluated in wild fish collected from a number of different river locations under varying degrees of influence from municipal wastewater effluents. Diphenhydramine and diltiazem were detected in the muscle of fish downstream of a local wastewater treatment plant. Based on this study, SPME demonstrated several important advantages such as simplicity, sensitivity, and robustness under laboratory and in vivo field sampling conditions.
Romanok, Kristin M.; Fischer, Jeffrey M.; Riva-Murray, Karen; Brightbill, Robin; Bilger, Michael
2006-01-01
As part of the National Water-Quality Assessment (NAWQA) program activities in the Delaware River Basin (DELR), samples of fish tissue from 21 sites and samples of bed sediment from 35 sites were analyzed for a suite of organic compounds and trace elements. The sampling sites, within subbasins ranging in size from 11 to 600 square miles, were selected to represent 5 main land-use categories in the DELR -forest, low-agricultural, agricultural, urban, and mixed use. Samples of both fish tissue and bed sediment were also collected from 4 'large-river' sites that represented drainage areas ranging from 1,300 to 6,800 square miles, areas in which the land is used for a variety of purposes. One or more of the organochlorine compounds-DDT and chlordane metabolites, polychlorinated biphenyls (total PCBs), and dieldrin- were detected frequently in samples collected over a wide geographic area. One or more of these compounds were detected in fish-tissue samples from 92 percent of the sites and in bed-sediment samples from 82 percent of the sites. Concentrations of total DDT, total chlordanes, total PCBs, and dieldrin in whole white suckers and in bed sediment were significantly related to urban/industrial basin characteristics, such as percentage of urban land use and population density. Semi-volatile organic compounds (SVOCs)-total polycyclic aromatic hydrocarbons (PAHs), total phthalates, and phenols- were detected frequently in bed-sediment samples. All three types of SVOCs were detected in samples from at least one site in each land-use category. The highest detection rates and concentrations typically were in samples from sites in the urban and mixed land-use categories, as well as from the large-river sites. Concentrations of total PAHs and total phthalates in bed-sediment samples were found to be statistically related to percentages of urban land use and to population density in the drainage areas represented by the sampling sites. The samples of fish tissue and bed sediment collected throughout the DELR were analyzed for a large suite of trace elements, but results of the analyses for eight elements-arsenic, cadmium, chromium, copper, lead, nickel, mercury, and zinc- that are considered contaminants of concern are described in this report. One or more of the eight trace elements were detected in samples from every fish tissue and bed-sediment sampling site, and all of the trace elements were detected in samples from 97 percent of the bed-sediment sites. The concentrations of organic compounds and trace elements in the DELR samples were compared to applicable guidelines for the protection of wildlife and other biological organisms. Concentrations of total DDT, total chlordanes, total PCBs, and dieldrin in fish-tissue samples from 14 sites exceeded one or more of the Wildlife Protective Guidelines established by the New York State Department of Environmental Conservation. Concentrations of one or more organic compounds in samples from 16 bed-sediment sites exceeded the Threshold Effects Concentrations (TEC) of the Canadian Sediment Quality Guidelines, and concentrations of one or more of the eight trace elements in samples from 38 bed-sediment sites exceeded the TEC. (The TEC is the concentration below which adverse biological effects in freshwater ecosystems are expected to be rare.) Concentrations of organic compounds in samples from some bed-sediment sites exceeded the Canadian Probable Effects Concentrations (PEC), and concentrations of trace elements in samples from 18 sites exceeded the PEC. (The PEC is the concentration above which adverse effects to biological organisms are expected to occur frequently). Concentrations of organic compounds and trace elements in samples from the DELR were compared to similar data from other NAWQA study units in the northeastern United States and also data from the Mobile River (Alabama) Basin and the Northern Rockies Intermontane Basin study units. Median concentrations of to
NASA Astrophysics Data System (ADS)
Connell, Matthew
Increased installation of polymer potable water pipes in United States plumbing systems has created a need to thoroughly evaluate their water quality impacts. Eleven brands of new polymer drinking water pipe were evaluated for assimilable organic carbon (AOC) release at room temperature for 28 days. They included polyvinyl chloride (PVC), high-density polyethylene (HDPE), polypropylene (PP), and cross-linked polyethylene (PEX) pipes. Three of eight PEX pipe brands exceeded a 100 microg/L AOC threshold for microbial regrowth for the first exposure period and no brands exceeded this value on day 28. No detectable increase in AOC was found for PP and PEX-a1 pipes; the remaining pipe brands contributed marginal AOC levels. Water quality impacts were more fully evaluated for two brands of PEX-b and one brand of PP pipe. PEX pipes released more total organic carbon (TOC), volatile organic compounds (VOC), and semivolatile organic compounds (SVOC) and caused greater odor than the PP pipe. All three materials showed reductions in these water quality parameters over 30 days. Three PEX pipe field studies revealed that aged systems did not display more intense odors than distribution systems. However, the organic releases from polymer pipes may still alter water quality and contribute to rapid microbial growth, even though the aesthetic impacts are temporary.
Post-Vietnam military herbicide exposures in UC-123 Agent Orange spray aircraft.
Lurker, Peter A; Berman, Fred; Clapp, Richard W; Stellman, Jeanne Mager
2014-04-01
During the Vietnam War, approximately 20 million gallons of herbicides, including ~10.5 million gallons of dioxin-contaminated Agent Orange, were sprayed by about 34 UC-123 aircraft that were subsequently returned to the United States, without decontamination or testing, to three Air Force reserve units for transport operations (~1971-1982). In 1996, observed dioxin contamination led to withdrawal of these UC-123s from public auction and to their smelting in 2009. Current Air Force and Department of Veterans Affairs policies stipulate that "dried residues" of chemical herbicides and dioxin had not lead to meaningful exposures to flight crew and maintenance personnel, who are thus ineligible for Agent Orange-related benefits or medical examinations and treatment. Sparse monitoring data are available for analysis. Three complementary approaches for modeling potential exposures to dioxin in the post-Vietnam war aircraft were employed: (1) using 1994 and 2009 Air Force surface wipe data to model personnel exposures and to estimate dioxin body burden for dermal-oral exposure for dried residues using modified generic US Environmental Protection Agency intake algorithms; (2) comparing 1979 Air Force 2,4- dichlorophenoxyacetic acid and 2,4-5-trichlorophenoxyacetic acid air samples to saturated vapor pressure concentrations to estimate potential dioxin exposure through inhalation, ingestion and skin contact with contaminated air and dust; and (3) applying emission models for semivolatile organic compounds from contaminated surfaces to estimate airborne contamination. Model (1): Body-burden estimates for dermal-oral exposure were 0.92 and 5.4pg/kg body-weight-day for flight crew and maintainers. The surface wipe concentrations were nearly two orders of magnitude greater than the US Army guidance level. Model (2): measured airborne concentrations were at least five times greater than saturated vapor pressure, yielding dioxin estimates that ranged from 13.2-27.0pg/m(3), thus supporting the likelihood of dioxin dust adsorption. Model (3): Theoretical models yielded consistent estimates to Model 2, 11-49pg/m(3), where the range reflects differences in experimental value of dioxin vapor pressure and surface area used. Model (3) results also support airborne contamination and dioxin dust adsorption. Inhalation, ingestion and skin absorption in aircrew and maintainers were likely to have occurred during post-Vietnam use of the aircraft based on the use of three complementary models. Measured and modeled values for dioxin exceeded several available guidelines. Deposition-aerosolization-redeposition homeostasis of semivolatile organic compound contaminants, particularly dioxin, is likely to have continually existed within the aircraft. Current Air Force and Department of Veterans Affairs policies are not consistent with the available industrial hygiene measurements or with the widely accepted models for semivolatile organic compounds. Copyright © 2014 Elsevier Inc. All rights reserved.
NASA Astrophysics Data System (ADS)
Ciarelli, Giancarlo; Aksoyoglu, Sebnem; El Haddad, Imad; Bruns, Emily A.; Crippa, Monica; Poulain, Laurent; Äijälä, Mikko; Carbone, Samara; Freney, Evelyn; O'Dowd, Colin; Baltensperger, Urs; Prévôt, André S. H.
2017-06-01
We evaluated a modified VBS (volatility basis set) scheme to treat biomass-burning-like organic aerosol (BBOA) implemented in CAMx (Comprehensive Air Quality Model with extensions). The updated scheme was parameterized with novel wood combustion smog chamber experiments using a hybrid VBS framework which accounts for a mixture of wood burning organic aerosol precursors and their further functionalization and fragmentation in the atmosphere. The new scheme was evaluated for one of the winter EMEP intensive campaigns (February-March 2009) against aerosol mass spectrometer (AMS) measurements performed at 11 sites in Europe. We found a considerable improvement for the modelled organic aerosol (OA) mass compared to our previous model application with the mean fractional bias (MFB) reduced from -61 to -29 %. We performed model-based source apportionment studies and compared results against positive matrix factorization (PMF) analysis performed on OA AMS data. Both model and observations suggest that OA was mainly of secondary origin at almost all sites. Modelled secondary organic aerosol (SOA) contributions to total OA varied from 32 to 88 % (with an average contribution of 62 %) and absolute concentrations were generally under-predicted. Modelled primary hydrocarbon-like organic aerosol (HOA) and primary biomass-burning-like aerosol (BBPOA) fractions contributed to a lesser extent (HOA from 3 to 30 %, and BBPOA from 1 to 39 %) with average contributions of 13 and 25 %, respectively. Modelled BBPOA fractions were found to represent 12 to 64 % of the total residential-heating-related OA, with increasing contributions at stations located in the northern part of the domain. Source apportionment studies were performed to assess the contribution of residential and non-residential combustion precursors to the total SOA. Non-residential combustion and road transportation sector contributed about 30-40 % to SOA formation (with increasing contributions at urban and near industrialized sites), whereas residential combustion (mainly related to wood burning) contributed to a larger extent, around 60-70 %. Contributions to OA from residential combustion precursors in different volatility ranges were also assessed: our results indicate that residential combustion gas-phase precursors in the semivolatile range (SVOC) contributed from 6 to 30 %, with higher contributions predicted at stations located in the southern part of the domain. On the other hand, the oxidation products of higher-volatility precursors (the sum of intermediate-volatility compounds (IVOCs) and volatile organic compounds (VOCs)) contribute from 15 to 38 % with no specific gradient among the stations. Although the new parameterization leads to a better agreement between model results and observations, it still under-predicts the SOA fraction, suggesting that uncertainties in the new scheme and other sources and/or formation mechanisms remain to be elucidated. Moreover, a more detailed characterization of the semivolatile components of the emissions is needed.
Characterization of Air Toxics from an Oil-Fired Firetube Boiler.
Miller, C Andrew; Ryan, Jeffrey V; Lombardo, Tony
1996-08-01
Tests were conducted on a commercially available firetube package boiler running on #2 through #6 oils to determine the emissions levels of hazardous air pollutants from the combustion of four fuel oils (a #2 oil, a #5 oil, a low sulfur #6 oil, and a high sulfur #6 oil). Measurements of carbon monoxide, nitrogen oxides, particulate matter, and sulfur dioxide stack gas concentrations were made for each oil. Flue gases were also sampled to determine levels of volatile and semivolatile organic compounds and of metals. Analytical procedures were used to provide more detailed information regarding the emissions rates for carbonyls (aldehydes and ketones), and polycyclic aromatic hydrocarbons (PAHs) in addition to the standard analyses for volatile and semivolatile organics. Metals emissions were greater than organic emissions for all oils tested, by an order of magnitude. Carbonyls dominated the organic emissions, with emission rates more than double the remaining organics for all four oils tested. Formaldehyde made up the largest percentage of carbonyls, at roughly 50% of these emissions for three of the four oils, and approximately 30% of the carbonyl emissions from the low sulfur #6 oil. Naphthalene was found to be the largest part of the PAH emissions for three of the four oils, with phenanthrene being greatest for the #2 fuel oil. The flue gases were also sampled for polychlorinated dibenzodioxins and polychlorinated dibenzofurans; however, inconsistent levels were found between repeat tests. For the boiler tested, no single hazardous air pollutant (HAP) was emitted at a rate which would require control under Title III of the Clean Air Act Amendments of 1990. The fuel emitting the largest amount of HAPs was the high sulfur #6 oil, which had a total HAP emission rate of less than 100 lb (45 kg)/year, based on operation for a full year at a firing rate of 1.25 x 106 Btu/hr (50% load of the unit tested).
Global-scale combustion sources of organic aerosols: sensitivity to formation and removal mechanisms
NASA Astrophysics Data System (ADS)
Tsimpidi, Alexandra P.; Karydis, Vlassis A.; Pandis, Spyros N.; Lelieveld, Jos
2017-06-01
Organic compounds from combustion sources such as biomass burning and fossil fuel use are major contributors to the global atmospheric load of aerosols. We analyzed the sensitivity of model-predicted global-scale organic aerosols (OA) to parameters that control primary emissions, photochemical aging, and the scavenging efficiency of organic vapors. We used a computationally efficient module for the description of OA composition and evolution in the atmosphere (ORACLE) of the global chemistry-climate model EMAC (ECHAM/MESSy Atmospheric Chemistry). A global dataset of aerosol mass spectrometer (AMS) measurements was used to evaluate simulated primary (POA) and secondary (SOA) OA concentrations. Model results are sensitive to the emission rates of intermediate-volatility organic compounds (IVOCs) and POA. Assuming enhanced reactivity of semi-volatile organic compounds (SVOCs) and IVOCs with OH substantially improved the model performance for SOA. The use of a hybrid approach for the parameterization of the aging of IVOCs had a small effect on predicted SOA levels. The model performance improved by assuming that freshly emitted organic compounds are relatively hydrophobic and become increasingly hygroscopic due to oxidation.
Jerković, Igor; Marijanović, Zvonimir; Kezić, Janja; Gugić, Mirko
2009-07-27
Volatile organic compounds of Amorpha fruticosa honey samples were isolated by headspace solid-phase microextraction (HS-SPME) and ultrasonic solvent extraction (USE), followed by gas chromatography and mass spectrometry analyses (GC, GC-MS), in order to obtain complementary data for overall characterization of the honey aroma. The headspace of the honey was dominated by 2-phenylethanol (38.3-58.4%), while other major compounds were trans- and cis-linalool oxides, benzaldehyde and benzyl alcohol. 2-Phenylethanol (10.5-16.8%) and methyl syringate (5.8-8.2%) were the major compounds of ultrasonic solvent extracts, with an array of small percentages of linalool, benzene and benzoic acid derivatives, aliphatic hydrocarbons and alcohols, furan derivatives and others. The scavenging ability of the series of concentrations of the honey ultrasonic solvent extracts and the corresponding honey samples was tested by a DPPH (1,1-diphenyl-2-picrylhydrazyl) assay. Approximately 25 times lower concentration ranges (up to 2 g/L) of the extracts exhibited significantly higher free radical scavenging potential with respect to the honey samples.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Not Available
1993-03-31
This decision document presents the selected remedial action for Operable Unit 3 of the William Dick Lagoons Site (Site), in West Caln Township, Pennsylvania. The remedy described in this Record of Decision is for Operable Unit 3 at the Site. The remedy selected for Operable Unit 3 will reduce the concentrations of hazardous substances in the Site soils so that leaching of contaminants into the groundwater will be minimized. Reduction of the volatile organic compounds and semi-volatile organic compounds in the soils is necessary in order the groundwater will not continue to be impacted above acceptable levels. In addition, themore » installation of a vegetative soil cover or multi-layer cap will prevent the surrounding community from exposure to Site-related contaminants through inhalation, ingestion, and dermal contact.« less
Mitjans, D; Ventura, F
2004-01-01
Closed loop stripping analysis (CLSA), a suitable tool for the determination of volatile and semivolatile compounds at low trace levels (ng/l), has been used to determine and quantify seven selected musks and two fragrances (Acetyl cedrene and Amberonne). The obtained extracts are analyzed by high resolution gas chromatography coupled to mass spectrometry (GC/MS) operating in the SIM mode. Quality parameters such as limit of detection; matrix effects; precision expressed as repeatability and reproducibility relative standard deviations of the method and an estimation of the uncertainty have been evaluated. The method has been applied to the analysis of wastewater effluents, surface water and tap water from different places in Europe. All samples contained differents musks at ng/l levels with the polycyclic musks Galaxolide and Tonalide and both fragrances, Amberonne and Acetyl cedrene, being the most abundant. These results suggest the importance of studying and controlling the presence of these ubiquitous environmental compounds in water systems.
COMPARISON OF METHODS FOR MEASURING CONCENTRATIONS OF SEMIVOLATILE PARTICULATE MATTER
The paper gives results of a comparison of methods for measuring concentrations of semivolatile particulate matter (PM) from indoor-environment, small, combustion sources. Particle concentration measurements were compared for methods using filters and a small electrostatic precip...
SELECTED ORGANIC POLLUTANT EMISSIONS FROM UNVENTED KEROSENE HEATERS
An exploratory study was performed to assess the semivolatile and nonvolatile organic pollutant emission rates from unvented kerosene space heaters. A well-tuned radiant heater and maltuned convective heater were tested for semivolatile and nonvolatile organic pollutant emiss...
SAMPLING AND ANALYSIS OF SEMIVOLATILE AEROSOLS
Denuder based samplers can effectively separate semivolatile gases from particles and 'freeze' the partitioning in time. Conversely, samples collected on filters partition mass according to the conditions of the influent airstream, which may change over time. As a result thes...
Hijazi, Hassan Y; Bottaro, Christina S
2018-02-26
Water-compatible molecularly imprinted polymer (MIP) thin films are coupled with headspace gas chromatography sulfur chemiluminescence detection (HS-GC-SCD) to create a new approach for the determination of trace concentrations of thiophene compounds in water samples. Thiophene compounds are persistent, typically petrogenic, organic pollutants of concern due to their potential for biomagnification and bioaccumulation, mutagenicity, and carcinogenicity in terrestrial and aquatic fauna. Identification and quantitation in water, particularly following oil spills, is a priority. Following adsorption of the thiophenes to the MIPs, the MIP-bound analytes are analyzed directly by HS-GC-SCD, with minimal sample manipulation and virtually no organic solvent. Calibration curves of spiked seawater were linear from 5 μg L -1 to 100 μg L -1 and limits of detection (LOD) were in the range of 0.24-0.82 μg L -1 . Low matrix effects were observed in the analysis of thiophene compounds in seawater making the method suitable for use in fresh and saline waters without modification. Acceptable reproducibility was obtained for analysis of thiophene compounds from spiked seawater samples at RSDs ≤7.0% (n = 3).
DOE Office of Scientific and Technical Information (OSTI.GOV)
Parthasarathy, Srinandini; McKone, Thomas E.; Apte, Michael G.
This report summarizes the screening procedure and its results for selecting contaminants of concern (COC), whose concentrations are affected by ventilation in commercial buildings. Many pollutants comprising criteria pollutants, volatile organic compounds (VOCs), semi-volatile organic compounds (SVOCs) and biological contaminants are found in commercial buildings. In this report, we focus primarily on identifying potential volatile organic COC, which are impacted by ventilation. In the future we plan to extend this effort to inorganic gases and particles. Our screening considers compounds detected frequently in indoor air and compares the concentrations to health-guidelines and thresholds. However, given the range of buildings undermore » consideration, the contaminant sources and their concentrations will vary depending on the activity and use of the buildings. We used a literature review to identify a large list of chemicals found in commercial-building indoor air. The VOCs selected were subject to a two stage screening process, and the compounds of greater interest are included in priority List A. Other VOCs that have been detected in commercial buildings are included in priority List B. The compounds in List B, were further classified into groups B1, B2, B3, B4 in order of decreasing interest.« less
Jerković, Igor; Tuberoso, Carlo I G; Tuberso, Carlo I G; Gugić, Mirko; Bubalo, Dragan
2010-09-09
Samples of unifloral sulla (Hedysarum coronarum L.) honey from Sardinia (Italy) were analysed. To investigate the chemical composition of the honey volatiles two solvent systems were used for ultrasonic solvent extraction (USE): 1) a 1:2 (v/v) pentane and diethyl ether mixture and 2) dichloromethane. All the extracts were analysed by GC and GC/MS. These procedures have permitted the identification of 56 compounds that include norisoprenoids, benzene derivatives, aliphatic compounds and Maillard reaction products. Norisoprenoids were the major compounds in both extracts, dominated by vomifoliol (5.3-11.2%; 9.6-14.0%) followed by minor percentages of other norisoprenoids such as α-isophorone, 4-ketoisophorone, 3-oxo-α-ionol or 3-oxo-α-ionone. Other abundant single compounds in the extracts were 3-hydroxy-4-phenylbutan-2-one (0.8-5.4%; 0.6-5.7%) and methyl syringate (3.0-5.7%; 2.2-4.1%). The composition of the volatiles and semi-volatiles in the obtained extracts suggests that sulla honey is quite distinctive relative to the other honeys that have been chemically studied by GC/MS, but no specific markers of the honey botanical origin were found.
Verifying Sensor Response to Difficult Chemicals with a New Test Chamber Concept
DOE Office of Scientific and Technical Information (OSTI.GOV)
Maughan, A. D.; Birnbaum, Jerome C.; Probasco, Kathleen M.
In this article we discuss the application of technology innovations to optimize detection of hard-to-measure (less- or semi-volatile) compounds. These chemicals are found all around us: in pesticides and herbicides, the higher boiling polyaromatic hydrocarbons in diesel exhaust, and linked polyurethane foams in products ranging from hiking boots to acoustic ceilings. They appear in low concentrations and evaporate very slowly. These heavier chemicals are rarely measured accurately because they stick to surfaces and sampling equipment and, consequently, are not reliably sampled or delivered to analytical detectors. It’s like trying to identify cold, sticky honey by getting it to flow inmore » through a sampling tube to a detector –it will hardly move. Honey generally coats out on surfaces and sample lines to the extent that even if it is detected, the amount present is vastly underestimated. Researchers at Pacific Northwest National Laboratory (PNNL) addressed the problem by developing a chamber facility with instrumentation that can overcome the under-reporting of these ubiquitous chemical compounds. The atmospheric chemistry chamber provides a controlled environment in which to certify the accuracy of and conditions under which sensors can best respond to volatile and semi-volatile chemicals. The facility is designed to handle and measure chemicals at the levels at which they are found in nature. Test environments can be created in which atmospheric concentrations are at low part-per-trillion concentrations. These concentrations are equivalent to an herbicide off-gassing from a commercially grown apple. The chamber can be set up to simulate releases ranging from industrial vents with high concentrations to releases from surfaces, soils, and/or vegetation where the concentrations are low.« less
Domínguez-Morueco, Noelia; Carvalho, Mariana; Sierra, Jordi; Schuhmacher, Marta; Domingo, José Luis; Ratola, Nuno; Nadal, Martí
2018-08-01
Tarragona County (Spain) is home to the most important chemical/petrochemical industrial complex in Southern Europe, which raises concerns about the presence and effects of the numerous environmental contaminants. In order to assess the levels and patterns of five classes of semi-volatile organic compounds (SVOCs) - polycyclic aromatic hydrocarbons (PAHs), synthetic musks (SMs), polychlorinated biphenyls (PCBs), brominated flame retardants (BFRs) and one organochlorine pesticide, hexachlorobenzene (HCB), 27 samples of soil and vegetation (Piptatherum L.) from different areas (petrochemical, chemical, urban/residential, and background) of Tarragona County were analysed. The results show that PAHs levels in soils ranged from 45.12 to 158.00ng/g and the urban areas presented the highest concentrations, mainly associated with the presence of a nearby highway and several roads with heavy traffic. PAHs levels in vegetation samples ranged from 42.13 to 80.08ng/g, where the greatest influence came from the urban and petrochemical areas. In the case of SMs, levels in soils and vegetation samples ranged from 5.42 to 10.04ng/g and from 4.08 to 17.94ng/g, respectively, and in both cases, background areas (at least 30km away from the main SVOCs emission sources) showed the highest levels, suggesting an influence of the personal care products derived from beach-related tourism in the coast. PCBs (from 6.62 to 14.07ng/g in soils; from 0.52 to 4.41ng/g in vegetation) prevailed in the chemical area in both matrices, probably associated with the presence of two sub-electrical stations located in the vicinities. In general terms, BFRs and HCB values recorded in soil and vegetation samples were quite similar between matrices and sampling areas. Copyright © 2018. Published by Elsevier B.V.
Feedbacks between microphysics and photochemical aging in viscous aerosol
NASA Astrophysics Data System (ADS)
Dou, Jing; Corral Arroyo, Pablo; Alpert, Peter A.; Ammann, Markus; Peter, Thomas; Krieger, Ulrich K.
2017-04-01
Fe(III)-citrate complex photochemistry, which plays an important role in aerosol aging, especially in lower troposphere, has been widely recognized in both solution and solid states. It can get excited by light below about 500 nm, inducing the oxidation of carboxylate ligands and the production of peroxides (e.g., OH•, HO2•), which have a significant impact on the climate, air quality and health. Recently, there is literature reporting that aqueous aerosol particles may attain highly viscous, semi-solid or even glassy physical states under a wide range of atmospheric conditions. However, systematic studies on the effect of high viscosity on photochemical processes are scarce. In this research, mass and size changes of a single, aqueous Fe(III)-citrate/citric acid particle levitated in an electrodynamic balance (EDB) are tracked during photochemical processing. We observe an overall mass loss during photochemical processing due to evaporation of volatile (e.g., CO2) and semi-volatile (e.g., ketones) compounds. It is known that relative humidity and temperature strongly effects the viscosity of citric acid. Hence, under light intensities large enough not limiting photochemical processing (at a wavelength of either 375 nm or 473 nm), the quasi-steady state evaporation rate in our experiments depends on relative humidity and temperature. The same holds true for the characteristic time scale for reaching thermodynamic equilibrium after switching off the light source. We are focusing on the high viscosity case (i.e., reduced molecular mobility and low water content), which slows down the transport of products but can also affect chemical reaction rates (e.g., initial absorption process, charge and energy transfer). Data are compared to kinetic modeling and diffusivities for semi-volatile compounds are estimated aiming at a more detailed understanding of the feedbacks between microphysics and photochemical aging.
Linak, W P; Ryan, J V; Perry, E; Williams, R W; DeMarini, D M
1989-06-01
Chemical and biological analyses were performed to characterize products of incomplete combustion emitted during the simulated open field burning of agricultural plastic. A small utility shed equipped with an air delivery system was used to simulate pile burning and forced-air-curtain incineration of a nonhalogenated agricultural plastic that reportedly consisted of polyethylene and carbon black. Emissions were analyzed for combustion gases; volatile, semi-volatile, and particulate organics; and toxic and mutagenic properties. Emission samples, as well as samples of the used (possibly pesticide-contaminated) plastic, were analyzed for the presence of several pesticides to which the plastic may have been exposed. Although a variety of alkanes, alkenes, and aromatic and polycyclic aromatic hydrocarbon (PAH) compounds were identified in the volatile, semi-volatile, and particulate fractions of these emissions, a substantial fraction of higher molecular weight organic material was not identified. No pesticides were identified in either combustion emission samples or dichloromethane washes of the used plastic. When mutagenicity was evaluated by exposing Salmonella bacteria (Ames assay) to whole vapor and vapor/particulate emissions, no toxic or mutagenic effects were observed. However, organic extracts of the particulate samples were moderately mutagenic. This mutagenicity compares approximately to that measured from residential wood heating on a revertant per unit heat release basis. Compared to pile burning, forced air slightly decreased the time necessary to burn a charge of plastic. There was not a substantial difference, however, in the variety or concentrations of organic compounds identified in samples from these two burn conditions. This study highlights the benefits of a combined chemical/biological approach to the characterization of complex, multi-component combustion emissions. These results may not reflect those of other types of plastic that may be used for agricultural purposes, especially those containing halogens.
The Henry's constant of monochloramine.
Garcia, Miguel A; Anderson, Michael A
2018-02-01
Monochloramine is a secondary disinfectant used in drinking water and is also formed in chlorinated wastewater. While known to hydrolyze over time and react with dissolved organic matter, its partitioning between the aqueous and gas phase has not been extensively studied. Preliminary experiments demonstrated that monochloramine concentrations in solutions open to the atmosphere or actively aerated decreased more rapidly than in sealed solutions, indicating significant losses to the atmosphere. For example, a monochloramine solution open to the atmosphere yielded a loss rate constant of 0.08 d -1 , a value twice that for sealed samples without headspace (0.04 d -1 ) where loss occurs exclusively as a result of hydrolysis. A solution aerated at 10 mL s -1 had a loss rate constant nearly 10× greater than that for hydrolysis alone (0.35 d -1 ). To better understand partitioning of monochloramine to the gas phase and potential for volatilization, the dimensionless Henry's law constants of monochloramine (K H ) were determined using an equilibrium headspace technique at five different temperatures (11, 16, 21, 27, and 32 °C). The resulting values ranged from 8 × 10 -3 to 4 × 10 -2 , indicating a semi-volatile compound, and were found to be consistent with quantitative structure activity relationship predictions. At 20 °C, monochloramine exhibits a dimensionless Henry's constant of about 1.7 × 10 -2 which is 35 times greater than ammonia but comparable to the Henry's constant of inorganic semi-volatile compounds such sulfur dioxide. The Henry's constant values for monochloramine suggests that volatilization could be a relevant loss process in open systems such as rivers receiving chlorinated wastewater effluent, swimming pools and cooling towers. Copyright © 2017 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Pourkhesalian, A. M.; Stevanovic, S.; Rahman, M. M.; Faghihi, E. M.; Bottle, S. E.; Masri, A. R.; Brown, R. J.; Ristovski, Z. D.
2015-08-01
In the prospect of limited energy resources and climate change, effects of alternative biofuels on primary emissions are being extensively studied. Our two recent studies have shown that biodiesel fuel composition has a significant impact on primary particulate matter emissions. It was also shown that particulate matter caused by biodiesels was substantially different from the emissions due to petroleum diesel. Emissions appeared to have higher oxidative potential with the increase in oxygen content and decrease of carbon chain length and unsaturation levels of fuel molecules. Overall, both studies concluded that chemical composition of biodiesel is more important than its physical properties in controlling exhaust particle emissions. This suggests that the atmospheric aging processes, including secondary organic aerosol formation, of emissions from different fuels will be different as well. In this study, measurements were conducted on a modern common-rail diesel engine. To get more information on realistic properties of tested biodiesel particulate matter once they are released into the atmosphere, particulate matter was exposed to atmospheric oxidants, ozone and ultra-violet light; and the change in their properties was monitored for different biodiesel blends. Upon the exposure to oxidative agents, the chemical composition of the exhaust changes. It triggers the cascade of photochemical reactions resulting in the partitioning of semi-volatile compounds between the gas and particulate phase. In most of the cases, aging lead to the increase in volatility and oxidative potential, and the increment of change was mainly dependent on the chemical composition of fuels as the leading cause for the amount and the type of semi-volatile compounds present in the exhaust.
Bohlin, Pernilla; Audy, Ondřej; Škrdlíková, Lenka; Kukučka, Petr; Vojta, Šimon; Přibylová, Petra; Prokeš, Roman; Čupr, Pavel; Klánová, Jana
2014-11-01
Indoor air pollution has been recognized as an important risk factor for human health, especially in areas where people tend to spend most of their time indoors. Many semi-volatile organic compounds (SVOCs) have primarily indoor sources and are present in orders of magnitude higher concentrations indoors than outdoors. Despite this, awareness of SVOCs in indoor air and assessment of the link between indoor concentrations and human health have lagged behind those of outdoor air. This is partially related to challenges associated with indoor sampling of SVOCs. Passive air samplers (PASs), which are widely accepted in established outdoor air monitoring networks, have been used to fill the knowledge gaps on indoor SVOCs distribution. However, their applicability for indoor environments and the assessment of human health risks lack sufficient experimental data. To address this issue, we performed an indoor calibration study of polyurethane foam (PUF) PAS deployed in a double-dome chamber, covering both legacy and new SVOC classes. PUF-PAS and a continuous low-volume active air sampler (AAS) were co-deployed for a calibration period of twelve weeks. Based on the results from this evaluation, PUF-PAS in a double-bowl chamber is recommended for indoor sampling and health risk assessment of gas phase SVOCs, including novel brominated flame retardants (nBFR) providing sufficient exposure time is applied. Data for particle associated SVOCs suffered from significant uncertainties caused by low level of detection and low precision in this study. A more open chamber design for indoor studies may allow for higher sampling rates (RS) and better performance for the particle associated SVOCs.
Coiner, R.L.; Pope, L.M.; Mehl, H.E.
2010-01-01
An assessment of energetic compounds (explosive and propellant residues) and associated semi-volatile organic compounds (SVOCs) and trace elements in streambed sediment and stream water from streams draining munitions firing points and impact areas at Fort Riley, northeast Kansas, was performed during 2007-08 by the U.S. Geological Survey (USGS) in cooperation with the U.S. Army. Streambed sediment from 16 sampling sites and stream-water samples from 5 sites were collected at or near Fort Riley and analyzed for as many as 17 energetic compounds, 65 SVOCs, and 27 trace elements. None of the energetic compounds or SVOCs were detected in streambed sediment collected from sites within the Fort Riley Military Reservation. This may indicate that these compounds either are not transported from dispersal areas or that analytical methods are not sensitive enough to detect the small concentrations that may be transported. Concentrations of munitions-associated trace elements did not exceed sediment-quality guidelines recommended by the U.S. Environmental Protection Agency (USEPA) and are not indicative of contamination of streambed sediment at selected streambed sampling sites, at least in regards to movement from dispersal areas. Analytical results of stream-water samples provided little evidence of contamination by energetic compounds, SVOCs, or associated trace elements. Perchlorate was detected in 19 of 20 stream-water samples at concentrations ranging from an estimated 0.057 to an estimated 0.236 ug/L (micrograms per liter) with a median concentration of an estimated 0.114 ug/L, substantially less than the USEPA Interim Health Advisory criterion (15 ug/L), and is in the range of documented background concentrations. Because of these small concentrations and possible natural sources (precipitation and groundwater), it is likely that the occurrence of perchlorate in stream water is naturally occurring, although a definitive identification of the source of perchlorate in stream water at Fort Riley is difficult. The only SVOCs detected in stream-water samples were bis(2-ethylhexyl) phthalate and di-n-butyl phthalate but at concentrations substantially less than the most stringent aquatic-life criteria established by the Kansas Department of Health and Environment. All trace element concentrations in stream-water samples were less than the most stringent aquatic-life criteria. The implication of these stream-water results is that contamination arising from firing-range activities, if it exists, is so small as to be nondetectable with current analytical methods or is not distinguishable from background concentrations for constituents that also are naturally occurring. Overall, the munitions-related constituents analyzed in streambed sediment and stream water, when detected, were at concentrations that were less than regulatory criteria
Organic solutes in ground water at the Idaho National Engineering Laboratory
Leenheer, Jerry A.; Bagby, Jefferson C.
1982-01-01
In August 1980, the U.S. Geological Survey started a reconnaissance survey of organic solutes in drinking water sources, ground-water monitoring wells, perched water table monitoring wells, and in select waste streams at the Idaho National Engineering Laboratory (INEL). The survey was to be a two-phase program. In the first phase, 77 wells and 4 potential point sources were sampled for dissolved organic carbon (DOC). Four wells and several potential point sources of insecticides and herbicides were sampled for insecticides and herbicides. Fourteen wells and four potential organic sources were sampled for volatile and semivolatile organic compounds. The results of the DOC analyses indicate no high level (>20 mg/L DOC) organic contamination of ground water. The only detectable insecticide or herbicide was a DDT concentration of 10 parts per trillion (0.01 microgram per liter) in one observation well. The volatile and semivolatile analyses do not indicate the presence of hazardous organic contaminants in significant amounts (>10 micrograms per liter) in the samples taken. Due to the lack of any significant organic ground-water contamination in this reconnaissance survey, the second phase of the study, which was to follow up the first phase by additional sampling of any contaminated wells, was canceled.
NASA Astrophysics Data System (ADS)
Sato, Kei; Fujitani, Yuji; Inomata, Satoshi; Morino, Yu; Tanabe, Kiyoshi; Ramasamy, Sathiyamurthi; Hikida, Toshihide; Shimono, Akio; Takami, Akinori; Fushimi, Akihiro; Kondo, Yoshinori; Imamura, Takashi; Tanimoto, Hiroshi; Sugata, Seiji
2018-04-01
Traditional yield curve analysis shows that semi-volatile organic compounds are a major component of secondary organic aerosols (SOAs). We investigated the volatility distribution of SOAs from α-pinene ozonolysis using positive electrospray ionization mass analysis and dilution- and heat-induced evaporation measurements. Laboratory chamber experiments were conducted on α-pinene ozonolysis, in the presence and absence of OH scavengers. Among these, we identified not only semi-volatile products, but also less volatile highly oxygenated molecules (HOMs) and dimers. Ozonolysis products were further exposed to OH radicals to check the effects of photochemical aging. HOMs were also formed during OH-initiated photochemical aging. Most HOMs that formed from ozonolysis and photochemical aging had 10 or fewer carbons. SOA particle evaporation after instantaneous dilution was measured at < 1 and ˜ 40 % relative humidity. The volume fraction remaining of SOAs decreased with time and the equilibration timescale was determined to be 24-46 min for SOA evaporation. The experimental results of the equilibration timescale can be explained when the mass accommodation coefficient is assumed to be 0.1, suggesting that the existence of low-volatility materials in SOAs, kinetic inhibition, or some combined effect may affect the equilibration timescale measured in this study.
Photochemical Aging of Organic Aerosols: A Laboratory Study
NASA Astrophysics Data System (ADS)
Papanastasiou, Dimitrios K.; Kostenidou, Evangelia; Gkatzelis, Georgios I.; Psichoudaki, Magdalini; Louvaris, Evangelos; Pandis, Spyros N.
2014-05-01
Organic aerosols (OA) are either emitted directly (primary OA) or formed (secondary OA) in the atmosphere and consist of an extremely complex mixture of thousands of organic compounds. Although the scientific community has put significant effort, in the past few decades, to understand organic aerosol (OA) formation, evolution and fate in the atmosphere, traditional models often fail to reproduce the ambient OA levels. Secondary organic aerosol (SOA) formed, in traditional laboratory chamber experiments, from the gas phase oxidation of known precursors, such as α-pinene, is semi-volatile and with an O:C ratio of around 0.4. In contrast, OA found in the atmosphere is significantly less volatile, while the O:C ratio often ranges from 0.5 to 1. In conclusion, there is a significant gap of knowledge in our understanding of OA formation and photochemical transformation in the atmosphere. There is increased evidence that homogeneous gas phase aging by OH radicals might be able to explain, at least in part, the significantly higher OA mass loadings observed and also the oxidation state and volatility of OA in the atmosphere. In this study, laboratory chamber experiments were performed to study the role of the continued oxidation of first generation volatile and semi-volatile species by OH radicals in the evolution of the SOA characteristics (mass concentration, volatility, and oxidation state). Ambient air mixtures or freshly formed SOA from α-pinene ozonolysis were used as the source of organic aerosols and semi-volatile species. The initial mixture of organic aerosols and gas phase species (volatile and semi-volatile) was then exposed to atmospheric concentrations of OH radicals to study the aging of aerosols. Experiments were performed with various OH radical sources (H2O2 or HONO) and under various NOx conditions. A suite of instruments was employed to characterize both the gas and the aerosol phase. A Scanning Mobility Particle Sizer (SMPS) and a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) were used to measure the organic aerosol mass production and oxidation degree (O:C ratio) following OH aging. A thermodenuder system was used to measure the volatility distribution change as organic aerosol aged upon continuous oxidation. Organic gas phase species were characterized with a Proton Transfer Reaction - Mass Spectrometer (PTR-MS) while NOx and O3 were measured with the use of corresponding analyzers. Results from this study show that organic mass production occurs upon exposure to OH radicals indicating that continuous OH aging of semi-volatile is probably responsible for at least some of the gap between observed and modeled OA levels in the atmosphere. Additionally, this chemical aging process leads to a decrease in volatility and an increase in O:C ratio while the level of change in both properties depends on OH exposure. The atmospheric implications of this study are discussed.
The Salt Lake City EPA Environmental
Monitoring for Public Access and Community Tracking (EMPACT) project,
initiated in October 1999, is designed to evaluate the usefulness of a
newly developed real-time continuous monitor (RAMS) for total
(non-volatil...
SEMI-VOLATILE SECONDARY AEROSOLS IN URBAN ATMOSPHERES: MEETING A MEASURED CHALLENGE
This presentation compares the results from various particle measurement methods as they relate to semi-volatile secondary aerosols in urban atmospheres. The methods include the PM2.5 Federal Reference Method; Particle Concentrator - BYU Organic Sampling System (PC-BOSS); the Re...
Offenthaler, I; Jakobi, G; Kaiser, A; Kirchner, M; Kräuchi, N; Niedermoser, B; Schramm, K-W; Sedivy, I; Staudinger, M; Thanner, G; Weiss, P; Moche, W
2009-12-01
High- and low-volume active air samplers as well as bulk deposition samplers were developed to sample atmospheric SOCs under the adverse conditions of a mountain environment. Active sampling employed separate filters for different European source regions. Filters were switched depending on daily trajectory forecasts, whose accuracy was evaluated post hoc. The sampling continued on three alpine summits over five periods of four months. The prevailing trajectories varied stronger between sampling periods than between stations. The sampling equipment (active and bulk deposition) proved dependable for operation in a mountain environment, with idle times being mainly due to non-routine manipulations and connectivity.
Reagen, William K; Lindstrom, Kent R; Thompson, Kathy L; Flaherty, John M
2004-09-01
The widespread use of semi- and nonvolatile organofluorochemicals in industrial facilities, concern about their persistence, and relatively recent advancements in liquid chromatography/mass spectrometry (LC/MS) technology have led to the development of new analytical methods to assess potential worker exposure to airborne organofluorochemicals. Techniques were evaluated for the determination of 19 organofluorochemicals and for total fluorine in ambient air samples. Due to the potential biphasic nature of most of these fluorochemicals when airborne, Occupational Safety and Health Administration (OSHA) versatile sampler (OVS) tubes were used to simultaneously trap fluorochemical particulates and vapors from workplace air. Analytical methods were developed for OVS air samples to quantitatively analyze for total fluorine using oxygen bomb combustion/ion selective electrode and for 17 organofluorochemicals using LC/MS and gas chromatography/mass spectrometry (GC/MS). The experimental design for this validation was based on the National Institute of Occupational Safety and Health (NIOSH) Guidelines for Air Sampling and Analytical Method Development and Evaluation, with some revisions of the experimental design. The study design incorporated experiments to determine analytical recovery and stability, sampler capacity, the effect of some environmental parameters on recoveries, storage stability, limits of detection, precision, and accuracy. Fluorochemical mixtures were spiked onto each OVS tube over a range of 0.06-6 microg for each of 12 compounds analyzed by LC/MS and 0.3-30 microg for 5 compounds analyzed by GC/MS. These ranges allowed reliable quantitation at 0.001-0.1 mg/m3 in general for LC/MS analytes and 0.005-0.5 mg/m3 for GC/MS analytes when 60 L of air are sampled. The organofluorochemical exposure guideline (EG) is currently 0.1 mg/m3 for many analytes, with one exception being ammonium perfluorooctanoate (EG is 0.01 mg/m3). Total fluorine results may be used to determine if the individual compounds quantified provide a suitable mass balance of total airborne organofluorochemicals based on known fluorine content. Improvements in precision and/or recovery as well as some additional testing would be needed to meet all NIOSH validation criteria. This study provided valuable information about the accuracy of this method for organofluorochemical exposure assessment.
Tang, Jing; Tang, Lin; Zhang, Chang; Zeng, Guangming; Deng, Yaocheng; Dong, Haoran; Wang, Jingjing; Wu, Yanan
2015-10-01
Semi-volatile organic compounds (SVOCs) derived from plastic pipes widely used in water distribution definitely influence our daily drinking water quality. There are still few scientific or integrated studies on the release and degradation of the migrating chemicals in pipelines. This investigation was carried out at field sites along a pipeline in Changsha, China. Two chemicals, 2, 4-tert-buthylphenol and 1, 3-diphenylguanidine, were found to be migrating from high density polyethylene (HDPE) pipe material. New pipes released more of these two compounds than older pipes, and microorganisms living in older pipes tended to degrade them faster, indicating that the aged pipes were safer for water transmission. Microorganism degradation in water plays a dominant role in the control of these substances. To minimize the potential harm to human, a more detailed study incorporating assessment of their risk should be carried out, along with seeking safer drinking pipes.
Epstein, Scott A; Riipinen, Ilona; Donahue, Neil M
2010-01-15
To model the temperature-induced partitioning of semivolatile organics in laboratory experiments or atmospheric models, one must know the appropriate heats of vaporization. Current treatments typically assume a constant value of the heat of vaporization or else use specific values from a small set of surrogate compounds. With published experimental vapor-pressure data from over 800 organic compounds, we have developed a semiempirical correlation between the saturation concentration (C*, microg m(-3)) and the heat of vaporization (deltaH(VAP), kJ mol(-1)) for organics in the volatility basis set. Near room temperature, deltaH(VAP) = -11 log(10)C(300)(*) + 129. Knowledge of the relationship between C* and deltaH(VAP) constrains a free parameter in thermodenuder data analysis. A thermodenuder model using our deltaH(VAP) values agrees well with thermal behavior observed in laboratory experiments.
DOE Office of Scientific and Technical Information (OSTI.GOV)
DeRosier, R.
1984-09-01
This volume describes emission results from sampling of flue-gas from a firetube boiler burning a coal/oil/water (COW) mixture and COW with soda ash added (COW+SA) to control SO/sub 2/ emissions. Measurements included: continuous monitoring of flue-gas emissions; source assessment sampling system (SASS) sampling of the flue gas with subsequent laboratory analysis of the samples to give total flue gas organics in two boiling point ranges, specific quantitation of the semivolatile organic priority pollutant species, and flue gas concentrations of 73 trace elements; Method 5 sampling for total particulate; and controlled condensation system sampling for SO/sub 2/ and SO/sub 3/ emissions.more » Flue-gas SO/sub 2/ emissions decreased almost 99% with soda ash addition from 1,089 to 13.6 ppm (3% O2). NOx emissions decreased slightly from 477 to 427 ppm, while CO emissions increased significantly from an average of 25 to 426 ppm (all at 3% O2). Particulate loading at the boiler outlet almost doubled (from 1,970 to 3,715 pg/dscm) with the additive. The size distribution of particulate also shifted to a much smaller mean diameter. Total organic emissions increased from 6.7 to 13.1 mg/dscm; most of the increase were nonvolatile (C16+) organics. Of the semivolatile organic priority pollutant species, only fluoranthene and phenanthrene were detected with the COW fuel, and phenanthrene with the COW+SA fuel.« less
This work develops a novel validation approach for studying how non-volatile aerosol matrices of considerably different chemical composition potentially affect the thermal extraction (TE)/GC/MS quantification of a wide range of trace semivolatile organic markers. The non-volatil...
COMPARISON OF SAMPLING METHODS FOR SEMI-VOLATILE ORGANIC CARBON (SVOC) ASSOCIATED WITH PM 2.5
This study evaluates the influence of denuder sampling methods and filter collection media on the measurement of semi-volatile organic carbon (SVOC) associated with PM2.5. Two types of collection media, charcoal (activated carbon) and XAD, were used both in diffusion denuders ...
COMPARISON OF SAMPLING METHODS FOR SEMI-VOLATILE ORGANIC CARBON ASSOCIATED WITH PM 2.5
This study evaluates the influence of denuder sampling methods and filter collection media on the measurement of semi-volatile organic carbon (SVOC) associated with PM2.5. Two types of collection media, charcoal (activated carbon) and XAD, were used both in diffusion denuders ...
Quantitative organic vapor-particle sampler
Gundel, Lara; Daisey, Joan M.; Stevens, Robert K.
1998-01-01
A quantitative organic vapor-particle sampler for sampling semi-volatile organic gases and particulate components. A semi-volatile organic reversible gas sorbent macroreticular resin agglomerates of randomly packed microspheres with the continuous porous structure of particles ranging in size between 0.05-10 .mu.m for use in an integrated diffusion vapor-particle sampler.
DOE Office of Scientific and Technical Information (OSTI.GOV)
DeRosier, R.
1984-09-01
This volume is a compendium of detailed emission and test data from field tests of a firetube industrial boiler burning a coal/oil/water (COW) mixture. The boiler was tested while burning COW fuel, and COW with soda ash added (COW+SA) to serve as an SO/sub 2/ sorbent. The test data include: preliminary equipment calibration data, boiler operating data for both tests, fuel analysis results, and complete flue gas emission measurement and laboratory analysis results. Flue gas emission measurements included: continuous monitoring for criteria gas pollutants; gas chromatography (GC) of gas grab samples for volatile organics (C1-C6); EPA Method 5 for particulate;more » controlled condensation system for SO2 emissions; and source assessment sampling system (SASS) for total organics in two boiling point ranges (100 to 300 C and > 300 C), organic compound category information using infrared spectrometry (IR) and low resolution mass spectrometry (LRMS), specific quantitation of the semivolatile organic priority pollutants using gas chromatography/mass spectrometry (GC/MS), liquid chromatography (LC) separation of organic extracts into seven polarity fractions with total organic and IR analyses of eluted fractions, flue gas concentrations of trace elements by spark source mass spectrometry (SSMS) and atomic absorption spectroscopy (AAS), and biological assays of organic extracts.« less
Pavilonis, Brian T.; Weisel, Clifford P.; Buckley, Brian; Lioy, Paul J.
2014-01-01
To reduce maintenance costs, municipalities and schools are starting to replace natural grass fields with a new generation synthetic turf. Unlike Astro-Turf, which was first introduced in the 1960’s, synthetic field turf provides more cushioning to athletes. Part of this cushioning comes from materials like crumb rubber infill, which is manufactured from recycled tires and may contain a variety of chemicals. The goal of this study was to evaluate potential exposures from playing on artificial turf fields and associated risks to trace metals, semivolatile organic compounds (SVOCs), and polycyclic aromatic hydrocarbons (PAHs) by examining typical artificial turf fibers (n=8), different types of infill (n=8), and samples from actual fields (n=7). Three artificial biofluids were prepared which included: lung, sweat, and digestive fluids. Artificial biofluids were hypothesized to yield a more representative estimation of dose than the levels obtained from total extraction methods. PAHs were routinely below the limit of detection across all three biofluids precluding completion of a meaningful risk assessment. No SVOCs were identified at quantifiable levels in any extracts based on a match of their mass spectrum to compounds that are regulated in soil. The metals were measurable but at concentrations for which human health risk was estimated to be low. The study demonstrated that for the products and fields we tested, exposure to infill and artificial turf was generally considered de minimus, with the possible exception of lead for some fields and materials. PMID:23758133
Reflections on the history of indoor air science, focusing on the last 50 years.
Sundell, J
2017-07-01
The scientific articles and Indoor Air conference publications of the indoor air sciences (IAS) during the last 50 years are summarized. In total 7524 presentations, from 79 countries, have been made at Indoor Air conferences held between 1978 (49 presentations) and 2014 (1049 presentations). In the Web of Science, 26 992 articles on indoor air research (with the word "indoor" as a search term) have been found (as of 1 Jan 2016) of which 70% were published during the last 10 years. The modern scientific history started in the 1970s with a question: "did indoor air pose a threat to health as did outdoor air?" Soon it was recognized that indoor air is more important, from a health point of view, than outdoor air. Topics of concern were first radon, environmental tobacco smoke, and lung cancer, followed by volatile organic compounds, formaldehyde and sick building syndrome, house dust-mites, asthma and allergies, Legionnaires disease, and other airborne infections. Later emerged dampness/mold-associated allergies and today's concern with "modern exposures-modern diseases." Ventilation, thermal comfort, indoor air chemistry, semi-volatile organic compounds, building simulation by computational fluid dynamics, and fine particulate matter are common topics today. From their beginning in Denmark and Sweden, then in the USA, the indoor air sciences now show increasing activity in East and Southeast Asia. © 2017 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.
NASA Astrophysics Data System (ADS)
Drozd, Greg T.; Worton, David R.; Aeppli, Christoph; Reddy, Christopher M.; Zhang, Haofei; Variano, Evan; Goldstein, Allen H.
2015-11-01
Releases of hydrocarbons from oil spills have large environmental impacts in both the ocean and atmosphere. Oil evaporation is not simply a mechanism of mass loss from the ocean, as it also causes production of atmospheric pollutants. Monitoring atmospheric emissions from oil spills must include a broad range of volatile organic compounds (VOC), including intermediate-volatile and semivolatile compounds (IVOC, SVOC), which cause secondary organic aerosol (SOA) and ozone production. The Deepwater Horizon (DWH) disaster in the northern Gulf of Mexico during Spring/Summer of 2010 presented a unique opportunity to observe SOA production due to an oil spill. To better understand these observations, we conducted measurements and modeled oil evaporation utilizing unprecedented comprehensive composition measurements, achieved by gas chromatography with vacuum ultraviolet time of flight mass spectrometry (GC-VUV-HR-ToFMS). All hydrocarbons with 10-30 carbons were classified by degree of branching, number of cyclic rings, aromaticity, and molecular weight; these hydrocarbons comprise ˜70% of total oil mass. Such detailed and comprehensive characterization of DWH oil allowed bottom-up estimates of oil evaporation kinetics. We developed an evaporative model, using solely our composition measurements and thermodynamic data, that is in excellent agreement with published mass evaporation rates and our wind-tunnel measurements. Using this model, we determine surface slick samples are composed of oil with a distribution of evaporative ages and identify and characterize probable subsurface transport of oil.
Ke, Hongwei; Chen, Mian; Liu, Mengyang; Chen, Meng; Duan, Mengshan; Huang, Peng; Hong, Jiajun; Lin, Yan; Cheng, Shayen; Wang, Xuran; Huang, Mengxue; Cai, Minggang
2017-10-01
Polycyclic aromatic hydrocarbons (PAHs) have accumulated ubiquitously inArctic environments, where re-volatilization of certain organic pollutants as a result of climate change has been observed. To investigate the fate of semivolatile organic compounds in the Arctic, dissolved PAHs in the surface seawaters from the temperate Pacific Ocean to the Arctic Ocean, as well as a water column in the Arctic Ocean, were collected during the 4th Chinese National Arctic Research Expedition in summer 2010. The total concentrations of seven dissolved PAHs in surface water ranged from 1.0 to 5.1 ng L -1 , decreasing with increasing latitude. The vertical profile of PAHs in the Arctic Ocean was generally characteristic of surface enrichment and depth depletion, which emphasized the role of vertical water stratification and particle settling processes. A level III fugacity model was developed in the Bering Sea under steady state assumption. Model results quantitatively simulated the transfer processes and fate of PAHs in the air and water compartments, and highlighted a summer air-to-sea flux of PAHs in the Bering Sea, which meant that the ocean served as a sink for PAHs, at least in summer. Acenaphthylene and acenaphthene reached equilibrium in air-water diffusive exchange, and any perturbation, such as a rise in temperature, might lead to disequilibrium and remobilize these compounds from their Arctic reservoirs. Copyright © 2017 Elsevier Ltd. All rights reserved.
Adelhelm, Christoph; Niessner, Reinhard; Pöschl, Ulrich
2008-01-01
The analysis of organic compounds in combustion exhaust particles and the chemical transformation of soot by nitrogen oxides are key aspects of assessment and mitigation of the climate and health effects of aerosol emissions from fossil fuel combustion and biomass burning. In this study we present experimental and analytical techniques for efficient investigation of oxygenated and nitrated derivatives of large polycyclic aromatic hydrocarbons (PAHs), which can be regarded as well-defined soot model substances. For coronene and hexabenzocoronene exposed to nitrogen dioxide under simulated diesel exhaust conditions, several reaction products with high molecular mass could be characterized by liquid chromatography-atmospheric pressure chemical (and photo) ionization-mass spectrometry (LC-APCI-MS and LC-APPI-MS). The main products of coronene contained odd numbers of nitrogen atoms (m/z 282, 256, 338), whereas one of the main products of hexabenzocoronene exhibited an even number of nitrogen atoms (m/z 391). Various reaction products containing carbonyl and nitro groups could be tentatively identified by combining chromatographic and mass spectrometric information, and changes of their relative abundance were observed to depend on the reaction conditions. This analytical strategy should highlight a relatively young technique for the characterization of various soot-contained, semi-volatile, and semi-polar reaction products of large PAHs. Figure LC-APCI-MS analysis of nitrated coronene (and HBC): Total-Ion-Chromatogram (TIC), Extracted Ion Chromatograms (EICs) and corresponding mass spectrum (top). PMID:18560812
Donahue, Neil M; Hartz, Kara E Huff; Chuong, Bao; Presto, Albert A; Stanier, Charles O; Rosenhørn, Thomas; Robinson, Allen L; Pandis, Spyros N
2005-01-01
A substantial fraction of the total ultrafine particulate mass is comprised of organic compounds. Of this fraction, a significant subfraction is secondary organic aerosol (SOA), meaning that the compounds are a by-product of chemistry in the atmosphere. However, our understanding of the kinetics and mechanisms leading to and following SOA formation is in its infancy. We lack a clear description of critical phenomena; we often don't know the key, rate limiting steps in SOA formation mechanisms. We know almost nothing about aerosol yields past the first generation of oxidation products. Most importantly, we know very little about the derivatives in these mechanisms; we do not understand how changing conditions, be they precursor levels, oxidant concentrations, co-reagent concentrations (i.e., the VOC/NOx ratio) or temperature will influence the yields of SOA. In this paper we explore the connections between fundamental details of physical chemistry and the multitude of steps associated with SOA formation, including the initial gas-phase reaction mechanisms leading to condensible products, the phase partitioning itself, and the continued oxidation of the condensed-phase organic products. We show that SOA yields in the alpha-pinene + ozone are highly sensitive to NOx, and that SOA yields from beta-caryophylene + ozone appear to increase with continued ozone exposure, even as aerosol hygroscopicity increases as well. We suggest that SOA yields are likely to increase substantially through several generations of oxidative processing of the semi-volatile products.
NASA Technical Reports Server (NTRS)
Cole, H.; Habercom, M.; Crenshaw, M.; Johnson, S.; Manuel, S.; Martindale, W.; Whitman, G.; Traweek, M.
1991-01-01
Examples of the application of various methods for characterizing samples for alcohols, fatty acids, detergents, and volatile/semivolatile basic, neutral, and phenolic acid contaminants are presented. Data, applications, and interpretations are given for a variety of methods including sample preparation/cleanup procedures, ion chromatography, and gas chromatography with various detectors. Summaries of the major organic contaminants that contribute to the total organic carbon content are presented.
NASA Astrophysics Data System (ADS)
Yahya, Khairunnisa; Glotfelty, Timothy; Wang, Kai; Zhang, Yang; Nenes, Athanasios
2017-06-01
Air quality and climate influence each other through the uncertain processes of aerosol formation and cloud droplet activation. In this study, both processes are improved in the Weather, Research and Forecasting model with Chemistry (WRF/Chem) version 3.7.1. The existing Volatility Basis Set (VBS) treatments for organic aerosol (OA) formation in WRF/Chem are improved by considering the following: the secondary OA (SOA) formation from semi-volatile primary organic aerosol (POA), a semi-empirical formulation for the enthalpy of vaporization of SOA, and functionalization and fragmentation reactions for multiple generations of products from the oxidation of VOCs. Over the continental US, 2-month-long simulations (May to June 2010) are conducted and results are evaluated against surface and aircraft observations during the Nexus of Air Quality and Climate Change (CalNex) campaign. Among all the configurations considered, the best performance is found for the simulation with the 2005 Carbon Bond mechanism (CB05) and the VBS SOA module with semivolatile POA treatment, 25 % fragmentation, and the emissions of semi-volatile and intermediate volatile organic compounds being 3 times the original POA emissions. Among the three gas-phase mechanisms (CB05, CB6, and SAPRC07) used, CB05 gives the best performance for surface ozone and PM2. 5 concentrations. Differences in SOA predictions are larger for the simulations with different VBS treatments (e.g., nonvolatile POA versus semivolatile POA) compared to the simulations with different gas-phase mechanisms. Compared to the simulation with CB05 and the default SOA module, the simulations with the VBS treatment improve cloud droplet number concentration (CDNC) predictions (normalized mean biases from -40.8 % to a range of -34.6 to -27.7 %), with large differences between CB05-CB6 and SAPRC07 due to large differences in their OH and HO2 predictions. An advanced aerosol activation parameterization based on the Fountoukis and Nenes (2005) series reduces the large negative CDNC bias associated with the default Abdul Razzak and Ghan (2000) parameterization from -35.4 % to a range of -0.8 to 7.1 %. However, it increases the errors due to overpredictions of CDNC, mainly over the northeastern US. This work indicates a need to improve other aerosol-cloud-radiation processes in the model, such as the spatial distribution of aerosol optical depth and cloud condensation nuclei, in order to further improve CDNC predictions.
Zhang, Wanfeng; Zhu, Shukui; He, Sheng; Wang, Yanxin
2015-02-06
Using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC/TOFMS), volatile and semi-volatile organic compounds in crude oil samples from different reservoirs or regions were analyzed for the development of a molecular fingerprint database. Based on the GC×GC/TOFMS fingerprints of crude oils, principal component analysis (PCA) and cluster analysis were used to distinguish the oil sources and find biomarkers. As a supervised technique, the geological characteristics of crude oils, including thermal maturity, sedimentary environment etc., are assigned to the principal components. The results show that tri-aromatic steroid (TAS) series are the suitable marker compounds in crude oils for the oil screening, and the relative abundances of individual TAS compounds have excellent correlation with oil sources. In order to correct the effects of some other external factors except oil sources, the variables were defined as the content ratio of some target compounds and 13 parameters were proposed for the screening of oil sources. With the developed model, the crude oils were easily discriminated, and the result is in good agreement with the practical geological setting. Copyright © 2014 Elsevier B.V. All rights reserved.
Sulfur driven nucleation mode formation in diesel exhaust under transient driving conditions.
Karjalainen, Panu; Rönkkö, Topi; Pirjola, Liisa; Heikkilä, Juha; Happonen, Matti; Arnold, Frank; Rothe, Dieter; Bielaczyc, Piotr; Keskinen, Jorma
2014-02-18
Sulfur driven diesel exhaust nucleation particle formation processes were studied in an aerosol laboratory, on engine dynamometers, and on the road. All test engines were equipped with a combination of a diesel oxidation catalyst (DOC) and a partial diesel particulate filter (pDPF). At steady operating conditions, the formation of semivolatile nucleation particles directly depended on SO2 conversion in the catalyst. The nucleation particle emission was most significant after a rapid increase in engine load and exhaust gas temperature. Results indicate that the nucleation particle formation at transient driving conditions does not require compounds such as hydrocarbons or sulfated hydrocarbons, however, it cannot be explained only by the nucleation of sulfuric acid. A real-world exhaust study with a heavy duty diesel truck showed that the nucleation particle formation occurs even with ultralow sulfur diesel fuel, even at downhill driving conditions, and that nucleation particles can contribute 60% of total particle number emissions. In general, due to sulfur storage and release within the exhaust aftertreatment systems and transients in driving, emissions of nucleation particles can even be the dominant part of modern diesel vehicle exhaust particulate number emissions.
Hageman, K.J.; Simonich, S.L.; Campbell, D.H.; Wilson, G.R.; Landers, D.H.
2006-01-01
The United States (U.S.) National Park Service has initiated research on the atmospheric deposition and fate of semi-volatile organic compounds in its alpine, sub-Arctic, and Arctic ecosystems in the Western U.S. Results for the analysis of pesticides in seasonal snowpack samples collected in spring 2003 from seven national parks are presented herein. From a target analyte list of 47 pesticides and degradation products, the most frequently detected current-use pesticides were dacthal, chlorpyrifos, endosulfan, and ??- hexachlorocyclohexane, whereas the most frequently detected historic-use pesticides were dieldrin, ??-hexachlorocyclohexane, chlordane, and hexachlorobenzene. Correlation analysis with latitude, temperature, elevation, particulate matter, and two indicators of regional pesticide use reveal that regional current and historic agricultural practices are largely responsible for the distribution of pesticides in the national parks in this study. Pesticide deposition in the Alaskan parks is attributed to long-range transport because there are no significant regional pesticide sources. The percentage of total pesticide concentration due to regional transport (%RT) was calculated for the other parks. %RT was highest at parks with higher regional cropland intensity and for pesticides with lower vapor pressures and shorter half-lives in air. ?? 2006 American Chemical Society.
Method 525.3 is an analytical method that uses solid phase extraction (SPE) and gas chromatography/mass spectrometry (GC/MS) for the identification and quantitation of 125 selected semi-volatile organic chemicals in drinking water.
Fitzpatrick, F.A.; Colman, J.A.
1993-01-01
This report contains data from the survey of manmade nonagricultural volatile and semivolatile organic chemicals in surface water in the upper Illinois River basin from May 1988 through March l990. In addition to the data, sampling methods and quality-assurance procedures are described. The survey was part of the upper Illinois River basin pilot project of the National Water-Quality Assessment program conducted by the U.S. Geological Survey. The organic chemicals analyzed from the water samples were those expected to be associated primarily with effluent from point sources in urban areas. A low-flow synoptic investigation of 52 volatile and 54 semivolatile organic chemicals was conducted at 31 sites in July 1988. Additional samples were collected monthly at two sites to continue to test for the presence of 43 volatile organic chemicals from December 1988 through March l990, and of all semivolatile organic chemicals at two sites from August through September 1988.
Electronic cigarette solutions and resultant aerosol profiles.
Herrington, Jason S; Myers, Colton
2015-10-30
Electronic cigarettes (e-cigarettes) are growing in popularity exponentially. Despite their ever-growing acceptance, their aerosol has not been fully characterized. The current study focused on evaluating e-cigarette solutions and their resultant aerosol for potential differences. A simple sampling device was developed to draw e-cigarette aerosol into a multi-sorbent thermal desorption (TD) tube, which was then thermally extracted and analyzed via a gas chromatography (GC) mass spectrometry (GC-MS) method. This novel application provided detectable levels of over one hundred fifteen volatile organic compounds (VOCs) and semivolatile organic compounds (SVOCs) from a single 40mL puff. The aerosol profiles from four commercially available e-cigarettes were compared to their respective solution profiles with the same GC-MS method. Solution profiles produced upwards of sixty four unidentified and identified (some only tentatively) constituents and aerosol profiles produced upwards of eighty two compounds. Results demonstrated distinct analyte profiles between liquid and aerosol samples. Most notably, formaldehyde, acetaldehyde, acrolein, and siloxanes were found in the aerosol profiles; however, these compounds were never present in the solutions. These results implicate the aerosolization process in the formation of compounds not found in solutions; have potential implications for human health; and stress the need for an emphasis on electronic cigarette aerosol testing. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.
Heavy Duty Diesel Exhaust Particles during Engine Motoring Formed by Lube Oil Consumption.
Karjalainen, Panu; Ntziachristos, Leonidas; Murtonen, Timo; Wihersaari, Hugo; Simonen, Pauli; Mylläri, Fanni; Nylund, Nils-Olof; Keskinen, Jorma; Rönkkö, Topi
2016-11-15
This study reports high numbers of exhaust emissions particles during engine motoring. Such particles were observed in the exhaust of two heavy duty vehicles with no diesel particle filter (DPF), driven on speed ramp tests and transient cycles. A significant fraction of these particles was nonvolatile in nature. The number-weighted size distribution peak was below 10 nm when a thermodenuder was used to remove semivolatile material, growing up to 40 nm after semivolatile species condensation. These particles were found to contribute to 9-13% of total particle number emitted over a complete driving cycle. Engine motoring particles originated from lube oil and evidence suggests that these are of heavy organic or organometallic material. Particles of similar characteristics have been observed in the core particle mode during normal fired engine operation. Their size and chemical character has implications primarily on the environmental toxicity of non-DPF diesel and, secondarily, on the performance of catalytic devices and DPFs. Lube oil formulation measures can be taken to reduce the emission of such particles.
NASA Astrophysics Data System (ADS)
Pereira, K. L.; Hamilton, J. F.; Rickard, A. R.; Bloss, W. J.; Alam, M. S.; Camredon, M.; Muñoz, A.; Vázquez, M.; Borrás, E.; Ródenas, M.
2014-06-01
The increasing demand for palm oil for uses in biofuel and food products is leading to rapid expansion of oil palm agriculture. Methyl chavicol (also known as estragole and 1-allyl-4-methoxybenzene) is an oxygenated biogenic volatile organic compound (VOC) that was recently identified as the main floral emission from an oil palm plantation in Malaysian Borneo. The emissions of methyl chavicol observed may impact regional atmospheric chemistry, but little is known of its ability to form secondary organic aerosol (SOA). The photo-oxidation of methyl chavicol was investigated at the European Photoreactor chamber as a part of the atmospheric chemistry of methyl chavicol (ATMECH) project. Aerosol samples were collected using a particle into liquid sampler (PILS) and analysed offline using an extensive range of instruments including; high-performance liquid chromatography mass spectrometry (HPLC-ITMS), high-performance liquid chromatography quadrupole time-of-flight mass spectrometry (HPLC-QTOFMS) and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). The SOA yield was determined as 18 and 29% for an initial VOC mixing ratio of 212 and 460 ppbv (parts per billion by volume) respectively; using a VOC:NOx ratio of ~5:1. In total, 59 SOA compounds were observed and the structures of 10 compounds have been identified using high-resolution tandem mass spectrometry. The addition of hydroxyl and/or nitro-functional groups to the aromatic ring appears to be an important mechanistic pathway for aerosol formation. This results in the formation of compounds with both low volatility and high O:C ratios, where functionalisation rather than fragmentation is mainly observed as a result of the stability of the ring. The SOA species observed can be characterised as semi-volatile to low-volatility oxygenated organic aerosol (SVOOA and LVOOA) components and therefore may be important in aerosol formation and growth.
Norwood, Daniel L; Mullis, James O; Davis, Mark; Pennino, Scott; Egert, Thomas; Gonnella, Nina C
2013-01-01
The structural analysis (i.e., identification) of organic chemical entities leached into drug product formulations has traditionally been accomplished with techniques involving the combination of chromatography with mass spectrometry. These include gas chromatography/mass spectrometry (GC/MS) for volatile and semi-volatile compounds, and various forms of liquid chromatography/mass spectrometry (LC/MS or HPLC/MS) for semi-volatile and relatively non-volatile compounds. GC/MS and LC/MS techniques are complementary for structural analysis of leachables and potentially leachable organic compounds produced via laboratory extraction of pharmaceutical container closure/delivery system components and corresponding materials of construction. Both hyphenated analytical techniques possess the separating capability, compound specific detection attributes, and sensitivity required to effectively analyze complex mixtures of trace level organic compounds. However, hyphenated techniques based on mass spectrometry are limited by the inability to determine complete bond connectivity, the inability to distinguish between many types of structural isomers, and the inability to unambiguously determine aromatic substitution patterns. Nuclear magnetic resonance spectroscopy (NMR) does not have these limitations; hence it can serve as a complement to mass spectrometry. However, NMR technology is inherently insensitive and its ability to interface with chromatography has been historically challenging. This article describes the application of NMR coupled with liquid chromatography and automated solid phase extraction (SPE-LC/NMR) to the structural analysis of extractable organic compounds from a pharmaceutical packaging material of construction. The SPE-LC/NMR technology combined with micro-cryoprobe technology afforded the sensitivity and sample mass required for full structure elucidation. Optimization of the SPE-LC/NMR analytical method was achieved using a series of model compounds representing the chemical diversity of extractables. This study demonstrates the complementary nature of SPE-LC/NMR with LC/MS for this particular pharmaceutical application. The identification of impurities leached into drugs from the components and materials associated with pharmaceutical containers, packaging components, and materials has historically been done using laboratory techniques based on the combination of chromatography with mass spectrometry. Such analytical techniques are widely recognized as having the selectivity and sensitivity required to separate the complex mixtures of impurities often encountered in such identification studies, including both the identification of leachable impurities as well as potential leachable impurities produced by laboratory extraction of packaging components and materials. However, while mass spectrometry-based analytical techniques have limitations for this application, newer analytical techniques based on the combination of chromatography with nuclear magnetic resonance spectroscopy provide an added dimension of structural definition. This article describes the development, optimization, and application of an analytical technique based on the combination of chromatography and nuclear magnetic resonance spectroscopy to the identification of potential leachable impurities from a pharmaceutical packaging material. The complementary nature of the analytical techniques for this particular pharmaceutical application is demonstrated.
Valle, Demetrio L; Puzon, Juliana Janet M; Cabrera, Esperanza C; Rivera, Windell L
2016-01-01
This study isolated and identified the antimicrobial compounds of Philippine Piper betle L. leaf ethanol extracts by thin layer chromatography- (TLC-) bioautography and gas chromatography-mass spectrometry (GC-MS). Initially, TLC separation of the leaf ethanol extracts provided a maximum of eight compounds with R f values of 0.92, 0.86, 0.76, 0.53, 0.40, 0.25, 0.13, and 0.013, best visualized when inspected under UV 366 nm. Agar-overlay bioautography of the isolated compounds demonstrated two spots with R f values of 0.86 and 0.13 showing inhibitory activities against two Gram-positive multidrug-resistant (MDR) bacteria, namely, methicillin-resistant Staphylococcus aureus and vancomycin-resistant Enterococcus. The compound with an R f value of 0.86 also possessed inhibitory activity against Gram-negative MDR bacteria, namely, carbapenem-resistant Enterobacteriaceae-Klebsiella pneumoniae and metallo-β-lactamase-producing Acinetobacter baumannii. GC-MS was performed to identify the semivolatile and volatile compounds present in the leaf ethanol extracts. Six compounds were identified, four of which are new compounds that have not been mentioned in the medical literature. The chemical compounds isolated include ethyl diazoacetate, tris(trifluoromethyl)phosphine, heptafluorobutyrate, 3-fluoro-2-propynenitrite, 4-(2-propenyl)phenol, and eugenol. The results of this study could lead to the development of novel therapeutic agents capable of dealing with specific diseases that either have weakened reaction or are currently not responsive to existing drugs.
Valle, Demetrio L.; Puzon, Juliana Janet M.; Cabrera, Esperanza C.
2016-01-01
This study isolated and identified the antimicrobial compounds of Philippine Piper betle L. leaf ethanol extracts by thin layer chromatography- (TLC-) bioautography and gas chromatography-mass spectrometry (GC-MS). Initially, TLC separation of the leaf ethanol extracts provided a maximum of eight compounds with R f values of 0.92, 0.86, 0.76, 0.53, 0.40, 0.25, 0.13, and 0.013, best visualized when inspected under UV 366 nm. Agar-overlay bioautography of the isolated compounds demonstrated two spots with R f values of 0.86 and 0.13 showing inhibitory activities against two Gram-positive multidrug-resistant (MDR) bacteria, namely, methicillin-resistant Staphylococcus aureus and vancomycin-resistant Enterococcus. The compound with an R f value of 0.86 also possessed inhibitory activity against Gram-negative MDR bacteria, namely, carbapenem-resistant Enterobacteriaceae-Klebsiella pneumoniae and metallo-β-lactamase-producing Acinetobacter baumannii. GC-MS was performed to identify the semivolatile and volatile compounds present in the leaf ethanol extracts. Six compounds were identified, four of which are new compounds that have not been mentioned in the medical literature. The chemical compounds isolated include ethyl diazoacetate, tris(trifluoromethyl)phosphine, heptafluorobutyrate, 3-fluoro-2-propynenitrite, 4-(2-propenyl)phenol, and eugenol. The results of this study could lead to the development of novel therapeutic agents capable of dealing with specific diseases that either have weakened reaction or are currently not responsive to existing drugs. PMID:27478476
Organic compounds in hydraulic fracturing fluids and wastewaters: A review.
Luek, Jenna L; Gonsior, Michael
2017-10-15
High volume hydraulic fracturing (HVHF) of shale to stimulate the release of natural gas produces a large quantity of wastewater in the form of flowback fluids and produced water. These wastewaters are highly variable in their composition and contain a mixture of fracturing fluid additives, geogenic inorganic and organic substances, and transformation products. The qualitative and quantitative analyses of organic compounds identified in HVHF fluids, flowback fluids, and produced waters are reviewed here to communicate knowledge gaps that exist in the composition of HVHF wastewaters. In general, analyses of organic compounds have focused on those amenable to gas chromatography, focusing on volatile and semi-volatile oil and gas compounds. Studies of more polar and non-volatile organic compounds have been limited by a lack of knowledge of what compounds may be present as well as quantitative methods and standards available for analyzing these complex mixtures. Liquid chromatography paired with high-resolution mass spectrometry has been used to investigate a number of additives and will be a key tool to further research on transformation products that are increasingly solubilized through physical, chemical, and biological processes in situ and during environmental contamination events. Diverse treatments have been tested and applied to HVHF wastewaters but limited information has been published on the quantitative removal of individual organic compounds. This review focuses on recently published information on organic compounds identified in flowback fluids and produced waters from HVHF. Copyright © 2017 Elsevier Ltd. All rights reserved.
Smoke aerosol chemistry and aging of Siberian biomass burning emissions in a large aerosol chamber
NASA Astrophysics Data System (ADS)
Kalogridis, A.-C.; Popovicheva, O. B.; Engling, G.; Diapouli, E.; Kawamura, K.; Tachibana, E.; Ono, K.; Kozlov, V. S.; Eleftheriadis, K.
2018-07-01
Vegetation open fires constitute a significant source of particulate pollutants on a global scale and play an important role in both atmospheric chemistry and climate change. To better understand the emission and aging characteristics of smoke aerosols, we performed small-scale fire experiments using the Large Aerosol Chamber (LAC, 1800 m3) with a focus on biomass burning from Siberian boreal coniferous forests. A series of burn experiments were conducted with typical Siberian biomass (pine and debris), simulating separately different combustion conditions, namely, flaming, smoldering and mixed phase. Following smoke emission and dispersion in the combustion chamber, we investigated aging of aerosols under dark conditions. Here, we present experimental data on emission factors of total, elemental and organic carbon, as well as individual organic compounds, such as anhydrosugars, phenolic and dicarboxylic acids. We found that total carbon accounts for up to 80% of the fine mode (PM2.5) smoke aerosol. Higher PM2.5 emission factors were observed in the smoldering compared to flaming phase and in pine compared to debris smoldering phase. For low-temperature combustion, organic carbon (OC) contributed to more than 90% of total carbon, whereas elemental carbon (EC) dominated the aerosol composition in flaming burns with a 60-70% contribution to the total carbon mass. For all smoldering burns, levoglucosan (LG), a cellulose decomposition product, was the most abundant organic species (average LG/OC = 0.26 for pine smoldering), followed by its isomer mannosan or dehydroabietic acid (DA), an important constituent of conifer resin (DA/OC = 0.033). A levoglucosan-to-mannosan ratio of about 3 was observed, which is consistent with ratios reported for coniferous biomass and more generally softwood. The rates of aerosol removal for OC and individual organic compounds were investigated during aging in the chamber in terms of mass concentration loss rates over time under dark conditions and compared to the loss rate of EC. The latter is used as an inert tracer for estimating aerosol mechanical deposition and wall losses of the otherwise chemically conserved aerosol species. The OC/EC ratio increased with smoke aging for the flaming phase, suggesting a production/partitioning of organic compounds after emission. On the other hand, for smoldering burns OC/EC ratios decreased further with aging due to additional sinks of OC, other than those related to deposition and wall losses alone, such as evaporation of semi-volatile compounds. The chemical fingerprints of the major PM components of fresh and aged smoke found in this study are proposed to be used for the assessment of contributions from Siberian biomass burning to atmospheric pollution in source apportionment studies like those using molecular marker approaches.
Brakstad, Odd G; Nordtug, Trond; Throne-Holst, Mimmi
2015-04-15
During the Deepwater Horizon (DWH) accident in 2010 a dispersant (Corexit 9500) was applied at the wellhead to disperse the Macondo oil and reduce the formation of surface slicks. A subsurface plume of small oil droplets was generated near the leaking well at 900-1300 m depth. A novel laboratory system was established to investigate biodegradation of small droplet oil dispersions (10 μm or 30 μm droplet sizes) of the Macondo oil premixed with Corexit 9500, using coastal Norwegian seawater at a temperature similar to the DWH plume (4-5°C). Biotransformation of volatile and semivolatile hydrocarbons and oil compound groups was generally faster in the 10 μm than in the 30 μm dispersions, showing the importance of oil droplet size for biodegradation. These data therefore indicated that dispersant treatment to reduce the oil droplet size may increase the biodegradation rates of oil compounds in the deepwater oil droplets. Copyright © 2015 Elsevier Ltd. All rights reserved.
Recent Discoveries and Future Challenges in Atmospheric Organic Chemistry.
Glasius, Marianne; Goldstein, Allen H
2016-03-15
Earth's atmosphere contains a multitude of organic compounds, which differ by orders of magnitude regarding fundamental properties such as volatility, reactivity, and propensity to form cloud droplets, affecting their impact on global climate and human health. Despite recent major research efforts and advances, there are still substantial gaps in understanding of atmospheric organic chemistry, hampering efforts to understand, model, and mitigate environmental problems such as aerosol formation in both polluted urban and more pristine regions. The analytical toolbox available for chemists to study atmospheric organic components has expanded considerably during the past decade, opening new windows into speciation, time resolution and detection of reactive and semivolatile compounds at low concentrations. This has provided unprecedented opportunities, but also unveiled new scientific challenges. Specific groundbreaking examples include the role of epoxides in aerosol formation especially from isoprene, the importance of highly oxidized, reactive organics in air-surface processes (whether atmosphere-biosphere exchange or aerosols), as well as the extent of interactions of anthropogenic and biogenic emissions and the resulting impact on atmospheric organic chemistry.
Shiraiwa, Manabu; Zuend, Andreas; Bertram, Allan K; Seinfeld, John H
2013-07-21
Atmospheric aerosols, comprising organic compounds and inorganic salts, play a key role in air quality and climate. Mounting evidence exists that these particles frequently exhibit phase separation into predominantly organic and aqueous electrolyte-rich phases. As well, the presence of amorphous semi-solid or glassy particle phases has been established. Using the canonical system of ammonium sulfate mixed with organics from the ozone oxidation of α-pinene, we illustrate theoretically the interplay of physical state, non-ideality, and particle morphology affecting aerosol mass concentration and the characteristic timescale of gas-particle mass transfer. Phase separation can significantly affect overall particle mass and chemical composition. Semi-solid or glassy phases can kinetically inhibit the partitioning of semivolatile components and hygroscopic growth, in contrast to the traditional assumption that organic compounds exist in quasi-instantaneous gas-particle equilibrium. These effects have significant implications for the interpretation of laboratory data and the development of improved atmospheric air quality and climate models.
NASA Astrophysics Data System (ADS)
Harrad, Stuart; Hassoun, Suzanne; Callén Romero, María. S.; Harrison, Roy M.
Concentrations of n-alkanes, petroleum biomarkers such as hopanes and steranes, n-alkanoic acids, n-alkanols, polycyclic aromatic hydrocarbons (PAH), dicarboxylic acids, and selected oxygenated PAH were separately determined in total suspended particulate matter and associated vapour phase in ambient air in Birmingham, UK. Samples were taken simultaneously at two locations on 24 separate occasions every 1-2 weeks between August 1999 and August 2000. Site A was 10 m from a busy road, 800 m from site B that was located within the "green space" of the University of Birmingham campus. Despite some differences in concentrations of some compounds, data from this study is in line with that reported in London, UK and in California. Differences between Sites A and B in both concentrations and carbon preference indices are consistent with greater traffic inputs at Site A, with some evidence of an appreciable biogenic input of n-alkanols and n-alkanes at the less-traffic influenced and more vegetated Site B. The biogenic input at Site B appears greater in the spring and summer months and suggests that biogenic emissions are appreciable even in British urban areas. Secondary formation mechanisms for some compounds including dicarboxylic acids and oxygenated PAH like fluoren-9-one are indicated by the lack of any significant intersite difference in concentrations. Intersite differences in concentrations provide new evidence that while petroleum biomarkers arise predominantly from local traffic, regional as well as local sources play an important rôle for the higher molecular weight PAH which exist predominantly in the particle phase.
Pavilonis, Brian T; Weisel, Clifford P; Buckley, Brian; Lioy, Paul J
2014-01-01
To reduce maintenance costs, municipalities and schools are starting to replace natural grass fields with a new generation synthetic turf. Unlike Astro-Turf, which was first introduced in the 1960s, synthetic field turf provides more cushioning to athletes. Part of this cushioning comes from materials like crumb rubber infill, which is manufactured from recycled tires and may contain a variety of chemicals. The goal of this study was to evaluate potential exposures from playing on artificial turf fields and associated risks to trace metals, semi-volatile organic compounds (SVOCs), and polycyclic aromatic hydrocarbons (PAHs) by examining typical artificial turf fibers (n = 8), different types of infill (n = 8), and samples from actual fields (n = 7). Three artificial biofluids were prepared, which included: lung, sweat, and digestive fluids. Artificial biofluids were hypothesized to yield a more representative estimation of dose than the levels obtained from total extraction methods. PAHs were routinely below the limit of detection across all three biofluids, precluding completion of a meaningful risk assessment. No SVOCs were identified at quantifiable levels in any extracts based on a match of their mass spectrum to compounds that are regulated in soil. The metals were measurable but at concentrations for which human health risk was estimated to be low. The study demonstrated that for the products and fields we tested, exposure to infill and artificial turf was generally considered de minimus, with the possible exception of lead for some fields and materials. © 2013 Society for Risk Analysis.
Garrison, Virginia H.; Majewski, Michael S.; Foreman, William T.; Genualdi, Susan A.; Mohammed, Azad; Massey Simonich, Stacy L.
2014-01-01
Anthropogenic semivolatile organic compounds (SOCs) that persist in the environment, bioaccumulate, are toxic at low concentrations, and undergo long-range atmospheric transport (LRT) were identified and quantified in the atmosphere of a Saharan dust source region (Mali) and during Saharan dust incursions at downwind sites in the eastern Caribbean (U.S. Virgin Islands, Trinidad and Tobago) and Cape Verde. More organochlorine and organophosphate pesticides (OCPPs), polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphenyl (PCB) congeners were detected in the Saharan dust region than at downwind sites. Seven of the 13 OCPPs detected occurred at all sites: chlordanes, chlorpyrifos, dacthal, dieldrin, endosulfans, hexachlorobenzene (HCB), and trifluralin. Total SOCs ranged from 1.9–126 ng/m3 (mean = 25 ± 34) at source and 0.05–0.71 ng/m3 (mean = 0.24 ± 0.18) at downwind sites during dust conditions. Most SOC concentrations were 1–3 orders of magnitude higher in source than downwind sites. A Saharan source was confirmed for sampled air masses at downwind sites based on dust particle elemental composition and rare earth ratios, atmospheric back trajectory models, and field observations. SOC concentrations were considerably below existing occupational and/or regulatory limits; however, few regulatory limits exist for these persistent organic compounds. Long-term effects of chronic exposure to low concentrations of SOCs are unknown, as are possible additive or synergistic effects of mixtures of SOCs, biologically active trace metals, and mineral dust particles transported together in Saharan dust air masses.
ACCELERATED SOLVENT EXTRACTION COMBINED WITH ...
A research project was initiated to address a recurring problem of elevated detection limits above required risk-based concentrations for the determination of semivolatile organic compounds in high moisture content solid samples. This project was initiated, in cooperation with the EPA Region 1 Laboratory, under the Regional Methods Program administered through the ORD Office of Science Policy. The aim of the project was to develop an approach for the rapid removal of water in high moisture content solids (e.g., wetland sediments) in preparation for analysis via Method 8270. Alternative methods for water removal have been investigated to enhance compound solid concentrations and improve extraction efficiency, with the use of pressure filtration providing a high-throughput alternative for removal of the majority of free water in sediments and sludges. In order to eliminate problems with phase separation during extraction of solids using Accelerated Solvent Extraction, a variation of a water-isopropanol extraction method developed at the USGS National Water Quality Laboratory in Denver, CO is being employed. The concentrations of target compounds in water-isopropanol extraction fluids are subsequently analyzed using an automated Solid Phase Extraction (SPE)-GC/MS method developed in our laboratory. The coupled approaches for dewatering, extraction, and target compound identification-quantitation provide a useful alternative to enhance sample throughput for Me
DOE Office of Scientific and Technical Information (OSTI.GOV)
Not Available
The Adrian Municipal Well Field is listed on the National Priorities List. Adrian is located in Nobles County which is in southwestern Minnesota. In September 1983, 1,2-dichloroethane (1,2-DCA), a volatile organic compound (VOC), was detected in Municipal Wells 3 and 4. Subsequent sampling in January 1984 indicated increased levels of VOC contamination in Wells 3 and 4. In these sampling events, a number of VOCs were detected. Source identification has also focused on a number of underground storage tanks (USTs) used to store gasoline and fuel oil. Twelve contaminants have been identified in ground water from the surficial aquifer. Subsurfacemore » soil contamination has also been detected. A Soil Organic Vapor survey measured both total ionizable hydrocarbons and the gasoline constituents benzene, toluene, and total xylenes at 2-3 feet feet above the water table. Because of the high concentrations of gasoline contaminants in the soil and ground water at the site, there exists the potential for combustion or explosion if gasoline vapors migrate from these media into nearby businesses or homes. Several of the USTs contained or did contain fuel oil. Fuel oil contains semi-volatile constituents (e.g., polynuclear aromatic hydrocarbons, etc.) not found in gasoline. Based on the available information, the site is considered to be of potential public health concern because of the risk to human health caused by the possibility of exposure to hazardous substances via ground water, and potentially surface water, air, and biota.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
DeRosier, R.; Waterland, L.R.
1986-02-01
The report describes results from field testing a watertube industrial boiler firing a coal/water slurry (CWS) containing about 60% coal. Emission measurements included continuous monitoring of flue-gas emissions; source assessment sampling system (SASS) sampling of the flue-gas, with subsequent analysis of samples to obtain total flue-gas organics in two boiling point ranges, compound category information within these ranges, specific quantitation of the semivolatile organic priority pollutants, and flue-gas concentrations of 73 trace elements: EPA Methods 5/8 sampling for particulate, SO/sub 2/, and SO/sub 3/ emissions; and grab sampling of fuel and ash for inorganic composition. NOx, SO/sub 2/, CO, andmore » TUHC emissions were in the 230-310, 880-960, 170-200, and 1-3 ppm ranges (corrected to 3% 02), respectively, over the two tests performed. Particulate levels at the boiler outlet (upstream of the unit's baghouse) were 7.3 g/dscm in the comprehensive test. Coarse particulate (>3 micrometers) predominated. Total organic emissions were almost 50 mg/dscm, with about 70% of the organic matter in the nonvolatile (>300 C) boiling point range. The bottom ash organic content was 8 mg/g, 80% of which was in the nonvolatile range. Of the PAHs, only naphthalene was detected in the flue gas particulate, with emission levels of 8.6 micrograms/dscm. Several PAHs were found in the bottom ash.« less
NASA Astrophysics Data System (ADS)
Fang, Zheng; Deng, Wei; Zhang, Yanli; Ding, Xiang; Tang, Mingjin; Liu, Tengyu; Hu, Qihou; Zhu, Ming; Wang, Zhaoyi; Yang, Weiqiang; Huang, Zhonghui; Song, Wei; Bi, Xinhui; Chen, Jianmin; Sun, Yele; George, Christian; Wang, Xinming
2017-12-01
Agricultural residues are among the most abundant biomass burned globally, especially in China. However, there is little information on primary emissions and photochemical evolution of agricultural residue burning. In this study, indoor chamber experiments were conducted to investigate primary emissions from open burning of rice, corn and wheat straws and their photochemical aging as well. Emission factors of NOx, NH3, SO2, 67 non-methane hydrocarbons (NMHCs), particulate matter (PM), organic aerosol (OA) and black carbon (BC) under ambient dilution conditions were determined. Olefins accounted for > 50 % of the total speciated NMHCs emission (2.47 to 5.04 g kg-1), indicating high ozone formation potential of straw burning emissions. Emission factors of PM (3.73 to 6.36 g kg-1) and primary organic carbon (POC, 2.05 to 4.11 gC kg-1), measured at dilution ratios of 1300 to 4000, were lower than those reported in previous studies at low dilution ratios, probably due to the evaporation of semi-volatile organic compounds under high dilution conditions. After photochemical aging with an OH exposure range of (1.97-4.97) × 1010 molecule cm-3 s in the chamber, large amounts of secondary organic aerosol (SOA) were produced with OA mass enhancement ratios (the mass ratio of total OA to primary OA) of 2.4-7.6. The 20 known precursors could only explain 5.0-27.3 % of the observed SOA mass, suggesting that the major precursors of SOA formed from open straw burning remain unidentified. Aerosol mass spectrometry (AMS) signaled that the aged OA contained less hydrocarbons but more oxygen- and nitrogen-containing compounds than primary OA, and carbon oxidation state (OSc) calculated with AMS resolved O / C and H / C ratios increased linearly (p < 0.001) with OH exposure with quite similar slopes.
Differences in BVOC oxidation and SOA formation above and below the forest canopy
NASA Astrophysics Data System (ADS)
Schulze, Benjamin C.; Wallace, Henry W.; Flynn, James H.; Lefer, Barry L.; Erickson, Matt H.; Jobson, B. Tom; Dusanter, Sebastien; Griffith, Stephen M.; Hansen, Robert F.; Stevens, Philip S.; VanReken, Timothy; Griffin, Robert J.
2017-02-01
Gas-phase biogenic volatile organic compounds (BVOCs) are oxidized in the troposphere to produce secondary pollutants such as ozone (O3), organic nitrates (RONO2), and secondary organic aerosol (SOA). Two coupled zero-dimensional models have been used to investigate differences in oxidation and SOA production from isoprene and α-pinene, especially with respect to the nitrate radical (NO3), above and below a forest canopy in rural Michigan. In both modeled environments (above and below the canopy), NO3 mixing ratios are relatively small (< 0.5 pptv); however, daytime (08:00-20:00 LT) mixing ratios below the canopy are 2 to 3 times larger than those above. As a result of this difference, NO3 contributes 12 % of total daytime α-pinene oxidation below the canopy while only contributing 4 % above. Increasing background pollutant levels to simulate a more polluted suburban or peri-urban forest environment increases the average contribution of NO3 to daytime below-canopy α-pinene oxidation to 32 %. Gas-phase RONO2 produced through NO3 oxidation undergoes net transport upward from the below-canopy environment during the day, and this transport contributes up to 30 % of total NO3-derived RONO2 production above the canopy in the morning (˜ 07:00). Modeled SOA mass loadings above and below the canopy ultimately differ by less than 0.5 µg m-3, and extremely low-volatility organic compounds dominate SOA composition. Lower temperatures below the canopy cause increased partitioning of semi-volatile gas-phase products to the particle phase and up to 35 % larger SOA mass loadings of these products relative to above the canopy in the model. Including transport between above- and below-canopy environments increases above-canopy NO3-derived α-pinene RONO2 SOA mass by as much as 45 %, suggesting that below-canopy chemical processes substantially influence above-canopy SOA mass loadings, especially with regard to monoterpene-derived RONO2.
Biogenic Potassium Salt Particles as Seeds for Secondary Organic Aerosol in the Amazon
NASA Astrophysics Data System (ADS)
Pöhlker, Christopher; Wiedemann, Kenia T.; Sinha, Bärbel; Shiraiwa, Manabu; Gunthe, Sachin S.; Smith, Mackenzie; Su, Hang; Artaxo, Paulo; Chen, Qi; Cheng, Yafang; Elbert, Wolfgang; Gilles, Mary K.; Kilcoyne, Arthur L. D.; Moffet, Ryan C.; Weigand, Markus; Martin, Scot T.; Pöschl, Ulrich; Andreae, Meinrat O.
2012-08-01
The fine particles serving as cloud condensation nuclei in pristine Amazonian rainforest air consist mostly of secondary organic aerosol. Their origin is enigmatic, however, because new particle formation in the atmosphere is not observed. Here, we show that the growth of organic aerosol particles can be initiated by potassium-salt-rich particles emitted by biota in the rainforest. These particles act as seeds for the condensation of low- or semi-volatile organic compounds from the atmospheric gas phase or multiphase oxidation of isoprene and terpenes. Our findings suggest that the primary emission of biogenic salt particles directly influences the number concentration of cloud condensation nuclei and affects the microphysics of cloud formation and precipitation over the rainforest.
Understanding sources of organic aerosol during CalNex-2010 using the CMAQ-VBS
NASA Astrophysics Data System (ADS)
Woody, Matthew C.; Baker, Kirk R.; Hayes, Patrick L.; Jimenez, Jose L.; Koo, Bonyoung; Pye, Havala O. T.
2016-03-01
Community Multiscale Air Quality (CMAQ) model simulations utilizing the traditional organic aerosol (OA) treatment (CMAQ-AE6) and a volatility basis set (VBS) treatment for OA (CMAQ-VBS) were evaluated against measurements collected at routine monitoring networks (Chemical Speciation Network (CSN) and Interagency Monitoring of Protected Visual Environments (IMPROVE)) and those collected during the 2010 California at the Nexus of Air Quality and Climate Change (CalNex) field campaign to examine important sources of OA in southern California. Traditionally, CMAQ treats primary organic aerosol (POA) as nonvolatile and uses a two-product framework to represent secondary organic aerosol (SOA) formation. CMAQ-VBS instead treats POA as semivolatile and lumps OA using volatility bins spaced an order of magnitude apart. The CMAQ-VBS approach underpredicted organic carbon (OC) at IMPROVE and CSN sites to a greater degree than CMAQ-AE6 due to the semivolatile POA treatment. However, comparisons to aerosol mass spectrometer (AMS) measurements collected at Pasadena, CA, indicated that CMAQ-VBS better represented the diurnal profile and primary/secondary split of OA. CMAQ-VBS SOA underpredicted the average measured AMS oxygenated organic aerosol (OOA, a surrogate for SOA) concentration by a factor of 5.2, representing a considerable improvement to CMAQ-AE6 SOA predictions (factor of 24 lower than AMS). We use two new methods, one based on species ratios (SOA/ΔCO and SOA/Ox) and another on a simplified SOA parameterization, to apportion the SOA underprediction for CMAQ-VBS to slow photochemical oxidation (estimated as 1.5 × lower than observed at Pasadena using -log(NOx : NOy)), low intrinsic SOA formation efficiency (low by 1.6 to 2 × for Pasadena), and low emissions or excessive dispersion for the Pasadena site (estimated to be 1.6 to 2.3 × too low/excessive). The first and third factors are common to CMAQ-AE6, while the intrinsic SOA formation efficiency for that model is estimated to be too low by about 7 × . From source-apportioned model results, we found most of the CMAQ-VBS modeled POA at the Pasadena CalNex site was attributable to meat cooking emissions (48 %, consistent with a substantial fraction of cooking OA in the observations). This is compared to 18 % from gasoline vehicle emissions, 13 % from biomass burning (in the form of residential wood combustion), and 8 % from diesel vehicle emissions. All "other" inventoried emission sources (e.g., industrial, point, and area sources) comprised the final 13 %. The CMAQ-VBS semivolatile POA treatment underpredicted AMS hydrocarbon-like OA (HOA) + cooking-influenced OA (CIOA) at Pasadena by a factor of 1.8 compared to a factor of 1.4 overprediction of POA in CMAQ-AE6, but it did capture the AMS diurnal profile of HOA and CIOA well, with the exception of the midday peak. Overall, the CMAQ-VBS with its semivolatile treatment of POA, SOA from intermediate volatility organic compounds (IVOCs), and aging of SOA improves SOA model performance (though SOA formation efficiency is still 1.6-2 × too low). However, continued efforts are needed to better understand assumptions in the parameterization (e.g., SOA aging) and provide additional certainty to how best to apply existing emission inventories in a framework that treats POA as semivolatile, which currently degrades existing model performance at routine monitoring networks. The VBS and other approaches (e.g., AE6) require additional work to appropriately incorporate IVOC emissions and subsequent SOA formation.
Understanding sources of organic aerosol during CalNex-2010 using the CMAQ-VBS
Woody, Matthew C.; Baker, Kirk R.; Hayes, Patrick L.; ...
2016-03-29
In this paper, Community Multiscale Air Quality (CMAQ) model simulations utilizing the traditional organic aerosol (OA) treatment (CMAQ-AE6) and a volatility basis set (VBS) treatment for OA (CMAQ-VBS) were evaluated against measurements collected at routine monitoring networks (Chemical Speciation Network (CSN) and Interagency Monitoring of Protected Visual Environments (IMPROVE)) and those collected during the 2010 California at the Nexus of Air Quality and Climate Change (CalNex) field campaign to examine important sources of OA in southern California. Traditionally, CMAQ treats primary organic aerosol (POA) as nonvolatile and uses a two-product framework to represent secondary organic aerosol (SOA) formation. CMAQ-VBS insteadmore » treats POA as semivolatile and lumps OA using volatility bins spaced an order of magnitude apart. The CMAQ-VBS approach underpredicted organic carbon (OC) at IMPROVE and CSN sites to a greater degree than CMAQ-AE6 due to the semivolatile POA treatment. However, comparisons to aerosol mass spectrometer (AMS) measurements collected at Pasadena, CA, indicated that CMAQ-VBS better represented the diurnal profile and primary/secondary split of OA. CMAQ-VBS SOA underpredicted the average measured AMS oxygenated organic aerosol (OOA, a surrogate for SOA) concentration by a factor of 5.2, representing a considerable improvement to CMAQ-AE6 SOA predictions (factor of 24 lower than AMS). We use two new methods, one based on species ratios (SOA/ΔCO and SOA/O x) and another on a simplified SOA parameterization, to apportion the SOA underprediction for CMAQ-VBS to slow photochemical oxidation (estimated as 1.5 × lower than observed at Pasadena using -log(NO x:NO y)), low intrinsic SOA formation efficiency (low by 1.6 to 2 × for Pasadena), and low emissions or excessive dispersion for the Pasadena site (estimated to be 1.6 to 2.3 × too low/excessive). The first and third factors are common to CMAQ-AE6, while the intrinsic SOA formation efficiency for that model is estimated to be too low by about 7 ×. From source-apportioned model results, we found most of the CMAQ-VBS modeled POA at the Pasadena CalNex site was attributable to meat cooking emissions (48 %, consistent with a substantial fraction of cooking OA in the observations). This is compared to 18 % from gasoline vehicle emissions, 13 % from biomass burning (in the form of residential wood combustion), and 8 % from diesel vehicle emissions. All "other" inventoried emission sources (e.g., industrial, point, and area sources) comprised the final 13 %. The CMAQ-VBS semivolatile POA treatment underpredicted AMS hydrocarbon-like OA (HOA) + cooking-influenced OA (CIOA) at Pasadena by a factor of 1.8 compared to a factor of 1.4 overprediction of POA in CMAQ-AE6, but it did capture the AMS diurnal profile of HOA and CIOA well, with the exception of the midday peak. Overall, the CMAQ-VBS with its semivolatile treatment of POA, SOA from intermediate volatility organic compounds (IVOCs), and aging of SOA improves SOA model performance (though SOA formation efficiency is still 1.6–2 × too low). However, continued efforts are needed to better understand assumptions in the parameterization (e.g., SOA aging) and provide additional certainty to how best to apply existing emission inventories in a framework that treats POA as semivolatile, which currently degrades existing model performance at routine monitoring networks. Finally, the VBS and other approaches (e.g., AE6) require additional work to appropriately incorporate IVOC emissions and subsequent SOA formation.« less
Bao, Zhongwen; Haberer, Christina M; Maier, Uli; Beckingham, Barbara; Amos, Richard T; Grathwohl, Peter
2016-11-01
Temperature changes can drive cycling of semi-volatile pollutants between different environmental compartments (e.g. atmosphere, soil, plants). To evaluate the impact of daily temperature changes on atmospheric concentration fluctuations we employed a physically based model coupling soil, plants and the atmosphere, which accounts for heat transport, effective gas diffusion, sorption and biodegradation in the soil as well as eddy diffusion and photochemical oxidation in the atmospheric boundary layer of varying heights. The model results suggest that temperature-driven re-volatilization and uptake in soils cannot fully explain significant diurnal concentration fluctuations of atmospheric pollutants as for example observed for polychlorinated biphenyls (PCBs). This holds even for relatively low water contents (high gas diffusivity) and high sorption capacity of the topsoil (high organic carbon content and high pollutant concentration in the topsoil). Observed concentration fluctuations, however, can be easily matched if a rapidly-exchanging environmental compartment, such as a plant layer, is introduced. At elevated temperatures, plants release organic pollutants, which are rapidly distributed in the atmosphere by eddy diffusion. For photosensitive compounds, e.g. some polycyclic aromatic hydrocarbons (PAHs), decreasing atmospheric concentrations would be expected during daytime for the bare soil scenario. This decline is buffered by a plant layer, which acts as a ground-level reservoir. The modeling results emphasize the importance of a rapidly-exchanging compartment above ground to explain short-term atmospheric concentration fluctuations. Copyright © 2016 Elsevier B.V. All rights reserved.
Ye, Penglin; Ding, Xiang; Ye, Qing; Robinson, Ellis S; Donahue, Neil M
2016-03-10
Semivolatile organic compounds (SVOCs) play an essential role in secondary organic aerosol (SOA) formation, chemical aging, and mixing of organic aerosol (OA) from different sources. Polyethylene glycol (PEG400) particles are liquid, polar, and nearly nonvolatile; they provide a new vehicle to study the interaction between SVOCs with OA. With a unique fragment ion C4H9O2(+) (m/z 89), PEG400 can be easily separated from α-pinene SOA in aerosol mass spectra. By injecting separately prepared PEG probe particles into a chamber containing SOA coated on ammonium sulfate seeds, we show that a substantial pool of SVOCs exists in equilibrium with the original SOA particles. Quantitative findings are based on bulk mass spectra, size-dependent composition, and the evolution of individual particle mass spectra, which we use to separate the two particle populations. We observed a larger fraction of SVOC vapors with increased amounts of reacted α-pinene. For the same amount of reacted α-pinene, the SOA formed from α-pinene oxidized by OH radicals had a higher fraction of SOA vapors than SOA formed by α-pinene ozonolysis. Compared to the PEG400 probe particles, we observed a lower mass fraction of SVOCs in poly(ethylene glycol) dimethyl ether (MePEG500) probe particles under otherwise identical conditions; this may be due to the lower polarity of the MePEG500 or caused by esterification reactions between the PEG400 and organic acids in the SOA.
Yee, Lindsay D; Craven, Jill S; Loza, Christine L; Schilling, Katherine A; Ng, Nga Lee; Canagaratna, Manjula R; Ziemann, Paul J; Flagan, Richard C; Seinfeld, John H
2012-06-21
The extended photooxidation of and secondary organic aerosol (SOA) formation from dodecane (C(12)H(26)) under low-NO(x) conditions, such that RO(2) + HO(2) chemistry dominates the fate of the peroxy radicals, is studied in the Caltech Environmental Chamber based on simultaneous gas and particle-phase measurements. A mechanism simulation indicates that greater than 67% of the initial carbon ends up as fourth and higher generation products after 10 h of reaction, and simulated trends for seven species are supported by gas-phase measurements. A characteristic set of hydroperoxide gas-phase products are formed under these low-NO(x) conditions. Production of semivolatile hydroperoxide species within three generations of chemistry is consistent with observed initial aerosol growth. Continued gas-phase oxidation of these semivolatile species produces multifunctional low volatility compounds. This study elucidates the complex evolution of the gas-phase photooxidation chemistry and subsequent SOA formation through a novel approach comparing molecular level information from a chemical ionization mass spectrometer (CIMS) and high m/z ion fragments from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). Combination of these techniques reveals that particle-phase chemistry leading to peroxyhemiacetal formation is the likely mechanism by which these species are incorporated in the particle phase. The current findings are relevant toward understanding atmospheric SOA formation and aging from the "unresolved complex mixture," comprising, in part, long-chain alkanes.
Monitoring industrial wastewater by online GC-MS with direct aqueous injection.
Wortberg, M; Ziemer, W; Kugel, M; Müller, H; Neu, H-J
2006-03-01
An online GC-MS-system for automated monitoring of crude wastewater at a complex chemical production site is presented. The modular system is, in principal, based on commercial equipment, but utilizes a special, two-stage injector, which consists of a splitless vaporization chamber on top of a PTV injector filled with Tenax. This set-up enables direct injection of wastewater. Almost 140 volatile and semi-volatile compounds are calibrated down to 1 mg L(-1), which is sufficient for analysis of the influent of the wastewater-treatment plant. Two instruments analyze alternately, every 20 min, and the instrument cycle time is 40 min. The quantitative results are transferred to a database which is connected to a process-control system. Depending on the nature and concentration of a compound, an alarm can be generated and the wastewater stream can be diverted into an "off spec tank" if necessary. The GC-MS-system operates quasi-continuously with a system availability >98%. Data quality is automatically controlled in each run and by daily analysis of a quality-control sample. The development of a novel stacked PTV-PTV injector design to expand the range of analytes to selected basic compounds is described.
Jerković, Igor; Marijanović, Zvonimir; Kranjac, Marina; Radonić, Ani
2015-02-01
Headspace solid-phase microextraction (HS-SPME), ultrasonic solvent extraction (USE) and solid phase extraction (SPE), followed by GC-FID/MS were used for screening of dandelion (Taraxacum officinale Weber) honey headspace, volatiles and semi-volatiles. The obtained results constitute a breakthrough towards screening of dandelion honey since dominant compounds identified in the extracts were not previously reported for this honey type. Nitriles dominated in the headspace, particularly 3-methylpentanenitrile (up to 29.9%) and phenylacetonitrile (up to 20.9%). Lower methyl branched aliphatic acids and norisoprenoids were relevant minor constituents of the headspace. The extracts contained phenylacetic acid (up to 24.0%) and dehydrovomifoliol (up to 19.3%) as predominant compounds, while 3-methylpentanenitrile and phenylacetonitrile were detected in the extracts in minor abundance. Dehydrovomifoliol can be considered more characteristic for dandelion honey in distinction from phenylacetic acid. Low molecular aliphatic acids, benzene derivatives and an array of higher aliphatic compounds were also found in the extracts. The results of SPE/GC-FID/MS were very similar to USE/GC-FID/MS with the solvent dichloromethane. The use of all applied methodologies was relevant for the comprehensive chemical fingerprinting of dandelion honey volatiles.
NASA Astrophysics Data System (ADS)
Wallace, Henry W.; Sanchez, Nancy P.; Flynn, James H.; Erickson, Mathew H.; Lefer, Barry L.; Griffin, Robert J.
2018-01-01
From February 7 to 27, 2015, a mobile air quality laboratory was deployed to a location proximate to a major refinery, the Port of Houston, and several neighborhoods to conduct measurements of atmospheric trace gases and particulate matter. Two statistical models were utilized to apportion the sources of pollution impacting this site and the denizens of the nearby neighborhoods. Positive matrix factorization (PMF) was performed on the organic signal of the aerosol mass spectra, resulting in five factors totaling an average of 4.1 μg/m3 of the organic aerosol: hydrocarbon-like (0.67 μg/m3), cooking (0.35 μg/m3) biomass burning (1.14 μg/m3), low-volatility oxidized (1.15 μg/m3), and semi-volatile oxidized (0.78 μg/m3). Principal component analysis was performed on daytime and nighttime data, including concentrations from PMF output, of other PM1 components, and of trace gases. This generated five daytime and five nighttime factors that explained 74.5% and 73.0% of the variance, respectively. The most important factors impacting this site were from mobile source exhaust and petrochemical aromatic compound emissions. Together these two factors also constitute most of the observed carcinogens.
Equilibrium Relationship between SVOCs in PVC Products and the Air in Contact with the Product.
Eichler, Clara M A; Wu, Yaoxing; Cao, Jianping; Shi, Shanshan; Little, John C
2018-03-06
Phthalates and phthalate alternatives are semivolatile organic compounds (SVOCs) present in many PVC products as plasticizers to enhance product performance. Knowledge of the mass-transfer parameters, including the equilibrium concentration in the air in contact with the product surface ( y 0 ), will greatly improve the ability to estimate the emission rate of SVOCs from these products and to assess human exposure. The objective of this study was to measure y 0 for different PVC products and to evaluate its relationship with the material-phase concentrations ( C 0 ). Also, C 0 and y 0 data from other sources were included, resulting in a substantially larger data set ( N total = 34, T = 25 °C) than found in previous studies. The results show that the material/gas equilibrium relationship does not follow Raoult's law and that therefore the assumption of an ideal solution is invalid. Instead, Henry's law applies, and the Henry's law constant for all target SVOCs consists of the respective pure liquid vapor pressure and an activity coefficient γ, which accounts for the nonideal nature of the solution. For individual SVOCs, a simple partitioning relationship exists, but Henry's law is more generally applicable and will be of greater value in rapid exposure assessment procedures.
New screening approach for risk assessment of pesticides in ambient air
NASA Astrophysics Data System (ADS)
Yusà, Vicent; Coscollà, Clara; Millet, Maurice
2014-10-01
We present a novel screening approach for inhalation risk assessment of currently used pesticides (CUPs) in ambient air, based on the measurements of pesticide levels in the inhalable fraction of the particulate matter (PM10). Total concentrations in ambient air (gas + particle phases) were estimated using a theoretical model of distribution of semi-volatile organic compounds between the gas and the particulate phase based on the octanol-air partition (Koa) of each pesticide. The proposed approach was used in a pilot study conducted in a rural station in Valencia (Spain) from April through to October 2010. Twenty out of 82 analysed pesticides were detected in average concentrations ranging from 1.63 to 117.01 pg m-3. For adults, children and infants the estimated chronic inhalation risk, expressed as Hazard Quotient (HQ) was <1 for all pesticides. Likewise, the cumulative exposure for detected organophosphorus, pyrethroids and carbamates pesticides, was estimated using as metrics the Hazard Index (HI), which was less than 1 for the three families of pesticides assessed. The cancer risk estimated for the detected pesticides classified as Likely or Possible carcinogens was less than 1.15E-7 for infants. In our opinion, the screening approach proposed could be used in the monitoring and risk assessment of pesticides in ambient air.
Falls, W. Fred; Caldwell, Andral W.; Guimaraes, Wladmir G.; Ratliff, W. Hagan; Wellborn, John B.; Landmeyer, James E.
2012-01-01
Soil-gas and groundwater assessments were conducted at the Gibson Road landfill in 201 to provide screening-level environmental contamination data to supplement the data collected during previous environmental studies at the landfill. Passive samplers were used in both assessments to detect volatile and semivolatile organic compounds and polycyclic aromatic hydrocarbons in soil gas and groundwater. A total of 56 passive samplers were deployed in the soil in late July and early August for the soil-gas assessment. Total petroleum hydrocarbons (TPH) were detected at masses greater than the method detection level of 0.02 microgram in all samplers and masses greater than 2.0 micrograms in 13 samplers. Three samplers located between the landfill and a nearby wetland had TPH masses greater than 20 micrograms. Diesel was detected in 28 of the 56 soil-gas samplers. Undecane, tridecane, and pentadecane were detected, but undecane was the most common diesel compound with 23 detections. Only five detections exceeded a combined diesel mass of 0.10 microgram, including the highest mass of 0.27 microgram near the wetland. Toluene was detected in only five passive samplers, including masses of 0.65 microgram near the wetland and 0.85 microgram on the southwestern side of the landfill. The only other gasoline-related compound detected was octane in two samplers. Naphthalene was detected in two samplers in the gully near the landfill and two samplers along the southwestern side of the landfill, but had masses less than or equal to 0.02 microgram. Six samplers located southeast of the landfill had detections of chlorinated compounds, including one perchloroethene detections (0.04 microgram) and five chloroform detections (0.05 to0.08 microgram). Passive samplers were deployed and recovered on August 8, 2011, in nine monitoring wells along the southwestern, southeastern and northeastern sides of the landfill and down gradient from the eastern corner of the landfill. Six of the nine samplers had TPH concentrations greater than 100 micrograms per liter. TPH concentrations declined from 320 micrograms per liter in a sampler near the landfill to 18 micrograms in a sampler near the wetland. Five of the samplers had detections of one or more diesel compounds but detections of individual diesel compounds had concentrations below a method detection level of 0.01 microgram per liter. Benzene was detected in three samplers and exceeded the national primary drinking-water standard of 5 micrograms per liter set by the U.S. Environmental Protection Agency. The concentrations of benzene, and therefore BTEX, were 6.1 micrograms per liter in the sampler near the eastern corner of the landfill, 27 micrograms per liter in the sampler near the wetland, and 37 micrograms per liter in the sampler at the southern corner of the landfill. Nonfuel-related compounds were detected in the four wells that are aligned between the eastern corner of the landfill and the wetland. The sampler deployed nearest the eastern corner of the landfill had the greatest number of detected organic compounds and had the only detections of two trimethylbenzene compounds, naphthalene, 2-methyl naphthalene, and 1,4-dichlorobenzene. The two up gradient samplers had the greatest number of chlorinated compounds with five compounds each, compared to detections of four compounds and one compound in the two down gradient samplers. All four samplers had detections of 1,1-dichloroethane which ranged from 42 to 1,300 micrograms per liter. Other detections of chlorinated compounds included trichloroethene, perchloroethene, cis-1,2-dichloroethene, 1,1,1-trichloroethane and chloroform.
Proboscis extension reflex platform for volatiles and semi-volatiles detection
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wingo, Robert M.; McCabe, Kirsten J.; Haarmann, Timothy K.
The present invention provides an apparatus for the detection of volatile and semi-volatile chemicals using the olfactory abilities of honey bees that are trained to respond to the presence of a specific chemical in a sample of gas with the proboscis extension reflex (PER). In particular, the geometry and arrangement of the parts of the apparatus are such that the amount of surface area in contact with the sample of gas prior to its introduction to the bees is minimized to improve the detection of particular volatile and semi-volatile that have a tendency to "stick" to contacting surfaces, especially certainmore » chemicals associated with explosives and narcotics. According to another aspect of the present invention, a pre-concentrating means is incorporated with the device to effectively increase the concentration of "sticky" chemicals presented to the insects.« less
NASA Astrophysics Data System (ADS)
Strickland, Jessica; Klinger, Andreas; Herbig, Jens; Holzinger, Rupert
2017-04-01
Semi-volatile organic compounds (SVOCs) are anthropogenically and naturally occurring chemical compounds that have vapor pressures such that they exist in both the gas and condensed phase at room temperature. Due to the fact SVOCs condense easily, they are interesting in the context of organic aerosol formation and these compounds impact atmospheric properties and human health. Proton Transfer Reaction Mass Spectrometry (PTR-MS, resolution 1200 FWHM) is a method that facilitates deeper analysis of SVOCs. Our setup, consisting of a PTR-MS with a time of flight mass spectrometer coupled to a denuder sampler (DS) was stationed as part of the European ACTRIS-2 program at 200m atop the Cabauw tower in the Netherlands as of September, 2016. The DS consists of three denuders in series. The first two denuders are coated with dimethylpolysiloxane (DB1, OD 4mm, 3cm long) and consists of an assemblage of micro-channels (ID 80 micrometer). The third denuder is an activated charcoal monolith of the same dimensions but with larger (thus fewer) channels (ID 800 micrometer). The air sampled at 800mL/min is pulled through these denuders as laminar flow and the SVOCs will collide and condense on the wall. Undesirable wall losses are minimized by using a short and high flow inlet lines. The collected SVOCs are thermally desorbed under a Nitrogen (N2) gas flow and transferred to the PTR-MS through heated lines to avoid re-condensation. Evaluation of the full mass spectra revealed over 200 different compounds in the range 15-500 Da. The majority of the mass of SVOCs was contained in m/z > 100 and typical mixing ratios of the detected SVOCs were a few pmol/mol in ambient air. Discernible contamination from the DB1 coating was detected and therefore, different blank methods have been tested and evaluated using a student T-test. Proper blank correction is an important issue of this method and will be discussed in detail. Data from October 19th, 2016, are used as case studies for analyzing the output and results. On Oct. 19th, the highest average concentrations pertained to m/z 75.028, 219.041, 77.017, 355.100, and 429.119, were 623, 196, 149, 144 and 135 pg/m^3, respectively. We observed significant carryover from the first to the second DB1 denuder. For instance, on Oct. 19th, compared to the Nitrogen blank, 193/251 compounds that collected in the first DB1 denuder were enhanced in ambient air, while 181/251 were enhanced in the second DB1 denuder. On the other hand, quantitatively, the carryover was relatively small, with roughly 76% in the first DB1 denuder and 24% in the second when considering m/z 100-475. Ambient SVOC mixing ratios of a two-week period in October 2016 will be discussed.
Minguillón, M C; Pérez, N; Marchand, N; Bertrand, A; Temime-Roussel, B; Agrios, K; Szidat, S; van Drooge, B; Sylvestre, A; Alastuey, A; Reche, C; Ripoll, A; Marco, E; Grimalt, J O; Querol, X
2016-07-18
Source contributions of organic aerosol (OA) are still not fully understood, especially in terms of quantitative distinction between secondary OA formed from anthropogenic precursors vs. that formed from natural precursors. In order to investigate the OA origin, a field campaign was carried out in Barcelona in summer 2013, including two periods characterized by low and high traffic conditions. Volatile organic compound (VOC) concentrations were higher during the second period, especially aromatic hydrocarbons related to traffic emissions, which showed a marked daily cycle peaking during traffic rush hours, similarly to black carbon (BC) concentrations. Biogenic VOC (BVOC) concentrations showed only minor changes from the low to the high traffic period, and their intra-day variability was related to temperature and solar radiation cycles, although a decrease was observed for monoterpenes during the day. The organic carbon (OC) concentrations increased from the first to the second period, and the fraction of non-fossil OC as determined by (14)C analysis increased from 43% to 54% of the total OC. The combination of (14)C analysis and Aerosol Chemical Speciation Monitor (ACSM) OA source apportionment showed that the fossil OC was mainly secondary (>70%) except for the last sample, when the fossil secondary OC only represented 51% of the total fossil OC. The fraction of non-fossil secondary OC increased from 37% of total secondary OC for the first sample to 60% for the last sample. This enhanced formation of non-fossil secondary OA (SOA) could be attributed to the reaction of BVOC precursors with NOx emitted from road traffic (or from its nocturnal derivative nitrate that enhances night-time semi-volatile oxygenated OA (SV-OOA)), since NO2 concentrations increased from 19 to 42 μg m(-3) from the first to the last sample.
NASA Astrophysics Data System (ADS)
Boudehane, A.; Lounas, A.; Moussaoui, Y.; Balducci, C.; Cecinato, A.
2016-11-01
Indoor environments are affected by a number of organic contaminants, whose concentrations can exceed by orders of magnitude those found outdoors in external air. At this regard, polycyclic aromatic hydrocarbons (PAHs) deserve a special concern. PAHs occur in the air both in the gaseous and particulate forms; they are associated to fine aerosols and soil dust, and deposit on surfaces. Nonetheless, scarce information exists about the PAH pollution of indoor locations in Northern Africa. PAHs were first investigated in dust of interiors in Ouargla (Saharan Algeria), concurrently with n-alkanes and polar organics. Settled dust was collected from pre-cleaned surfaces (0.5 m2 each) at 7 internal locations in total from a school, the city hospital and university, and a home. Three sample series were collected 15, 30 days and random after the preliminary cleaning of surfaces. Contemporarily, organic compounds were collected at 15 locations of the target sites by deploying diffusive samplers over the whole study period to obtain molecular signatures of semi-volatile organic fraction. A consolidated procedure consisting of ultra-sonic bath extraction, semi-preparative column chromatography and gas chromatographic - mass spectrometric analysis was applied for chemical characterization of dusts. n-Alkanes ranged from 3.8 to 41 μg/m2 in dust and 0.17-2.42 μg/m3 in gas phase. PAHs concentrations were 17-89 ng/m2 and 45-182 ng/m3, respectively. Caffeine and nicotine were found both in dust (63-2,02 ng/m2 and 7-284 ng/m2, respectively) and as vapors in air (4-416 ng/m3 and 3.5-60 ng/m3). Two sites were affected by cannabinoids, while traces of nonylphenols occurred at all locations. External air was, on the average, more affected by PAHs than the interiors of school and hospital, but not of university. The compound concentrations show that Ouargla city is seriously polluted and requires actions to improve air quality.
NASA Astrophysics Data System (ADS)
Staudt, M.; Bourgeois, I.; Al Halabi, R.; Song, W.; Williams, J.
2017-03-01
Phytogenic emission of large volatile organic compounds (VOCs) such as monoterpenes (MTs) and sesquiterpenes (SQTs) are key precursors to the formation and growth of atmospheric particles. However, controlled environment studies to elucidate emission responses to temperature and light are still sparse. In this study, the volatile contents and emission responses of Aleppo pine and Rosemary have been investigated. These two common Mediterranean species store semivolatiles inside (resin ducts) and outside (trichomes) their foliage tissues respectively. Both species emitted mainly MTs with basal emission rates of around 5 (Rosemary) and 10 (pine) μg g-1 h-1 and SQTs about one order of magnitude lower. In Aleppo pine, two volatile sources could be clearly distinguished: 1) de-novo synthesized emission of (E)-β-ocimene and linalool, which accounted for about 70% of the total VOC release, were not found in foliar VOC extracts and expressed light dependency (LD) and temperature responses typical for enzyme driven emissions; and 2) storage-derived emissions of various MTs and SQTs whose emissions increased exponentially with temperature, showed no light dependency and were all present in leaf extracts. In Rosemary, all emitted MTs and SQTs including many oxygenated compounds, showed responses typical for stored volatiles and were all found in leaf extracts. The emissions of individual volatiles or volatile classes could be well described with the commonly applied empirical algorithms developed for LD or non LD emissions. However, the shapes of the temperature responses, and hence the deduced coefficient values, were significantly different between oxygenated and non-oxygenated compounds. They also differed between the storage-derived emissions of the two plant species, for individual VOCs or VOC classes. We address the possible reasons for this variation in temperature responses and argue that they are mostly due to molecular interactions along the species specific leaf-internal diffusion paths including the build-up of transient VOC pools and degradation.
Polyfluorinated compounds in ambient air from ship- and land-based measurements in northern Germany
NASA Astrophysics Data System (ADS)
Dreyer, Annekatrin; Ebinghaus, Ralf
Neutral volatile and semi-volatile polyfluorinated organic compounds (PFC) and ionic perfluorinated compounds were determined in air samples collected at two sites in the vicinity of Hamburg, Germany, and onboard the German research vessel Atair during a cruise in the German Bight, North Sea, in early November 2007. PUF/XAD-2/PUF cartridges and glass fiber filters as sampling media were applied to collect several fluorotelomer alcohols (FTOH), fluorotelomer acrylates (FTA), perfluoroalkyl sulfonamides (FASA), and perfluoroalkyl sulfonamido ethanols (FASE) in the gas- and particle-phase as well as a set of perfluorinated carboxylates (PFCA) and sulfonates (PFSA) in the particle-phase. This study presents the distribution of PFC in ambient air of the German North Sea and in the vicinity of Hamburg for the first time. Average total PFC concentrations in and around Hamburg (180 pg m -3) were higher than those observed in the German Bight (80 pg m -3). In the German Bight, minimum-maximum gas-phase concentrations of 17-82 pg m -3 for ΣFTOH, 2.6-10 pg m -3 for ΣFTA, 10-15 pg m -3 for ΣFASA, and 2-4.4 pg m -3 for ΣFASE were determined. In the vicinity of Hamburg, minimum-maximum gas-phase concentrations of 32-204 pg m -3 for ΣFTOH, 3-26 pg m -3 for ΣFTA, 3-18 pg m -3 for ΣFASA, and 2-15 pg m -3 for ΣFASE were detected. Concentrations of perfluorinated acids were in the range of 1-11 pg m -3. FTOH clearly dominated the substance spectrum; 8:2 FTOH occurred in maximum proportions. Air mass back trajectories, cluster, and correlation analyses revealed that the air mass origin and thus medium to long range atmospheric transport was the governing parameter for the amount of PFC in ambient air. Southwesterly located source regions seemed to be responsible for elevated PFC concentrations, local sources appeared to be of minor importance.
NASA Astrophysics Data System (ADS)
Saha, Provat K.; Khlystov, Andrey; Grieshop, Andrew P.
2018-02-01
We present spatial measurements of particle volatility and mixing state at a site near a North Carolina interstate highway (I-40) applying several heating (thermodenuder; TD) experimental approaches. Measurements were conducted in summer 2015 and winter 2016 in a roadside trailer (10 m from road edge) and during downwind transects at different distances from the highway under favorable wind conditions using a mobile platform. Results show that the relative abundance of semi-volatile species (SVOCs) in ultrafine particles decreases with downwind distance, which is consistent with the dilution and mixing of traffic-sourced particles with background air and evaporation of semi-volatile species during downwind transport. An evaporation kinetics model was used to derive particle volatility distributions by fitting TD data. While the TD-derived distribution apportions about 20-30 % of particle mass as semi-volatile (SVOCs; effective saturation concentration, C∗ ≥ 1µm-3) at 10 m from the road edge, approximately 10 % of particle mass is attributed to SVOCs at 220 m, showing that the particle-phase semi-volatile fraction decreases with downwind distance. The relative abundance of semi-volatile material in the particle phase increased during winter. Downwind spatial gradients of the less volatile particle fraction (that remaining after heating at 180 °C) were strongly correlated with black carbon (BC). BC size distribution and mixing state measured using a single-particle soot photometer (SP2) at the roadside trailer showed that a large fraction (70-80 %) of BC particles were externally mixed. Heating experiments with a volatility tandem differential mobility analyzer (V-TDMA) also showed that the nonvolatile fraction in roadside aerosols is mostly externally mixed. V-TDMA measurements at different distances downwind from the highway indicate that the mixing state of roadside aerosols does not change significantly (e.g., BC mostly remains externally mixed) within a few hundred meters from the highway. Our analysis indicates that a superposition of volatility distributions measured in laboratory vehicle tests and of background
aerosol can be used to represent the observed partitioning of near-road particles. The results from this study show that exposures and impacts of BC and semi-volatile organics-containing particles in a roadside microenvironment may differ across seasons and under changing ambient conditions.
Srinivasan, Rangesh; Sorial, George A
2011-01-01
Problems due to the taste and odor in drinking water are common in treatment facilities around the world. Taste and odor are perceived by the public as the primary indicators of the safely and acceptability of drinking water and are mainly caused by the presence of two semi-volatile compounds--2-methyl isoborneol (MIB) and geosmin. A review of these two taste and odor causing compounds in drinking water is presented. The sources for the formation of these compounds in water are discussed along with the health and regulatory implications. The recent developments in the analysis of MIB/geosmin in water which have allowed for rapid measurements in the nanogram per liter concentrations are also discussed. This review focuses on the relevant treatment alternatives, that are described in detail with emphasis on their respective advantages and problems associated with their implementation in a full-scale facility. Conventional treatment processes in water treatment plants, such as coagulation, sedimentation and chlorination have been found to be ineffective for removal of MIB/geosmin. Studies have shown powdered activated carbon, ozonation and biofiltration to be effective in treatment of these two compounds. Although some of these technologies are more effective and show more promise than the others, much work remains to be done to optimize these technologies so that they can be retrofitted or installed with minimal impact on the overall operation and effectiveness of the treatment system.
NASA Astrophysics Data System (ADS)
He, J.; Zielinska, B.; Balasubramanian, R.
2010-04-01
An intensive field study was conducted in the urban atmosphere of Singapore to investigate the composition of organic compounds in both gaseous and particulate phases during the period of August to early November 2006. 17 atmospheric samples were collected. These samples were subjected to accelerated solvent extraction with a mixture of dichloromethane and acetone and separated into functional group fractions for analyses by GC/MS. Over 180 organic compounds belonging to three major fractions (n-alkanes, polycyclic aromatic hydrocarbons (PAHs), and polar organic compounds (POCs)) were identified and quantified. The characteristics and abundance of the n-alkanes, PAHs, mono and dicarboxylic acids, methoxylated phenols and other POCs were determined. The composition of these organic compounds fluctuated temporally with most of them being relatively higher in October than those in other months of the sampling period. 3-D backward air mass trajectory analyses together with the carbon preference index (CPI), molecular diagnostic ratios and molecular markers were used to investigate the origin of organic species measured in this study. Based on these diagnostic tools, the increased abundance of atmospheric organic species during October could be attributed to the occurrence of regional smoke haze episodes due to biomass burning in Indonesia. Among the POCs investigated, phthalic acid and cis-pinonic acid showed a strong linear relationship with maximum daily ozone concentration, indicating secondary organic aerosols (SOA) to be an important contributor to ambient atmospheric organics over Singapore.
Baurès, Estelle; Blanchard, Olivier; Mercier, Fabien; Surget, Emilie; le Cann, Pierre; Rivier, Alexandre; Gangneux, Jean-Pierre; Florentin, Arnaud
2018-06-09
In addition to being influenced by the environment, the indoor air pollution in hospitals may be associated with specific compounds emitted from various products used, health care activities and building materials. This study has enabled assessment of the chemical and microbiological concentrations of indoor air in two French hospitals. Based on an integrated approach, the methodology defined aims to measure concentrations of a wide range of chemical compounds (>50 volatile and semi-volatile organic compounds), particle concentrations (PM 10 and PM 2.5 ), microorganisms (fungi, bacteria and viruses) and ambient parameters (temperature, relative humidity, pressure and carbon dioxide). Chemical and microbiological air concentrations were measured during two campaigns (winter and summer) and across seven rooms (for spatial variability). The results have shown that indoor air contains a complex mixture of chemical, physical and microbiological compounds. Concentrations in the same order of magnitude were found in both hospitals. Compared to dwelling indoor air, our study shows low, at least equivalent, contamination for non-hospital specific parameters (aldehydes, limonene, phthalates, aromatic hydrocarbons), which is related to ventilation efficiency. Chemical compounds retrieved at the highest concentration and frequencies are due to healthcare activities, for example alcohol - most commonly ethanol - and hand rubbing (median concentration: ethanol 245.7 μg/m 3 and isopropanol 13.6 μg/m 3 ); toluene and staining in parasitology (highest median concentration in Nancy laboratory: 2.1 μg/m 3 )). Copyright © 2018. Published by Elsevier B.V.
2015-01-01
To estimate exposures to smokers from cigarettes, smoking topography is typically measured and programmed into a smoking machine to mimic human smoking, and the resulting smoke emissions are tested for relative levels of harmful constituents. However, using only the summary puff data—with a fixed puff frequency, volume, and duration—may underestimate or overestimate actual exposure to smoke toxins. In this laboratory study, we used a topography-driven smoking machine that faithfully reproduces a human smoking session and individual human topography data (n = 24) collected during previous clinical research to investigate if replicating the true puff profile (TP) versus the mathematically derived smoothed puff profile (SM) resulted in differences in particle size distributions and selected toxic/carcinogenic organic compounds from mainstream smoke emissions. Particle size distributions were measured using an electrical low pressure impactor, the masses of the size-fractionated fine and ultrafine particles were determined gravimetrically, and the collected particulate was analyzed for selected particle-bound, semivolatile compounds. Volatile compounds were measured in real time using a proton transfer reaction-mass spectrometer. By and large, TP levels for the fine and ultrafine particulate masses as well as particle-bound organic compounds were slightly lower than the SM concentrations. The volatile compounds, by contrast, showed no clear trend. Differences in emissions due to the use of the TP and SM profiles are generally not large enough to warrant abandoning the procedures used to generate the simpler smoothed profile in favor of the true profile. PMID:25536227
Zhang, Hua; Bibi, Aisha; Lu, Haiyan; Han, Jing; Chen, Huanwen
2017-08-01
It is of sustainable interest to improve the sensitivity and selectivity of the ionization process, especially for direct analysis of complex samples without matrix separation. Herein, four ambient ionization methods including desorption atmospheric pressure chemical ionization (DAPCI), heat-assisted desorption atmospheric pressure chemical ionization (heat-assisted DAPCI), microwave plasma torch (MPT) and internal extractive electrospray ionization (iEESI) were employed for comparative analysis of the navel orange tissue samples by mass spectrometry. The volatile organic compounds (e.g. ethanol, vanillin, leaf alcohol and jasmine lactone) were successfully detected by non-heat-assisted DAPCI-MS, while semi-volatile organic compounds (e.g. 1-nonanol and ethyl nonanoate) together with low abundance of non-volatile organic compounds (e.g. sinensetin and nobiletin) were obtained by heat-assisted DAPCI-MS. Typical nonvolatile organic compounds [e.g. 5-(hydroxymethyl)furfural and glucosan] were sensitively detected with MPT-MS. Compounds of high polarity (e.g. amino acids, alkaloids and sugars) were easily profiled with iEESI-MS. Our data showed that more analytes could be detected when more energy was delivered for the desorption ionization purpose; however, heat-sensitive analytes would not be detected once the energy input exceeded the dissociation barriers of the analytes. For the later cases, soft ionization methods such as iEESI were recommended to sensitively profile the bioanalytes of high polarity. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.
NASA Astrophysics Data System (ADS)
Khare, Peeyush; Gentner, Drew R.
2018-04-01
Decades of policy in developed regions has successfully reduced total anthropogenic emissions of gas-phase organic compounds, especially volatile organic compounds (VOCs), with an intentional, sustained focus on motor vehicles and other combustion-related sources. We examine potential secondary organic aerosol (SOA) and ozone formation in our case study megacity (Los Angeles) and demonstrate that non-combustion-related sources now contribute a major fraction of SOA and ozone precursors. Thus, they warrant greater attention beyond indoor environments to resolve large uncertainties in their emissions, oxidation chemistry, and outdoor air quality impacts in cities worldwide. We constrain the magnitude and chemical composition of emissions via several bottom-up approaches using chemical analyses of products, emissions inventory assessments, theoretical calculations of emission timescales, and a survey of consumer product material safety datasheets. We demonstrate that the chemical composition of emissions from consumer products as well as commercial and industrial products, processes, and materials is diverse across and within source subcategories. This leads to wide ranges of SOA and ozone formation potentials that rival other prominent sources, such as motor vehicles. With emission timescales from minutes to years, emission rates and source profiles need to be included, updated, and/or validated in emissions inventories with expected regional and national variability. In particular, intermediate-volatility and semi-volatile organic compounds (IVOCs and SVOCs) are key precursors to SOA, but are excluded or poorly represented in emissions inventories and exempt from emissions targets. We present an expanded framework for classifying VOC, IVOC, and SVOC emissions from this diverse array of sources that emphasizes a life cycle approach over longer timescales and three emission pathways that extend beyond the short-term evaporation of VOCs: (1) solvent evaporation, (2) solute off-gassing, and (3) volatilization of degradation by-products. Furthermore, we find that ambient SOA formed from these non-combustion-related emissions could be misattributed to fossil fuel combustion due to the isotopic signature of their petroleum-based feedstocks.
Keyte, Ian J; Albinet, Alexandre; Harrison, Roy M
2016-10-01
Vehicular emissions are a key source of polycyclic aromatic compounds (PACs), including polycyclic aromatic hydrocarbons (PAHs) and their oxygenated (OPAH) and nitrated (NPAH) derivatives, in the urban environment. Road tunnels are a useful environment for the characterisation of on-road vehicular emissions, providing a realistic traffic fleet and a lack of direct sunlight, chemical reactivity and non-traffic sources. In the present investigation the concentrations of selected PAHs, OPAHs and NPAHs have been measured in the Parc des Princes Tunnel in Paris (PdPT, France), and at the Queensway Road Tunnel and an urban background site in Birmingham (QT, U.K). A higher proportion of semi-volatile (3-4 ring) PAH, OPAH and NPAH compounds are associated with the particulate phase compared with samples from the ambient environment. A large (~85%) decline in total PAH concentrations is observed between 1992 and 2012 measurements in QT. This is attributed primarily to the introduction of catalytic converters in the U.K as well as increasingly stringent EU vehicle emissions legislation. In contrast, NPAH concentrations measured in 2012 are similar to those measured in 1996. This observation, in addition to an increased proportion of (Phe+Flt+Pyr) in the observed PAH burden in the tunnel, is attributed to the increased number of diesel passenger vehicles in the U.K during this period. Except for OPAHs, comparable PAH and NPAH concentrations are observed in both investigated tunnels (QT and PdP). Significant differences are shown for specific substances between PAC chemical profiles in relation with the national traffic fleet differences (33% diesel passenger cars in U.K. vs 69% in France and up to 80% taking into account all vehicle categories). The dominating and sole contribution of 1-Nitropyrene observed in the PdPT NPAH profile strengthens the promising use of this compound as a diesel exhaust marker for PM source apportionment studies. Copyright © 2016 British Geological Survey, NERC. Published by Elsevier B.V. All rights reserved.
Impedance matching of a coaxial antenna for microwave in-situ processing of polluted soils.
Pauli, Mario; Kayser, Thorsten; Wiesbeck, Werner; Komarov, Vyacheslav
2011-01-01
The present paper is focused on the minimization of return loss of a slotted coaxial radiator proposed for a decontamination system for soils contaminated by volatile or semi-volatile organic compounds such as oils or fuels. The antenna upgrade is achieved by coating it with a 5 mm thick Teflon layer. The electromagnetic characteristics reflection coefficient and power density distribution around the antenna surrounded by soils with different moisture levels are analyzed numerically. Simplified analytical approaches are employed to accelerate the optimization of the given antenna for microwave heating systems. The improved antenna design shows a good matching of the antenna to the surrounding soil with varying moisture levels. This ensures a high efficiency of the proposed in-situ soil decontamination system.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Not Available
The Reich Farm site is located in Dover Township, Ocean County, New Jersey. The site is currently owned by Mr. and Mrs. Samuel Reich. In August 1971, they rented a portion of their land to Mr. Nicholas Fernicola for temporary storage of used 55-gallon drums. Most of the drums had Union Carbide Corporation (UCC) markings on them, with labels reading 'tar pitch,' 'lab waste solvent,' 'blend of resin and oil,' and 'solvent wash of process stream' among others. The site first came to the attention of the New Jersey Superior Court when the Reichs filed suit against Mr. Fernicola andmore » UCC. The primary contaminants of concern affecting the ground water and soils are VOCs including 1,1,1-trichloroethane (TCA), TCE, PCE, and semi-volatile organics compounds (SVOCs). The selected remedial action for the site is included.« less
Feasibility studies for the treatment and reuse of contaminated marine sediments.
Bonomoa, L; Careghini, A; Dastoli, S; De Propris, L; Ferrari, G; Gabellini, M; Saponaro, S
2009-07-01
This paper presents preliminary results of laboratory tests aimed at evaluating the easibility of the remediation of marine sediments, which are polluted by mercury and petroleum hydrocarbons, dredged at the bay of Augusta (SR, Italy). The treatment is composed of two sequential steps: in the first, a cement-based granular material is produced (based on a high performance concrete approach); then, the volatile and the semi-volatile compounds in the granular material are removed by a thermal desorption step. Treated materials could be reused or put into caissons, according to their mechanical properties and environmental compatibility. The experiments were focused on evaluating the effect of the process parameter values on: (i) the evolution of cement hydration reactions, (ii) thermal desorption removal efficiencies, (iii) leaching behaviour of the treated material.
Understanding the fate and transport of petroleum hydrocarbons from coal tar within gasholders.
Coulon, Frédéric; Orsi, Roberto; Turner, Claire; Walton, Chris; Daly, Paddy; Pollard, Simon J T
2009-02-01
Coal tars have been identified as posing a threat to human health due to their toxic, mutagenic and carcinogenic characteristics. Workers involved in former gasholders decommissioning are potentially exposed to relevant concentrations of volatile and semi-volatile hydrocarbons upon opening up derelict tanks and during tar excavation/removal. While information on contaminated sites air-quality and its implications on medium-long term exposure is available, acute exposure issues associated with the execution of critical tasks are less understood. Calculations indicated that the concentration of a given contaminant in the gasholder vapour phase only depends on the coal tar composition, being only barely affected by the presence of water in the gasholder and the tar volume/void space ratio. Fugacity modelling suggested that risk-critical compounds such as benzene, naphthalene and other monocyclic and polycyclic aromatic hydrocarbons may gather in the gasholder air phase at significant concentrations. Gasholder emissions were measured on-site and compared with the workplace exposure limits (WELs) currently in use in UK. While levels for most of the toxic compounds were far lower than WELs, benzene air-concentrations where found to be above the accepted threshold. In addition due to the long exposure periods involved in gasholder decommissioning and the significant contribution given by naphthalene to the total coal tar vapour concentration, the adoption of a WEL for naphthalene may need to be considered to support operators in preventing human health risk at the workplace. The Level I fugacity approach used in this study demonstrated its suitability for applications to sealed environments such as gasholders and its further refining could provide a useful tool for land remediation risk assessors.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Monroy, G.J. Keene, F.E.
A study to address Ambos (Both) Nogales' air quality concerns was conducted by the Arizona Department of Environmental Quality (ADEQ), in conjunction with Mexico's Secretaria de Medio Ambiente, Recursos Naturales y Pesca (SEMARNAP), from 1994 to 1998. The study, which is part of the US-Mexico Border XXI Program, consisted of the following tasks: (1) air sampling/monitoring; (2) emissions inventory; (3) meteorological modeling; and, (4) health risk assessment. The following types of samples were collected: particulate matter (PM); volatile organic compounds; semi-volatile organic compounds; and aldehydes. All samples were collected for a 24-hour period; every sixth day during the warm monthsmore » (April--September), and every third day during the cold months (October--March). There were a total of six sampling stations; three on each side of the border. PM samples were collected at all six sites, while samples for Hazardous Air Pollutants (HAPs) were collected at four of those sites. Sample analyses were performed at the Desert Research Institute (DRI) in Reno, Nevada. Furthermore, four of the sites were outfitted with meteorological equipment, in order to gather data on wind speed and direction. PM and meteorological data are still being collected at two sampling sites, one in Arizona and one in Sonora. An emissions inventory of point, mobile and area sources for the Ambos Nogales area (12 x 19 km. domain), was developed following completion of the sampling effort. In order to accomplish this task, ADEQ contracted the services of RADIAN International and Powers Engineering; which in turn enlisted the services of Heuristica Ambiental of Hermosillo, Sonora. This task was completed in July, 1997. Vehicular emissions were found to be one of the main contributors of air emissions in the Ambos Nogales area. The third task of this project consisted developing meteorological models of the study area.« less
Stormwater-runoff data, Madison, Wisconsin, 1993-94
Waschbusch, R.J.
1996-01-01
As required by Section 402(P) of the Water Quality Control Act of 1987, stormwater-runoff samples collected during storms that met three criteria (rainfall depths 50 to 150 percent of average depth range, rainfall durations 50 to 150 percent of average duration, and antecedent dry-weather period of at least 72 hours) were analyzed for semivolatile organic chemicals, total metals, pesticides, polychlorinated biphenyls, inorganic constituents, bacteria, oil and grease, pH, and water temperature. Two of the seven sites also had samples analyzed for volatile organic chemicals. In addition to the required sampling, additional runoff samples that did not necessarily meet the three rainfall criteria, were analyzed for total metals and inorganic constituents. Storm loads of selected constituents were computed.
Cocker, David R; Shah, Sandip D; Johnson, Kent; Miller, J Wayne; Norbeck, Joseph M
2004-04-01
Information about in-use emissions from diesel engines remains a critical issue for inventory development and policy design. Toward that end, we have developed and verified the first mobile laboratory that measures on-road or real-world emissions from engines at the quality level specified in the U.S. Congress Code of Federal Regulations. This unique mobile laboratory provides information on integrated and modal regulated gaseous emission rates and integrated emission rates for speciated volatile and semivolatile organic compounds and particulate matter during real-world operation. Total emissions are captured and collected from the HDD vehicle that is pulling the mobile laboratory. While primarily intended to accumulate data from HDD vehicles, it may also be used to measure emission rates from stationary diesel sources such as back-up generators. This paper describes the development of the mobile laboratory, its measurement capabilities, and the verification process and provides the first data on total capture gaseous on-road emission measurements following the California Air Resources Board (ARB) 4-mode driving cycle, the hot urban dynamometer driving schedule (UDDS), the modified 5-mode cycle, and a 53.2-mi highway chase experiment. NOx mass emission rates (g mi(-1)) for the ARB 4-mode driving cycle, the hot UDDS driving cycle, and the chase experimentwerefoundto exceed current emission factor estimates for the engine type tested by approximately 50%. It was determined that congested traffic flow as well as "off-Federal Test Procedure cycle" emissions can lead to significant increases in per mile NOx emission rates for HDD vehicles.
High Molecular Weight Dimer Esters in α-Pinene Secondary Organic Aerosol
NASA Astrophysics Data System (ADS)
Kristensen, Kasper; Cui, Tianqu; Zhang, Haofei; Gold, Avram; Glasius, Marianne; Surratt, Jason D.
2014-05-01
Monoterpenes, such as α-pinene, constitute an important group of biogenic volatile organic compounds (BVOC). Once emitted into the atmosphere α-pinene is removed by oxidization by the hydroxyl radical (OH), reactions with ozone (O3), and with nitrate radicals (NO3) resulting in the formation of first-generation oxidation products, such as semi-volatile carboxylic acids. In addition, higher molecular weight dimer esters originating from the oxidation of α-pinene have been observed in both laboratory-generated and ambient secondary organic aerosols (SOA). While recent studies suggest that the dimers are formed through esterification between carboxylic acids in the particle phase, the formation mechanism of the dimer esters is still ambiguous. In this work, we present the results of a series of smog chamber experiments to assess the formation of dimer esters formed from the oxidation of α-pinene. Experiments were conducted in the University of North Carolina (UNC) dual outdoor smog chamber facility to investigate the effect of oxidant species (OH versus O3), relative humidity (RH), and seed aerosol acidity in order to obtain a better understanding of the conditions leading to the formation of the dimer esters and how these parameters may affect the formation and chemical composition of SOA. The chemical composition of α-pinene SOA was investigated by ultra-performance liquid chromatography/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-Q-TOFMS), and a total of eight carboxylic acids and four dimer esters were identified, constituting between 8 and 12 % of the total α-pinene SOA mass.
Emissions of Selected Semivolatile Organic Chemicals from Forest and Savannah Fires.
Wang, Xianyu; Thai, Phong K; Mallet, Marc; Desservettaz, Maximilien; Hawker, Darryl W; Keywood, Melita; Miljevic, Branka; Paton-Walsh, Clare; Gallen, Michael; Mueller, Jochen F
2017-02-07
The emission factors (EFs) for a broad range of semivolatile organic chemicals (SVOCs) from subtropical eucalypt forest and tropical savannah fires were determined for the first time from in situ investigations. Significantly higher (t test, P < 0.01) EFs (μg kg -1 dry fuel, gas + particle-associated) for polycyclic aromatic hydrocarbons (∑ 13 PAHs) were determined from the subtropical forest fire (7,000 ± 170) compared to the tropical savannah fires (1,600 ± 110), due to the approximately 60-fold higher EFs for 3-ring PAHs from the former. EF data for many PAHs from the eucalypt forest fire were comparable with those previously reported from pine and fir forest combustion events. EFs for other SVOCs including polychlorinated biphenyl (PCB), polychlorinated naphthalene (PCN), and polybrominated diphenyl ether (PBDE) congeners as well as some pesticides (e.g., permethrin) were determined from the subtropical eucalypt forest fire. The highest concentrations of total suspended particles, PAHs, PCBs, PCNs, and PBDEs, were typically observed in the flaming phase of combustion. However, concentrations of levoglucosan and some pesticides such as permethrin peaked during the smoldering phase. Along a transect (10-150-350 m) from the forest fire, concentration decrease for PCBs during flaming was faster compared to PAHs, while levoglucosan concentrations increased.
Gonçalves, Luís Moreira; Magalhães, Paulo Jorge; Valente, Inês Maria; Pacheco, João Grosso; Dostálek, Pavel; Sýkora, David; Rodrigues, José António; Barros, Aquiles Araújo
2010-06-11
In this work, a recently developed extraction technique for sample preparation aiming the analysis of volatile and semi-volatile compounds named gas-diffusion microextraction (GDME) is applied in the chromatographic analysis of aldehydes in beer. Aldehydes-namely acetaldehyde (AA), methylpropanal (MA) and furfural (FA)-were simultaneously extracted and derivatized with 2,4-dinitrophenylhydrazine (DNPH), then the derivatives were separated and analyzed by high-performance liquid chromatography with spectrophotometric detection (HPLC-UV). The identity of the eluted compounds was confirmed by high-performance liquid chromatography-atmospheric pressure chemical ionization-mass-spectrometry detection in the negative ion mode (HPLC-APCI-MS). The developed methodology showed good repeatability (ca. 5%) and linearity as well as good limits of detection (AA-12.3, FA-1.5 and MA 5.4microgL(-1)) and quantification (AA-41, FA-4.9 and MA 18microgL(-1)); it also appears to be competitive in terms of speed and cost of analysis. Copyright 2010 Elsevier B.V. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Not Available
1989-04-17
The Lang Property National Priorities List Site is located in Pemberton Township, Burlington County, New Jersey. Unauthorized disposal of hazardous wastes occurred on approximately two acres of the 40-acre site. The contaminant classes that were identified on the site are volatile organic compounds (VOCs), semi-volatile organic compounds (semi-VOCs), polynuclear aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), pesticides, and metals. The contaminant classes of concern are PCBs, VOCs, and semi-VOCs for on-site ground water. VOCs is the contaminant class of concern for sediments and surface water. The on-site ground water is highly contaminated; at the maximum chemical concentrations detected, use of thismore » water without treatment would pose a human health concern. The potential does exist for human exposure to ground water contaminants by ingestion, inhalation of volatilized VOCs from ground water, and dermal absorption. The surface soils are also highly contaminated and represent a current possible as well as future human health concern for trespassers, blueberry farm workers and harvesters, and construction and remedial workers.« less
Morino, Yu; Takahashi, Katsuyuki; Fushimi, Akihiro; Tanabe, Kiyoshi; Ohara, Toshimasa; Hasegawa, Shuichi; Uchida, Masao; Takami, Akinori; Yokouchi, Yoko; Kobayashi, Shinji
2010-11-15
Diurnal variations of fossil secondary organic carbon (SOC) and nonfossil SOC were determined for the first time using a combination of several carbonaceous aerosol measurement techniques, including radiocarbon (¹⁴C) determinations by accelerator mass spectrometry, and a receptor model (chemical mass balance, CMB) at a site downwind of Tokyo during the summer of 2007. Fossil SOC showed distinct diurnal variation with a maximum during daytime, whereas diurnal variation of nonfossil SOC was relatively small. This behavior was reproduced by a chemical transport model (CTM). However, the CTM underestimated the concentration of anthropogenic secondary organic aerosol (ASOA) by a factor of 4-7, suggesting that ASOA enhancement during daytime is not explained by production from volatile organic compounds that are traditionally considered major ASOA precursors. This result suggests that unidentified semivolatile organic compounds or multiphase chemistry may contribute largely to ASOA production. As our knowledge of production pathways of secondary organic aerosol (SOA) is still limited, diurnal variations of fossil and nonfossil SOC in our estimate give an important experimental constraint for future development of SOA models.
Correlation between the pattern volatiles and the overall aroma of wild edible mushrooms.
de Pinho, P Guedes; Ribeiro, Bárbara; Gonçalves, Rui F; Baptista, Paula; Valentão, Patrícia; Seabra, Rosa M; Andrade, Paula B
2008-03-12
Volatile and semivolatile components of 11 wild edible mushrooms, Suillus bellini, Suillus luteus, Suillus granulatus, Tricholomopsis rutilans, Hygrophorus agathosmus, Amanita rubescens, Russula cyanoxantha, Boletus edulis, Tricholoma equestre, Fistulina hepatica, and Cantharellus cibarius, were determined by headspace solid-phase microextraction (HS-SPME) and by liquid extraction combined with gas chromatography-mass spectrometry (GC-MS). Fifty volatiles and nonvolatiles components were formally identified and 13 others were tentatively identified. Using sensorial analysis, the descriptors "mushroomlike", "farm-feed", "floral", "honeylike", "hay-herb", and "nutty" were obtained. A correlation between sensory descriptors and volatiles was observed by applying multivariate analysis (principal component analysis and agglomerative hierarchic cluster analysis) to the sensorial and chemical data. The studied edible mushrooms can be divided in three groups. One of them is rich in C8 derivatives, such as 3-octanol, 1-octen-3-ol, trans-2-octen-1-ol, 3-octanone, and 1-octen-3-one; another one is rich in terpenic volatile compounds; and the last one is rich in methional. The presence and contents of these compounds give a considerable contribution to the sensory characteristics of the analyzed species.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Mumford, J.L.; Lewtas, J.; Burton, R.M.
1990-01-01
The study was conducted to assess human exposure to air pollutants resulting from the use of kerosene heaters in mobile homes. It has been estimated that 15-17 million unvented kerosene heaters have been sold in the United States, and 33% of these heaters have been sold to mobile home residents. The emissions from kerosene heaters can result in high pollutants levels in mobile homes that have a small air volume and low ventilation rate. Indoor air exchange rate, temperature, and humidity were measured. Chemical analyses, including polycyclic aromatic hydrocarbon (PAH) and nitro PAH, also were performed on the indoor airmore » samples from a selected home with the kerosene heater on and off. Increases in CO and organic concentrations resulting from the use of kerosene heaters were found in most homes monitored. Chemical analysis data also suggested the presence of evaporated, unburned kerosene fuel present in semivolatile organics collected in the XAD samples. When kerosene heaters were on, 56% of the sampling days (in all homes) showed dose-response mutagenic activity and 19% showed mutagenic activity on the heater-off days. In comparison with the U.S. national ambient air standards, four out of the eight heaters investigated in this study emitted pollutants that exceeded the ambient air standards some days. These data suggested that emissions from unvented kerosene heaters can significantly impact indoor air quality in mobile homes and that these emissions contain carcinogenic compounds and can be potentially carcinogenic in humans.« less
Seagrave, JeanClare; Gigliotti, Andrew; McDonald, Jacob D; Seilkop, Steven K; Whitney, Kevin A; Zielinska, Barbara; Mauderly, Joe L
2005-09-01
Particulate matter (PM) and vapor-phase semivolatile organic compounds (SVOC) were collected from three buses fueled by compressed natural gas. The bus engines included a well-functioning, conventional engine; a "high emitter" engine; and a new technology engine with an oxidation catalyst. Chemical analysis of the emissions showed differences among these samples, with the high emitter sample containing markers of engine oil constituents. PM + SVOC samples were also collected for mutagenicity and toxicity testing. Extraction efficiencies from the collection media were lower than for similarly collected samples from gasoline or diesel vehicles. Responses to the recovered samples were compared on the basis of exhaust volume, to incorporate the emission rates into the potency factors. Mutagenicity was assessed by Salmonella reverse mutation assay. Mutagenicity was greatest for the high emitter sample and lowest for the new technology sample. Metabolic activation reduced mutagenicity in strain TA100, but not TA98. Toxicity, including inflammation, cytotoxicity, and parenchymal changes, was assessed 24 h after intratracheal instillation into rat lungs. Lung responses were generally mild, with little difference between the responses to equivalent volumes of emissions from the normal emitter and the new technology, but greater responses for the high emitter. These emission sample potencies are further compared on the basis of recovered mass with previously reported samples from normal and high-emitter gasoline and diesel vehicles. While mutagenic potencies for the CNG emission samples were similar to the range observed in the gasoline and diesel emission samples, lung toxicity potency factors were generally lower than those for the gasoline and diesel samples.
Westgate, John N; Wania, Frank
2011-10-15
Air mass origin as determined by back trajectories often aids in explaining some of the short-term variability in the atmospheric concentrations of semivolatile organic contaminants. Airsheds, constructed by amalgamating large numbers of back trajectories, capture average air mass origins over longer time periods and thus have found use in interpreting air concentrations obtained by passive air samplers. To explore some of their key characteristics, airsheds for 54 locations on Earth were constructed and compared for roundness, seasonality, and interannual variability. To avoid the so-called "pole problem" and to simplify the calculation of roundness, a "geodesic grid" was used to bin the back-trajectory end points. Departures from roundness were seen to occur at all latitudes and to correlate significantly with local slope but no strong relationship between latitude and roundness was revealed. Seasonality and interannual variability vary widely enough to imply that static models of transport are not sufficient to describe the proximity of an area to potential sources of contaminants. For interpreting an air measurement an airshed should be generated specifically for the deployment time of the sampler, especially when investigating long-term trends. Samples taken in a single season may not represent the average annual atmosphere, and samples taken in linear, as opposed to round, airsheds may not represent the average atmosphere in the area. Simple methods are proposed to ascertain the significance of an airshed or individual cell. It is recommended that when establishing potential contaminant source regions only end points with departure heights of less than ∼700 m be considered.
Carbonyl group containing products from nopinone oxidation
NASA Astrophysics Data System (ADS)
Kahnt, A.; Iinuma, Y.; Heinold, A.; Böge, O.; Herrmann, H.
2010-12-01
Biogenic volatile organic compounds (BVOC) such as isoprene, monoterpenes and sesquiterpenes account for a large fraction of the fluxes of atmospheric non-methane hydrocarbons. Their atmospheric degradation leads to multifunctional oxidation products that can contribute to aerosol growth. In particular, semi-volatile carbonyl compounds that are formed during the early stage of the BVOC oxidation play an important role in the formation of subsequent secondary organic aerosol (SOA) compounds. In this study, a series of aerosol chamber experiments were performed to better understand the OH initiated oxidation of nopinone and subsequent oxidation products in both the gas- and particle-phase. Nopinone is a first generation oxidation product of β-pinene and has been rarely studied for its oxidation products (Calogirou et al., 1999). The gas- and particle-phase products were sampled using a denuder/filter setup. The combination of XAD-4 and 2,4-dinitrophenylhydrazine was applied on the denuder surface to enable in-situ derivatisation of carbonyl compounds. After extraction and sample purification, the derivatised carbonyl compounds were analysed with HPLC/(-)ESI-TOFMS. The data obtained from the denuder sample analysis were compared to the data obtained from the concurrent PTR-MS measurement. The PTR-MS was used in the scan mode during the OH reactions to detect unknown gaseous oxidation products. The selected ion mode was used for some of the experiments to determine the time evolution of certain compounds. The off-line denuder sample analysis enabled us to elucidate the structures of unknown compounds whereas the PTR-MS delivers the time series of oxidation products . The influences of NOx and seed particle acidity on gas- and particle-phase product distributions will be presented. References: A. Calogirou, N.R. Jensen, C.J. Nielsen, D. Kotzias, J. Hjorth, Environmental Science & Technology 33 (1999) 453.
NASA Astrophysics Data System (ADS)
Konovalov, I. B.; Beekmann, M.; Berezin, E. V.; Petetin, H.; Mielonen, T.; Kuznetsova, I. N.; Andreae, M. O.
2015-03-01
Chemistry transport models (CTMs) are an indispensable tool for studying and predicting atmospheric and climate effects associated with carbonaceous aerosol from open biomass burning (BB); this type of aerosol is known to contribute significantly to both global radiative forcing and to episodes of air pollution in regions affected by wildfires. Improving model performance requires systematic comparison of simulation results with measurements of BB aerosol and elucidating possible reasons for discrepancies between them, which, "by default", are frequently attributed in the literature to uncertainties in emission data. Based on published laboratory data regarding atmospheric evolution of BB aerosol and by using the volatility basis set (VBS) approach to organic aerosol modeling along with a "conventional" approach, we examined the importance of taking gas-particle partitioning and oxidation of semi-volatile organic compounds (SVOCs) into account in simulations of the mesoscale evolution of smoke plumes from intense wildfires that occurred in western Russia in 2010. BB emissions of primary aerosol components were constrained with the PM10 and CO data from the air pollution monitoring network in the Moscow region. The results of the simulations performed with the CHIMERE CTM were evaluated by considering, in particular, the ratio of smoke-related enhancements in PM10 and CO concentrations (ΔPM10 and ΔCO) measured in Finland (in the city of Kuopio), nearly 1000 km downstream of the fire emission sources. It is found that while the conventional approach (disregarding oxidation of SVOCs and assuming organic aerosol material to be non-volatile) strongly underestimates values of ΔPM10/ΔCO observed in Kuopio (by almost a factor of two), the VBS approach is capable to bring the simulations to a reasonable agreement with the ground measurements both in Moscow and in Kuopio. Using the VBS instead of the conventional approach is also found to result in a major improvement of the agreement of simulations and satellite measurements of aerosol optical depth, as well as in considerable changes in predicted aerosol composition and top-down BB aerosol emission estimates derived from AOD measurements.
NASA Astrophysics Data System (ADS)
Konovalov, I. B.; Beekmann, M.; Berezin, E. V.; Petetin, H.; Mielonen, T.; Kuznetsova, I. N.; Andreae, M. O.
2015-12-01
Chemistry transport models (CTMs) are an indispensable tool for studying and predicting atmospheric and climate effects associated with carbonaceous aerosol from open biomass burning (BB); this type of aerosol is known to contribute significantly to both global radiative forcing and to episodes of air pollution in regions affected by wildfires. Improving model performance requires systematic comparison of simulation results with measurements of BB aerosol and elucidation of possible reasons for discrepancies between them, which, by default, are frequently attributed in the literature to uncertainties in emission data. Based on published laboratory data on the atmospheric evolution of BB aerosol and using the volatility basis set (VBS) framework for organic aerosol modeling, we examined the importance of taking gas-particle partitioning and oxidation of semi-volatile organic compounds (SVOCs) into account in simulations of the mesoscale evolution of smoke plumes from intense wildfires that occurred in western Russia in 2010. Biomass burning emissions of primary aerosol components were constrained with PM10 and CO data from the air pollution monitoring network in the Moscow region. The results of the simulations performed with the CHIMERE CTM were evaluated by considering, in particular, the ratio of smoke-related enhancements in PM10 and CO concentrations (ΔPM10 and ΔCO) measured in Finland (in the city of Kuopio), nearly 1000 km downstream of the fire emission sources. It is found that while the simulations based on a "conventional" approach to BB aerosol modeling (disregarding oxidation of SVOCs and assuming organic aerosol material to be non-volatile) strongly underestimated values of ΔPM10/ΔCO observed in Kuopio (by a factor of 2), employing the "advanced" representation of atmospheric processing of organic aerosol material resulted in bringing the simulations to a much closer agreement with the ground measurements. Furthermore, taking gas-particle partitioning and oxidation of SVOCs into account is found to result in a major improvement of the agreement of simulations and satellite measurements of aerosol optical depth, as well as in considerable changes in predicted aerosol composition and top-down BB aerosol emission estimates derived from AOD measurements.
Oil Sands Operations in Alberta, Canada: A large source of secondary organic aerosol
NASA Astrophysics Data System (ADS)
Liggio, J.; Li, S. M.; Hayden, K.; Taha, Y. M.; Stroud, C.; Darlington, A. L.; Drollette, B.; Gordon, M.; Lee, P.; Liu, P.; Leithead, A.; Moussa, S.; Wang, D.; O'Brien, J.; Mittermeier, R. L.; Brook, J.; Lu, G.; Staebler, R. M.; Han, Y.; Tokarek, T. W.; Osthoff, H. D.; Makar, P.; Zhang, J.; Plata, D.; Gentner, D. R.
2015-12-01
Little is known of the reaction products of emissions to the atmosphere from extraction of oil from unconventional sources in the oil sands (OS) region of Alberta, Canada. This study examines these reaction products, and in particular, the extent to which they form secondary organic aerosol (SOA), which can significantly contribute to regional particulate matter formation. An aircraft measurement campaign was conducted over the Athabasca oil sands region between August 13 and September 7, 2013. A broad suite of measurements were made during 22 flights, including organic aerosol mass and composition with a High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and organic aerosol gas-phase precursors by Proton Transfer Reaction (PTR) and off-line gas chromatography mass spectrometry. Large concentrations of organic aerosol were measured downwind of the OS region, which we show to be entirely secondary in nature. Laboratory experiments demonstrated that bitumen (the mined product) contains semi-volatile vapours in the C12-C18 range that will be emitted at ambient temperatures. When oxidized, these vapours form SOA with highly similar HR-ToF-AMS spectra to the SOA measured in the flights. Box modelling of the OS plume evolution indicated that the measured levels of traditional volatile organic compounds (VOCs) are not capable of accounting for the amount of SOA formed in OS plumes. This discrepancy is only reconciled in the model by including bitumen vapours along with their oxidation and condensation into the model. The concentration of bitumen vapours required to produce SOA matching observations is similar to that of traditional VOC precursors of SOA. It was further estimated that the cumulative SOA mass formation approximately 100 km downwind of the OS during these flights, and under these meteorological conditions was up to 82 tonnes/day. The combination of airborne measurements, laboratory experiments and box modelling indicated that semi-volatile organic compounds (SVOC) are emitted from OS operations which accounted for >85% of the formed SOA mass in these plumes. Implications of this SOA formation will be discussed.
NASA Astrophysics Data System (ADS)
Pagonis, Demetrios; Krechmer, Jordan E.; de Gouw, Joost; Jimenez, Jose L.; Ziemann, Paul J.
2017-12-01
Recent studies have demonstrated that organic compounds can partition from the gas phase to the walls in Teflon environmental chambers and that the process can be modeled as absorptive partitioning. Here these studies were extended to investigate gas-wall partitioning of organic compounds in Teflon tubing and inside a proton-transfer-reaction mass spectrometer (PTR-MS) used to monitor compound concentrations. Rapid partitioning of C8-C14 2-ketones and C11-C16 1-alkenes was observed for compounds with saturation concentrations (c∗) in the range of 3 × 104 to 1 × 107 µg m-3, causing delays in instrument response to step-function changes in the concentration of compounds being measured. These delays vary proportionally with tubing length and diameter and inversely with flow rate and c∗. The gas-wall partitioning process that occurs in tubing is similar to what occurs in a gas chromatography column, and the measured delay times (analogous to retention times) were accurately described using a linear chromatography model where the walls were treated as an equivalent absorbing mass that is consistent with values determined for Teflon environmental chambers. The effect of PTR-MS surfaces on delay times was also quantified and incorporated into the model. The model predicts delays of an hour or more for semivolatile compounds measured under commonly employed conditions. These results and the model can enable better quantitative design of sampling systems, in particular when fast response is needed, such as for rapid transients, aircraft, or eddy covariance measurements. They may also allow estimation of c∗ values for unidentified organic compounds detected by mass spectrometry and could be employed to introduce differences in time series of compounds for use with factor analysis methods. Best practices are suggested for sampling organic compounds through Teflon tubing.
Littin, Gregory R.; Truini, Margot; Pierce, Herbert A.; Baum, Brad M.
2000-01-01
The Yavapai-Prescott Indian Reservation encompasses about 1,395 acres in central Arizona adjacent to the city of Prescott. From October 1994 to September 1997, the annual average rainfall was 14.9 inches and the total annual streamflow leaving the reservation along Granite Creek was about 430 acre-feet more than the amount of streamflow entering the reservation. The channel-fill and valley-fill sediments within the flood plain of Granite Creek make up the principal aquifer. The only ground-water development is from spring discharge that is being contained for livestock and wildlife use. About 29 acre-feet of ground water leaves the reservation each year after discharging into Granite Creek. Water levels in wells throughout the reservation reflect seasonal variations in rainfall and snowmelt. Surface water and ground water on the reservation are calcium bicarbonate types. Specific-conductance field measurements ranged from 187 to 724 microsiemens per centimeter for surface water and 381 to 990 microsiemens per centimeter for ground water. Fecal streptococcal bacteria and fecal coliform bacteria in the surface water make the water unsuitable for domestic use. Some volatile and semivolatile organic compounds were detected in samples of surface water, ground water, and streambed sediment. The potential for contamination exists from point and nonpoint sources on and off the reservation.
Hu, Jinhua; Li, Nianping; Lv, Yang; Liu, Jing; Xie, Jingchao; Zhang, Huibo
2017-01-01
Greater attention is currently being paid to the relationship between indoor environment and childhood allergies, however, the lack of reliable data and the disparity among different areas hinders reliable assessment of the relationship. This study focuses on the effect of indoor pollution on Chinese schoolchildren and the relationship between specific household and health problems suffered. The epidemiological questionnaire survey and the field measurement of the indoor thermal environment and primary air pollutants including CO2, fine particulate matter (PM2.5), chemical pollutants and fungi were performed in six Chinese cities. A total of 912 questionnaires were eligible for statistical analyses and sixty houses with schoolchildren aged 9–12 were selected for field investigation. Compared with Chinese national standards, inappropriate indoor relative humidity (<30% or >70%), CO2 concentration exceeding 1000 ppm and high PM2.5 levels were found in some monitored houses. Di(2-ethylhexyl) phthalate (DEHP) and dibutyl phthalate (DBP) were the most frequently detected semi-volatile organic compounds (SVOCs) in house dust. Cladosporium, Aspergillus and Penicillium were detected in both indoor air and house dust. This study indicates that a thermal environment with CO2 exceeding 1000 ppm, DEHP and DBP exceeding 1000 μg/g, and high level of PM2.5, Cladosporium, Aspergillus and Penicillium increases the risk of children’s allergies. PMID:28850091
Hu, Jinhua; Li, Nianping; Lv, Yang; Liu, Jing; Xie, Jingchao; Zhang, Huibo
2017-08-29
Greater attention is currently being paid to the relationship between indoor environment and childhood allergies, however, the lack of reliable data and the disparity among different areas hinders reliable assessment of the relationship. This study focuses on the effect of indoor pollution on Chinese schoolchildren and the relationship between specific household and health problems suffered. The epidemiological questionnaire survey and the field measurement of the indoor thermal environment and primary air pollutants including CO₂, fine particulate matter (PM 2.5 ), chemical pollutants and fungi were performed in six Chinese cities. A total of 912 questionnaires were eligible for statistical analyses and sixty houses with schoolchildren aged 9-12 were selected for field investigation. Compared with Chinese national standards, inappropriate indoor relative humidity (<30% or >70%), CO₂ concentration exceeding 1000 ppm and high PM 2.5 levels were found in some monitored houses. Di(2-ethylhexyl) phthalate (DEHP) and dibutyl phthalate (DBP) were the most frequently detected semi-volatile organic compounds (SVOCs) in house dust. Cladosporium , Aspergillus and Penicillium were detected in both indoor air and house dust. This study indicates that a thermal environment with CO₂ exceeding 1000 ppm, DEHP and DBP exceeding 1000 μg/g, and high level of PM 2.5 , Cladosporium , Aspergillus and Penicillium increases the risk of children's allergies.
Evaluation of Ruthenium Capture Methods for Tritium Pretreatment Off-Gas Streams
DOE Office of Scientific and Technical Information (OSTI.GOV)
Spencer, Barry B.; Jubin, Robert Thomas; Bruffey, Stephanie H.
2017-07-01
In the reprocessing of used nuclear fuel, radioactive elements are released into various plant off-gas streams. While much research and development has focused on the abatement of the volatile nuclides 3H, 14C, 85Kr, and 129I, the potential release of semivolatile isotopes that could also report to the off-gas streams in a reprocessing facility has been examined. Ruthenium (as 106Ru) has been identified as one of the semivolatile nuclides requiring the greatest degree of abatement prior to discharging the plant off-gas to the environment.
NASA Astrophysics Data System (ADS)
He, J.; Zielinska, B.; Balasubramanian, R.
2010-12-01
An intensive field study was conducted in the urban atmosphere of Singapore to investigate the composition of organic compounds in both gaseous and particulate phases during the period of August to early November 2006. 17 atmospheric samples were collected. These samples were subjected to accelerated solvent extraction with a mixture of dichloromethane and acetone and separated into functional group fractions for analyses by GC/MS. Over 180 organic compounds belonging to three major fractions (n-alkanes, polycyclic aromatic hydrocarbons - PAHs, and polar organic compounds - POCs) were identified and quantified. The characteristics and abundance of the n-alkanes, PAHs, mono and dicarboxylic acids, methoxylated phenols and other POCs were determined. The composition of these organic compounds fluctuated temporally with most of them being relatively higher in October than those in other months of the sampling period. 3-D backward air mass trajectory analyses together with the carbon preference index (CPI), molecular diagnostic ratios and molecular markers were used to investigate the origin of organic species measured in this study. Based on these diagnostic tools, the increased abundance of atmospheric organic species during October could be attributed to the occurrence of regional smoke haze episodes due to biomass burning in Indonesia. Among the POCs investigated, phthalic acid and cis-pinonic acid were abundant during October 2006. These two acids showed strong linear relationships with maximum daily ozone concentrations throughout the entire sampling period. This correlation with ozone suggested that the secondary aerosol constituents such as phthalic and cis-pinonic acids were probably formed through O3-induced photochemical transformation.
Environmental complex mixture toxicity assessment.
Gardner, H S; Brennan, L M; Toussaint, M W; Rosencrance, A B; Boncavage-Hennessey, E M; Wolfe, M J
1998-12-01
Trichloroethylene (TCE) was found as a contaminant in the well supplying water to an aquatic testing laboratory. The groundwater was routinely screened by a commercial laboratory for volatile and semivolatile compounds, metals, herbicides, pesticides, and polychlorinated biphenyls using U.S. Environmental Protection Agency methods. Although TCE was the only reportable peak on the gas chromatograph, with average concentrations of 0.200 mg/l, other small peaks were also present, indicating the possibility that the contamination was not limited to TCE alone. A chronic 6-month carcinogenicity assay was conducted on-site in a biomonitoring trailer, using the Japanese medaka fish (Oryzias latipes) in an initiation-promotion protocol, with diethylnitrosamine (DEN) as the initiator and the TCE-contaminated groundwater as a promoter. Study results indicated no evidence of carcinogenic potential of the groundwater without initiation. There was, however, a tumor-promotional effect of the groundwater after DEN initiation. A follow-up laboratory study was conducted using reagent grade TCE added to carbon-filtered groundwater to simulate TCE concentrations comparable to those found in the contaminated groundwater. Study results indicated no promotional effects of TCE. These studies emphasize the necessity for on-site bioassays to assess potential environmental hazards. In this instance, chemical analysis of the groundwater identified TCE as the only reportable contaminant, but other compounds present below reportable limits were noted and may have had a synergistic effect on tumor promotion observed with the groundwater exposure. Laboratory toxicity testing of single compounds can produce toxicity data specific to that compound for that species but cannot take into account the possible toxic effects of mixtures of compounds.
NASA Astrophysics Data System (ADS)
Fujitani, Yuji; Saitoh, Katsumi; Fushimi, Akihiro; Takahashi, Katsuyuki; Hasegawa, Shuich; Tanabe, Kiyoshi; Kobayashi, Shinji; Furuyama, Akiko; Hirano, Seishiro; Takami, Akinori
2012-11-01
To investigate the effect of isothermal dilution (30 °C) on emission factors (EFs) of semivolatile and nonvolatile compounds of heavy-duty diesel exhaust, we measured EFs for particulate matter (PM), organic carbon (OC), and elemental carbon (EC) in the particle phase, and EFs for n-alkanes in both the particle phase and the gas phase of exhaust produced under high-idle engine operating conditions at dilution ratios (DRs) ranging from 8 to 1027. The EC EFs did not vary with DR, whereas the OC EFs in the particle phase determined at DR = 1027 were 13% of the EFs determined at DR = 8, owing to evaporation of organic compounds. Using partitioning theory and n-alkane EFs measured at DR = 14 and 238, we calculated the distributions of compounds between the particle and gas phases at DR = 1760, which corresponds to the DR for tailpipe emissions as they move from the tailpipe to the roadside atmosphere. The gas-phase EF of a compound with a vapor pressure of 10-7 Pa was 0.01 μg kg-1-fuel at DR = 14, and this value is 1/330 the value derived at DR = 1760. Our results suggest that the EFs of high-volatility compounds in the particle phase will be overestimated and that the EFs of low-volatility compounds in the gas phase will be underestimated if the estimates are derived from data obtained at the low DRs and they are applied to the real world. Therefore, extrapolation from EFs derived at low DR values to EFs at atmospherically relevant DRs will be a source of error in predictions of the concentrations of particulate matter and gas-phase precursors to secondary organic aerosols in air quality models.
2010-01-01
Interest in the health effects of potential endocrine-disrupting compounds (EDCs) that are high production volume chemicals used in consumer products has made exposure assessment and source identification a priority. We collected paired indoor and outdoor air samples in 40 nonsmoking homes in urban, industrial Richmond, CA, and 10 in rural Bolinas, CA. Samples were analyzed by GC-MS for 104 analytes, including phthalates (11), alkylphenols (3), parabens (3), polybrominated diphenyl ether (PBDE) flame retardants (3), polychlorinated biphenyls (PCBs) (3), polycyclic aromatic hydrocarbons (PAHs) (24), pesticides (38), and phenolic compounds (19). We detected 39 analytes in outdoor air and 63 in indoor air. For many of the phenolic compounds, alkylphenols, phthalates, and PBDEs, these represent some of the first outdoor measures and the first analysis of the relative importance of indoor and outdoor sources in paired samples. Data demonstrate higher indoor concentrations for 32 analytes, suggesting primarily indoor sources, as compared with only 2 that were higher outdoors. Outdoor air concentrations were higher in Richmond than Bolinas for 3 phthalates, 10 PAHs, and o-phenylphenol, while indoor air levels were more similar between communities, except that differences observed outdoors were also seen indoors. Indoor concentrations of the most ubiquitous chemicals were generally correlated with each other (4-t-butylphenol, o-phenylphenol, nonylphenol, several phthalates, and methyl phenanthrenes; Kendall correlation coefficients 0.2−0.6, p < 0.05), indicating possible shared sources and highlighting the importance of considering mixtures in health studies. PMID:20681565
NASA Astrophysics Data System (ADS)
Shu, Qian; Koo, Bonyoung; Yarwood, Greg; Henderson, Barron H.
2017-12-01
Differences between two air quality modeling systems reveal important uncertainties in model representations of secondary organic aerosol (SOA) fate. Two commonly applied models (CMAQ: Community Multiscale Air Quality; CAMx: Comprehensive Air Quality Model with extensions) predict very different OA concentrations over the eastern U.S., even when using the same source data for emissions and meteorology and the same SOA modeling approach. Both models include an option to output a detailed accounting of how each model process (e.g., chemistry, deposition, etc.) alters the mass of each modeled species, referred to as process analysis. We therefore perform a detailed diagnostic evaluation to quantify simulated tendencies (Gg/hr) of each modeled process affecting both the total model burden (Gg) of semi-volatile organic compounds (SVOC) in the gas (g) and aerosol (a) phases and the vertical structures to identify causes of concentration differences between the two models. Large differences in deposition (CMAQ: 69.2 Gg/d; CAMx: 46.5 Gg/d) contribute to significant OA bias in CMAQ relative to daily averaged ambient concentration measurements. CMAQ's larger deposition results from faster daily average deposition velocities (VD) for both SVOC (g) (VD,cmaq = 2.15 × VD,camx) and aerosols (VD,cmaq = 4.43 × Vd,camx). Higher aerosol deposition velocity would be expected to cause similar biases for inert compounds like elemental carbon (EC), but this was not seen. Daytime low-biases in EC were also simulated in CMAQ as expected but were offset by nighttime high-biases. Nighttime high-biases were a result of overly shallow mixing in CMAQ leading to a higher fraction of EC total atmospheric mass in the first layer (CAMx: 5.1-6.4%; CMAQ: 5.6-6.9%). Because of the opposing daytime and nighttime biases, the apparent daily average bias for EC is reduced. For OA, there are two effects of reduced vertical mixing: SOA and SVOC are concentrated near the surface, but SOA yields are reduced near the surface by nighttime enhancement of NOx. These results help to characterize model processes in the context of SOA and provide guidance for model improvement.
Fujita, Eric M; Zielinska, Barbara; Campbell, David E; Arnott, W Patrick; Sagebiel, John C; Mazzoleni, Lynn; Chow, Judith C; Gabele, Peter A; Crews, William; Snow, Richard; Clark, Nigel N; Wayne, W Scott; Lawson, Douglas R
2007-06-01
The U.S. Department of Energy Gasoline/Diesel PM Split Study examined the sources of uncertainties in using an organic compound-based chemical mass balance receptor model to quantify the contributions of spark-ignition (SI) and compression-ignition (CI) engine exhaust to ambient fine particulate matter (PM2.5). This paper presents the chemical composition profiles of SI and CI engine exhaust from the vehicle-testing portion of the study. Chemical analysis of source samples consisted of gravimetric mass, elements, ions, organic carbon (OC), and elemental carbon (EC) by the Interagency Monitoring of Protected Visual Environments (IMPROVE) and Speciation Trends Network (STN) thermal/optical methods, polycyclic aromatic hydrocarbons (PAHs), hopanes, steranes, alkanes, and polar organic compounds. More than half of the mass of carbonaceous particles emitted by heavy-duty diesel trucks was EC (IMPROVE) and emissions from SI vehicles contained predominantly OC. Although total carbon (TC) by the IMPROVE and STN protocols agreed well for all of the samples, the STN/IMPROVE ratios for EC from SI exhaust decreased with decreasing sample loading. SI vehicles, whether low or high emitters, emitted greater amounts of high-molecular-weight particulate PAHs (benzo[ghi]perylene, indeno[1,2,3-cd]pyrene, and coronene) than did CI vehicles. Diesel emissions contained higher abundances of two- to four-ring semivolatile PAHs. Diacids were emitted by CI vehicles but are also prevalent in secondary organic aerosols, so they cannot be considered unique tracers. Hopanes and steranes were present in lubricating oil with similar composition for both gasoline and diesel vehicles and were negligible in gasoline or diesel fuels. CI vehicles emitted greater total amounts of hopanes and steranes on a mass per mile basis, but abundances were comparable to SI exhaust normalized to TC emissions within measurement uncertainty. The combustion-produced high-molecular-weight PAHs were found in used gasoline motor oil but not in fresh oil and are negligible in used diesel engine oil. The contributions of lubrication oils to abundances of these PAHs in the exhaust were large in some cases and were variable with the age and consumption rate of the oil. These factors contributed to the observed variations in their abundances to total carbon or PM2.5 among the SI composition profiles.
Tang, X L; Bi, X H; Sheng, G Y; Tan, J H; Fu, J M
2006-06-01
Seasonal aerosol samples have been collected by Andersen Hi-Vol pumping system equipped with a five stage cascade impactor and a backup filter (size range: 10-7.2 microm, 7.2-3.0 microm, 3.0-1.5 microm, 1.5-0.95 microm, 0.95-0.49 microm,
NASA Astrophysics Data System (ADS)
Jordan, C. E.; Ziemann, P. J.; Griffin, R. J.; Lim, Y. B.; Atkinson, R.; Arey, J.
2006-12-01
Recent laboratory studies have shown significant formation of secondary organic aerosol (SOA) from OH reactions with a homologous series of n-alkanes. SOA mass yields of 56% were observed for pentadecane (C15), while only 0.5% yield was observed from octane (C8, the smallest alkane in the series). A rapid transition in SOA yield is observed from C10 to C13, with SOA yields increasing from 4% to 49%. In standard gas-aerosol partitioning theory, the vapor pressure controls the amount of material that can condense into the particle phase. However, the rapid transition observed here suggests there may also be a shift in the predominant reaction pathways for longer chain alkanes, leading to greater production of lower vapor pressure products. Here we present an investigation of the role of vapor pressure versus the role of shifting branching ratios to test the influence of each of these on SOA mass yields. We have added each of the alkanes in this series to the Caltech Atmospheric Chemistry Mechanism (CACM). This mechanism was developed in part to predict explicitly concentrations of secondary and tertiary semivolatile oxidation products that potentially form SOA. Although it is has been developed to lump similar compounds together for computational efficiency, it is nonetheless easily adapted and ideally suited for a detailed zero-dimensional modeling study of this kind. This gas-phase mechanism is linked to the aerosol partitioning module MPMPO (Model to Predict the Multi- phase Partitioning of Organics). MPMPO is a fully coupled module that allows the simultaneous partitioning of semi-volatile species to both an aqueous and an organic aerosol phase.
Characterization of particulate matter from diesel passenger cars tested on chassis dynamometers.
Jung, Sungwoon; Lim, Jaehyun; Kwon, Sangil; Jeon, Sangwoo; Kim, Jeongsoo; Lee, Jongtae; Kim, Sunmoon
2017-04-01
Emission characterization of particle number as well as particle mass from three diesel passenger cars equipped with diesel particulate filter (DPF), diesel oxidation catalyst (DOC) and exhaust gas recirculation (EGR) under the vehicle driving cycles and regulatory cycle. Total particle number emissions (PNEs) decreased gradually during speed-up of vehicle from 17.3 to 97.3km/hr. As the average vehicle speed increases, the size-segregated peak of particle number concentration shifts to smaller size ranges of particles. The correlation analysis with various particulate components such as particle number concentration (PNC), ultrafine particle number concentration (UFPNC) and particulate matter (PM) mass was conducted to compare gaseous compounds (CO, CO 2 , HC and NO x ). The UFPNC and PM were not only emitted highly in Seoul during severe traffic jam conditions, but also have good correlation with hydrocarbons and NO x influencing high potential on secondary aerosol generation. The effect of the dilution temperature on total PNC under the New European Driving Cycle (NEDC), was slightly higher than the dilution ratio. In addition, the nuclei mode (D P : ≤13nm) was confirmed to be more sensitive to the dilution temperature rather than other particle size ranges. Comparison with particle composition between vehicle speed cycles and regulatory cycle showed that sulfate was slightly increased at regulatory cycle, while other components were relatively similar. During cold start test, semivolatile nucleation particles were increased due to effect of cold environment. Research on particle formation dependent on dilution conditions of diesel passenger cars under the NEDC is important to verify impact on vehicular traffic and secondary aerosol formation in Seoul. Copyright © 2016. Published by Elsevier B.V.
1991-07-01
for archive. b. Except where noted, includes 2,3,7,8-TCDO, 2,3,7,8-TCOF, and total PCOD /PCOF. c. Except where noted, includes acid-type semivolatiles...TCDD- 3 7C14, P5CDD- 13 C12 , H pCOD - 13 C12, CD-13 C12, and P5CDF-13C 12 were used to calculate the accuracy of recovery efficiencies. Whereas for...burns are shown in Table 17. None of these PCOD congeners were detected, including the specific analysis for 2,3,7,8-TCDD. DLVs ranged between 30.02 and
Burton, Carmen A.
2002-01-01
Organcochlorine compounds, semivolatile-organic compounds (SVOC), and trace elements were analyzed in reservoir sediment cores, streambed sediment, and fish tissue in the Santa Ana River Basin as part of the U.S. Geological Survey's National Water-Quality Assessment Program. Three reservoirs were sampled in areas that have different degrees of urbanization. Streambed sediment and fish tissue collected at 12 sites were divided into two groups, urban and nonurban. More organochlorine compounds were detected in reservoir sediment cores, streambed sediment and fish tissue, and at higher concentrations at urban sites than at nonurban sites. At all sites, except West Street Basin, concentrations of organochlorine compounds were lower than the probable-effect concentration (PEC). At the highly urbanized West Street Basin, chlordane and p,p'-DDE exceeded the PEC throughout the historical record. The less stringent threshold-effect concentration (TEC) was exceeded for six compounds at eight sites. Most of the organochlorine compounds detected in streambed sediment and fish tissue were at urban sites on the Santa Ana River as opposed to its tributaries, suggesting accumulation and persistence in the river. More SVOCs were detected in reservoir sediment cores and streambed sediment, and at higher concentrations, at urban sites than at nonurban sites. At all the sites, except West Street Basin, concentrations of SVOCs were lower than the PEC. At West Street Basin, chrysene, pyrene, and total polycyclic-aromatic hydrocarbons exceeded the PEC throughout the historical record. The TEC was exceeded for 10 compounds at 3 sites. Most of the SVOCs were detected in streambed sediment at urban sites on tributaries to the Santa Ana River rather than the mainstem itself. The less frequent occurrence and lower concentrations in the Santa Ana River suggest that SVOCs are less persistent than organochlorine compounds, possibly as a result of volatization, gradation, or dilution. Most trace-element detections in reservoir sediment cores and streambed sediment were at urban sites, and the concentrations were generally higher than at nonurban sites. Lead and zinc exceeded their PECs at West Street Basin throughout the historical record; copper exceeded its PEC at Canyon Lake, an area of urban growth. The TEC was exceeded for 10 compounds at 11 sites. Frequency of detection and concentration did not differ between tributary and Santa Ana River sites, which may be attributed to the fact that trace elements occur naturally. Four trace elements (arsenic, copper, mercury, and selenium) had higher concentrations in fish tissue at nonurban sites than at urban sites. Concentrations decreased over time for organochlorine compounds at all three reservoirs, probably a result of the discontinued use of many of the compounds. Decreasing trends in SVOCs and trace elements were observed at West Street Basin, but increasing trends were observed at Canyon Lake. Concentrations of organochlorine compounds, SVOCs, and trace elements were higher during periods of above average rainfall at both West Street Basin and Canyon Lake.
Chemical constituents of the fermentation broth of the marine-derived fungus Penicillium roqueforti.
Mioso, Roberto; Marante, Francisco Javier Toledo; Laguna, Irma Herrera Bravo de
2015-01-01
The filamentous fungus Penicillium roqueforti is a well-known multifunctional cell factory of high added-value biomolecules. The objective of this work was to carry out a detailed analysis of the metabolites present in the culture broth of a new marine-derived Penicillium roqueforti strain isolated in the Canary Islands, Spain. The fungal biomass production was carried out in liquid-state fermentation, and after 10-12 days of incubation at 22-25°C, the supernatant mycelia was separated by filtration, and the culture broth (12l) was stored in a refrigerator at 4°C for a subsequent liquid-liquid extraction with dichloromethane (3×), in accordance with the modified Kupchan method. The volatile and semi-volatile organic compounds were separated by chromatography and analyzed using GC-MS and NMR spectroscopy analyses. Several volatile organic compounds involved in the fatty acid pathway were identified: a terpenoid, a cyclic dipeptide, phthalates, and an alkyl adipate. In addition, three categories of non-volatile compounds (alkanes, fatty acids and 1-alkanols) were identified by spectroscopy. The results show that the fermented broth of this fungal strain has no mycotoxins under the culture conditions applied. It is hoped that this chemo-specific information will offer critical input for improving the biotechnological applications of this filamentous fungus. Copyright © 2013 Revista Iberoamericana de Micología. Published by Elsevier Espana. All rights reserved.
Preparation and application of in-fibre internal standardization solid-phase microextraction.
Zhao, Wennan; Ouyang, Gangfeng; Pawliszyn, Janusz
2007-03-01
The in-fibre standardization method is a novel approach that has been developed for field sampling/sample preparation, in which an internal standard is pre-loaded onto a solid-phase microextraction (SPME) fibre for calibration of the extraction of target analytes in field samples. The same method can also be used for in-vial sample analysis. In this study, different techniques to load the standard to a non-porous SPME fibre were investigated. It was found that the appropriateness of the technique depends on the physical properties of the standards that are used for the analysis. Headspace extraction of the standard dissolved in pumping oil works well for volatile compounds. Conversely, headspace extraction of the pure standard is an effective approach for semi-volatile compounds. For compounds with low volatility, a syringe-fibre transfer method and direct extraction of the standard dissolved in a solvent exhibited a good reproducibility (<5% RSD). The main advantage of the approaches investigated in this study is that the standard generation vials can be reused for hundreds of analyses without exhibiting significant loss. Moreover, most of the standard loading processes studied can be performed automatically, which is efficient and precise. Finally, the standard loading technique and in-fibre standardization method were applied to a complex matrix (milk) and the results illustrated that the matrix effect can be effectively compensated for with this approach.
Potential of secondary aerosol formation from Chinese gasoline engine exhaust.
Du, Zhuofei; Hu, Min; Peng, Jianfei; Guo, Song; Zheng, Rong; Zheng, Jing; Shang, Dongjie; Qin, Yanhong; Niu, He; Li, Mengren; Yang, Yudong; Lu, Sihua; Wu, Yusheng; Shao, Min; Shuai, Shijin
2018-04-01
Light-duty gasoline vehicles have drawn public attention in China due to their significant primary emissions of particulate matter and volatile organic compounds (VOCs). However, little information on secondary aerosol formation from exhaust for Chinese vehicles and fuel conditions is available. In this study, chamber experiments were conducted to quantify the potential of secondary aerosol formation from the exhaust of a port fuel injection gasoline engine. The engine and fuel used are common in the Chinese market, and the fuel satisfies the China V gasoline fuel standard. Substantial secondary aerosol formation was observed during a 4-5hr simulation, which was estimated to represent more than 10days of equivalent atmospheric photo-oxidation in Beijing. As a consequence, the extreme case secondary organic aerosol (SOA) production was 426±85mg/kg-fuel, with high levels of precursors and OH exposure. The low hygroscopicity of the aerosols formed inside the chamber suggests that SOA was the dominant chemical composition. Fourteen percent of SOA measured in the chamber experiments could be explained through the oxidation of speciated single-ring aromatics. Unspeciated precursors, such as intermediate-volatility organic compounds and semi-volatile organic compounds, might be significant for SOA formation from gasoline VOCs. We concluded that reductions of emissions of aerosol precursor gases from vehicles are essential to mediate pollution in China. Copyright © 2017. Published by Elsevier B.V.
Van Loy, M D; Riley, W J; Daisey, J M; Nazaroff, W W
2001-02-01
The surface interactions of nicotine and phenanthrene with carpet, painted wallboard, and stainless steel were investigated in a room-sized environmental test chamber. Adsorption kinetics were tested by flash evaporating a known mass of each compound into a sealed 20 m3 chamber containing one or more of the tested sorbents. In each experiment, one or more emissions were performed after the gas-phase concentration had reached an apparent plateau. At the end of each experiment, the chamber was ventilated and resealed to monitor reemission of the compound from the sorbents. Kinetic sorption parameters were determined by fitting a mass-balance model to the experimental results. The sorption capacity of stainless steel was of similar magnitude for nicotine and phenanthrene. Sorption of nicotine on carpet and wallboard was much stronger, with equilibrium partitioning values 2-3 orders of magnitude higher. The sorption capacities of phenanthrene on carpet and wallboard were smaller, approximately 10-20% of the stainless steel values. The rates of uptake are of similar magnitude for all sorbate--sorbent pairs and are consistent with the limit imposed by gas-phase boundary-layer mass transport. The rates of desorption are much faster for phenanthrene than for nicotine. Model simulations predict average nicotine levels in a typical smoking residence that are consistent with published data.
Feng, Jialiang; Chan, Chak K; Fang, Ming; Hu, Min; He, Lingyan; Tang, Xiaoyan
2005-11-01
Twenty-eight PM2.5 samples collected in Summer (July 2002) and Winter (November 2002) at two sites in Beijing, China were analyzed using GC/MS to investigate the impact of meteorology and coal burning on the solvent extractable organic compounds (SEOC). The characteristics and abundance of the n-alkanes, polycyclic aromatic hydrocarbons (PAHs), n-fatty acids and n-alkanols were determined. Source identification was made using organic species as molecular markers. Semi-volatile compounds of alkanes and PAHs had much higher concentrations in winter than summer because of the large difference in the temperature between the seasons. Plant wax emission was a major contributor to n-alkanes in summer, but fossil fuel residue was a major source (>80%) in winter. The seasonal differences in the distribution of pentacyclic triterpanes clearly shows the impact of coal burning for space heating in winter. The yield of PAHs in winter (148 ng m(-3) at the urban site and 277 ng m(-3) at the suburban site) was six to eight times higher than that in summer and was found to be mainly from coal burning. Higher pollutant concentrations were measured at the suburban site than the urban site in winter due to the rapid expansion of the city limit and the relocation of factories from urban to suburban areas over the last two decades.
Cao, Jianping; Xiong, Jianyin; Wang, Lixin; Xu, Ying; Zhang, Yinping
2016-09-06
Solid-phase microextraction (SPME) is regarded as a nonexhaustive sampling technique with a smaller extraction volume and a shorter extraction time than traditional sampling techniques and is hence widely used. The SPME sampling process is affected by the convection or diffusion effect along the coating surface, but this factor has seldom been studied. This paper derives an analytical model to characterize SPME sampling for semivolatile organic compounds (SVOCs) as well as for volatile organic compounds (VOCs) by considering the surface mass transfer process. Using this model, the chemical concentrations in a sample matrix can be conveniently calculated. In addition, the model can be used to determine the characteristic parameters (partition coefficient and diffusion coefficient) for typical SPME chemical samplings (SPME calibration). Experiments using SPME samplings of two typical SVOCs, dibutyl phthalate (DBP) in sealed chamber and di(2-ethylhexyl) phthalate (DEHP) in ventilated chamber, were performed to measure the two characteristic parameters. The experimental results demonstrated the effectiveness of the model and calibration method. Experimental data from the literature (VOCs sampled by SPME) were used to further validate the model. This study should prove useful for relatively rapid quantification of concentrations of different chemicals in various circumstances with SPME.
Iwata, H; Tanabe, S; Sakai, N; Nishimura, A; Tatsukawa, R
1994-01-01
Persistent organochlorines in air, river water and sediment samples were analysed from eastern and southern Asia (India, Thailand, Vietnam, Malaysia, Indonesia) and Oceania (Papua New Guinea and Solomon Islands) to elucidate their geographical distribution in tropical environment. The concentrations of organochlorines in these abiotic samples collected from Taiwan, Japan and Australia were also monitored for comparison. Atmospheric and hydrospheric concentrations of HCHs (hexachlorocyclohexanes) and DDTs (DDT and its metabolites) in the tropical developing countries were apparently higher than those observed in the developed nations, suggesting extensive usage of these chemicals in the lower latitudes. CHLs (chlordane compounds) and PCBs (polychlorinated biphenyls) were also occasionally observed at higher levels in the tropics, implying that their usage area is also expanding southward. Distribution patterns of organochlorines in sediments showed smaller spatial variations on global terms, indicating that the chemicals released in the tropical environment are dispersed rapidly through air and water and retained less in sediments. The ratios of organochlorine concentrations in sediment and water phases were positively correlated with the latitude of sampling, suggesting that persistent and semivolatile compounds discharged in the tropics tend to be redistributed on a global scale.
Smoking Behavior and Smoke Constituents from Cigarillos and Little Cigars
Koszowski, Bartosz; Rosenberry, Zachary R.; Yi, Daniel; Stewart, Sean; Pickworth, Wallace B.
2017-01-01
Objective Although most cigarillos and little cigars smokers also smoke cigarettes (dual use), there are few studies comparing toxicant exposure and smoking behavior in cigars and cigarettes. Methods Two groups of dual users smoked their usual brand of cigarette and either a Winchester unflavored little cigar (N = 21) or a Black & Mild cigarillo (N = 23). Acute exposure of nicotine and exhaled carbon monoxide (CO) and puffing topography parameters were collected. Individual cigar puffing data were used to machine-replicate smoking for analysis of volatile organic compounds (VOC) and semi-volatile organic compounds (SVOC) in mainstream smoke. Results There were significant differences in puff topography, plasma nicotine and exhaled CO after cigarettes, little cigars, and cigarillos. Puff topography differences between cigarillos and cigarettes were due to the difference in the size of the article. Mainstream cigar and cigarette smoke was qualitatively similar; the yield was dependent on the smoking behavior. When smoke yield was adjusted for weight of tobacco burned or puff volume, exposure differences decreased. Conclusions There is a wide range of delivery of both SVOC and VOC components of cigar and cigarillo smoke. The difference in exposure is largely dependent on the article size and the amount consumed. PMID:28944278
Cat serum contamination by phthalates, PCBs, and PBDEs versus food and indoor air.
Braouezec, Clélie; Enriquez, Brigitte; Blanchard, Martine; Chevreuil, Marc; Teil, Marie-Jeanne
2016-05-01
A wide variety of endocrine disrupting compounds (EDCs) with semi-volatile properties are emitted to indoor air and, thus, humans might get exposed to these compounds. Pet cats spend the major part of their lifetime at home and might integrate indoor contamination so that they could mirror the human exposure. Three classes of EDCs, polybromodiphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), and phthalates (PAEs), were simultaneously considered and quantified in the serum of cats (Felis silvestris catus) living in the Paris area (France). The main compound concentrations by decreasing importance order were as follows: for PAEs, di-n-butyl phthalate (79,900 ng L(-1)) next di-iso-butyl phthalate (53,200 ng L(-1)), di-iso-nonyl phthalate (43,800 ng L(-1)), and di-ethylhexyl phthalate (32,830 ng L(-1)); for PCBs, CB153 (1378 ng L(-1)) next CB52 (509 ng L(-1)), CB101 (355 ng L(-1)), CB110 (264 ng L(-1)), and CB118 (165 ng L(-1)); and for PBDEs, BDE 153/154 (35 ng L(-1)) next BDE47 (10.7 ng L(-1)). Total serum concentrations as mean ± standard deviation were 107 ± 98 μg L(-1) for ∑9PAEs, 2799 ± 944 ng L(-1) for ∑19PCBs, and 56 ± 21 ng L(-1) for ∑9BDEs. The three chemical groups were found in cat food: 0.088 ng g(-1) for ∑9BDEs, 1.7 ng g(-1) for ∑19PCBs, and 2292 ng g(-1) for ∑9PAEs and in indoor air: 0.063 ng m(-3) for ∑9BDEs, 1.5 ng m(-3) for ∑19PCBs, and 848 ng m(-3) for ∑9PAEs. Contaminant intake by food ingestion was approximately 100-fold higher than that by indoor air inhalation.
Characterization of gaseous emissions and ashes from the combustion of furniture waste.
Moreno, Ana Isabel; Font, Rafael; Conesa, Juan A
2016-12-01
Gaseous emissions and ash obtained in the combustion of furniture waste have been studied, with particular emphasis on the emissions of hazardous pollutants, such as PCDD/Fs and dl-PCBS. Two different combustion procedures were carried out, one of them in a conventional residential stove (without an automatic control of combustion air and bad mixing of combustion gases with air), and the other in a laboratory-scale reactor (operating under substoichiometric conditions). Three different experiments were carried out in the residential stove, in which the gaseous emissions and ashes obtained were analysed. The fuel burnt out in two of the experiments was furniture wood waste and in one of the experiments, the fuel burnt out was briquettes composed of a mixture of furniture wood with 10wt.% of polyurethane foam. One of the purposes of these experiments was the evaluation of the possible inhibition effect of the higher nitrogen content on the formation of PCDD/Fs. Slight inhibition of the PCDD/F formation was found although, it is noteworthy that the lowest yield of PAHs, volatile and semi-volatile compounds were obtained in the combustion of these briquettes. In all experiments, the emission factors of polychlorinated dibenzo-p-dioxins and dibenzofurans and dioxin-like polychlorinated biphenyls (PCDD/Fs and dl-PCBs) were between 29 and 74ng WHO-TEQ/kg sample burnt, lower than that obtained by other authors in the burning of pine needles and cones. PCDD/Fs and dl-PCBs emissions from furniture wood waste combustion were also analysed in the laboratory scale reactor at 850°C and the results were compared with the values obtained from the combustion of solid wood (untreated wood). The total equivalent toxicity obtained was 21.1ng WHO-TEQ/kg sample for combustion of furniture wood waste, which is low in comparison with those obtained for other waste combustion in similar conditions. In the laboratory scale reactor, PCDFs were the dominant compounds in the profiles of PCDD/Fs, by contrast, in the combustion in the residential stove, the majority compounds were PCDDs, due to the different operation conditions. Copyright © 2016 Elsevier Ltd. All rights reserved.
Thermal decomposition of electronic wastes: Mobile phone case and other parts
DOE Office of Scientific and Technical Information (OSTI.GOV)
Molto, Julia, E-mail: julia.molto@ua.es; Egea, Silvia; Conesa, Juan Antonio
Highlights: > Pyrolysis and combustion of different parts of mobile phones produce important quantities of CO and CO{sub 2}. > Naphthalene is the most abundant PAH obtained in the thermal treatment of mobile phones. > Higher combustion temperature increases the chlorinated species evolved. - Abstract: Pyrolysis and combustion runs at 850 {sup o}C in a horizontal laboratory furnace were carried out on different parts of a mobile phone (printed circuit board, mobile case and a mixture of both materials). The analyses of the carbon oxides, light hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), polychlorodibenzo-p-dioxin, polychlorodibenzofurans (PCDD/Fs), and dioxin-like PCBs are shown. Regardingmore » semivolatile compounds, phenol, styrene, and its derivatives had the highest yields. In nearly all the runs the same PAHs were identified, naphthalene being the most common component obtained. Combustion of the printed circuit board produced the highest emission factor of PCDD/Fs, possibly due to the high copper content.« less
A source of PCB contamination in modified high-volume air samplers
DOE Office of Scientific and Technical Information (OSTI.GOV)
Basu, I.; O'Dell, J.M.; Arnold, K.
2000-02-01
Modified Anderson High Volume (Hi-Vol) air samplers are widely used for the collection of semi-volatile organic compounds (such as PCBs) from air. The foam gasket near the main air flow path in these samplers can become contaminated with PCBs if the sampler or the gasket is stored at a location with high indoor air PCB levels. Once the gasket is contaminated, it releases PCBs back into the air stream during sampling, and as a result, incorrectly high air PCB concentrations are measured. This paper presents data demonstrating this contamination problem using measurements from two Integrated Atmospheric Deposition Network sites: onemore » at Sleeping Bear Dunes on Lake Michigan and the other at Point Petre on Lake Ontario. The authors recommend that these gaskets be replaced by Teflon tape and that the storage history of each sampler be carefully tracked.« less
Zhang, Zunzhen; Che, Wangjun; Liang, Ying; Wu, Mei; Li, Na; Shu, Ya; Liu, Fang; Wu, Desheng
2007-09-01
Gasoline engine exhaust has been considered a major source of air pollution in China, and methanol is considered as a potential substitute for gasoline fuel. In this study, the genotoxicity and cytotoxicity of organic extracts of condensate, particulate matters (PM) and semivolatile organic compounds (SVOC) of gasoline and absolute methanol engine exhaust were examined by using MTT assay, micronucleus assay, comet assay and Ames test. The results have showed that gasoline engine exhaust exhibited stronger cytotoxicity to human lung carcinoma cell lines (A549 cell) than methanol engine exhaust. Furthermore, gasoline engine exhaust increased micronucleus formation, induced DNA damage in A549 cells and increased TA98 revertants in the presence of metabolic activating enzymes in a concentration-dependent manner. In contrast, methanol engine exhaust failed to exhibit these adverse effects. The results suggest methanol may be used as a cleaner fuel for automobile.
Analysis of isocyanates in indoor dust.
Bekki, Kanae; Uchiyama, Shigehisa; Kunugita, Naoki
2018-05-04
Isocyanates are harmful semi-volatile organic compounds that are emitted from various consumer products like polyurethane foam-based mattresses. Although it is a concern that isocyanates might accumulate in indoor dust, causing infants and toddlers, in particular, to be exposed to them, little information is available on the levels of isocyanates in the indoor environment. In this study, we investigated the suitability of an analytical method for determining the presence and level of isocyanates in the indoor dust. The method we developed displayed acceptable linearity, accuracy, and precision in the analysis of eleven different isocyanates. By using this analytical method, we could detect five isocyanates (ICA, MIC, EIC, PIC, and PHI) and quantify three isocyanates (MIC, EIC, and PHI) in indoor dust collected in different houses. This study is the first to focus on the pollution of indoor dust by isocyanates, and the tested method is suitable for the estimation of the level of isocyanate exposure. Graphical abstract ᅟ.
Nakazawa, Akira; Tang, Ning; Inoue, Yoshinori; Kamichatani, Waka; Katoh, Toshifumi; Saito, Mitsuru; Obara, Kenji; Toriba, Akira; Hayakawa, Kazuichi
2017-01-01
Diallylamine-maleic acid copolymer (DAM)-nonwoven fabric (DAM-f), a fibrous adsorbent, contains DAM with zwitter-ionic functional groups and forms a hydration layer on the surface. The aim of this report was to evaluate the adsorption selectivity of DAM-f to semi-volatile organic acid (C1-C5). In the aqueous phase, formic acid dissolved in the hydration layer bound to the imino group of DAM-f due to anion exchange interaction. In the gas phase, the adsorption amounts of organic acids increased with the exposure time. Moreover, the adsorption rate constants correlated with the air/water partition coefficients (log K aw ) for formic acid, propionic acid, butyric acid, valeric acid and isovaleric acid, except for acetic acid. These results indicate that DAM-f is highly selective to hydrophilic compounds which easily move from the air to the hydration layer of DAM-f.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Not Available
1992-06-19
The Old City of York Landfill National Priority List (NPL) site is adjacent to South Road, approximately two miles southeast of the borough of Seven Valleys in Springfield Township, York County, Pennsylvania. Site soils, groundwater, springs, seeps, and collection vaults were contaminated with volatile and semi-volatile organic compounds. Human exposure could occur through ingestion or dermal absorption of site contaminants from the aforementioned media. The population at potential risk includes children, hunters, hikers, or other trespassers on the site who may come into direct contact with contaminated site soils. However, environmental media associated with the site appear minimally affected bymore » the landfill. The site represents no apparent public health hazard because there is no evidence of trespassing on the site, and because nearby residents have been provided municipal water.« less
Lability of Secondary Organic Particulate Matter
Liu, Pengfei; Li, Yong Jie; Wang, Yan; ...
2016-10-24
Accurate simulations of the consenctrations of atmospheric organic particulate matter (PM) are needed for predicting energy flow in the Earth’s climate system. In the past, simulations of organic PM widely assume equilibrium partitioning of semivolatile organic compounds (SVOCs) between the PM and surrounding vapor. Herein, we test this assumption by measuring evaporation rates and associated vapor mass concentration of organic films representative of atmospheric PM. For films representing anthropogenic PM, evaporation rates and vapor mass concentrations increased above a threshold relative humidity (RH), indicating equilibrium partitioning above a transition RH but not below. In contrast for films representing biogenic PM,more » no threshold was observed, indicating equilibrium partitioning at all RHs. The results suggest that the mass lability of atmospheric organic PM can differ in consequential ways among Earth’s natural biomes, polluted regions, and regions of land-use change, and these differences need to be considered when simulating atmospheric organic PM.« less
NASA Astrophysics Data System (ADS)
Dusek, Ulrike; Broekema, Elise; Holzinger, Rupert; Röckmann, Thomas; Meijer, Harro
2017-04-01
The origin of carbonaceous aerosol differs during day- and night-time, because emissions from major sources such as traffic, biomass combustion, and secondary organic aerosol formation show a distinct diurnal pattern. Moreover, photochemical processing and evaporation of semi-volatile organic compounds are enhanced during day-time, due to the availability of sunlight and higher temperatures. Assessing day-night differences in sources and chemical composition can give an indication of the importance of local/regional carbon sources and processing, since day-night differences should be averaged out during long-range transport. If local sources dominate, one could expect a strong diurnal variation in the source profile, but if long-range transport dominates the diurnal variation would be much weaker. In this study we measure the isotopic (14C and 13C) and detailed chemical composition of the organic fraction of the aerosol on high volume PM2.5 filter samples that were collected separately during day and night time. Radiocarbon (14C) measurements are used to estimate three main aerosol sources of organic and elemental carbon (OC and EC): Fossil fuel combustion (ff), biomass combustion (bb), and biogenic sources (bio). The detailed chemical and stable isotopic composition are measured at different desorption temperatures from the filter, which separates the more and less refractory organic compounds. The composition of the organic aerosol is measured using an thermal-desporption Proton Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-ToF-MS) method (Holzinger et al, 2010) and the stable isotopic composition is measured using a thermal desorption IRMS method (Dusek et al., 2013). Source apportionment results using 14C show that the contribution of fossil fuel combustion to EC and OC is higher during day-time than during night-time. This is valid for all seasons. During night-time biomass combustion plays a bigger role as a source of carbonaceous aerosol. Even in the summer, when biomass combustion is a small source, its relative contribution increases between 19:00 and 07:00. However, the diurnal changes in source contributions are relatively moderate (e.g., the biomass burning contribution to TC increased from 31% to 43% for the winter sample with the most distinct day-night difference.) This highlights the importance of long-range transport as a source of the carbonaceous aerosol in this region. First results from chemical composition measurements on four of the samples show that the concentration of less refractory organic carbon (desorption temperature up to 200 °C) increases at night-time much more strongly than the concentration of the more refractory carbon. Similarly, the concentration of small organic compounds with m/z < 100 also increases more strongly than heavier compounds. This indicates partitioning of semi-volatile OC as a possible additional night-time source. The chemical composition will be studied in more detail, focusing on diurnal changes in O/C ratios, individual compounds and compound classes, such as hydrocarbons or organic acids. Dusek, U., Meusinger, C., Oyama, B., Ramon, W., de Wilde, P., Holzinger, R., and Röckmann, T.: A thermal desorption system for measuring δ 13 C ratios on organic aerosol, Journal of aerosol science, 66, 72-82, 2013. Holzinger, R., Williams, J., Herrmann, F., Lelieveld, J., Donahue, N., Röckmann, T., 2010. Aerosol analysis using a Thermal-Desorption Proton-Transfer-Reaction Mass Spectrometer (TD-PTR-MS): a new approach to study processing of organic aerosols. Atmospheric chemistry and physics 10, 2257-2267.
Burkhardt, M.R.; Zaugg, S.D.; Burbank, T.L.; Olson, M.C.; Iverson, J.L.
2005-01-01
Polycyclic aromatic hydrocarbons (PAH) are recognized as environmentally relevant for their potential adverse effects on human and ecosystem health. This paper describes a method to determine the distribution of PAH and alkylated homolog groups in sediment samples. Pressurized liquid extraction (PLE), coupled with solid-phase extraction (SPE) cleanup, was developed to decrease sample preparation time, to reduce solvent consumption, and to minimize background interferences for full-scan GC-MS analysis. Recoveries from spiked Ottawa sand, environmental stream sediment, and commercially available topsoil, fortified at 1.5-15 ??g per compound, averaged 94.6 ?? 7.8%, 90.7 ?? 5.8% and 92.8 ?? 12.8%, respectively. Initial method detection limits for single-component compounds ranged from 20 to 302 ??g/kg, based on 25 g samples. Results from 28 environmental sediment samples, excluding homologs, show 35 of 41 compounds (85.4%) were detected in at least one sample with concentrations ranging from 20 to 100,000 ??g/kg. The most frequently detected compound, 2,6-dimethylnaphthalene, was detected in 23 of the 28 (82%) environmental samples with a concentration ranging from 15 to 907 ??g/kg. The results from the 28 environmental sediment samples for the homolog series showed that 27 of 28 (96%) samples had at least one homolog series present at concentrations ranging from 20 to 89,000 ??g/kg. The most frequently detected homolog series, C2-alkylated naphthalene, was detected in 26 of the 28 (93%) environmental samples with a concentration ranging from 25 to 3900 ??g/kg. Results for a standard reference material using dichloromethane Soxhlet-based extraction also are compared. ?? 2005 Elsevier B.V. All rights reserved.
Lacey, Steven; Alexander, Barbara M; Baxter, C Stuart
2014-01-01
Chemical exposures may be responsible for firefighters' elevated incidences of cancer and cardiovascular disease. This study characterized semivolatile chemical contamination on firefighter personal protective clothing to assess exposure of firefighters to these chemicals. Samples from used firefighter protective clothing, including gloves, hood, and one coat wristlet, were extracted with methylene chloride and analyzed by EPA method 8270 for semivolatile contaminants, including 20 polycyclic aromatic hydrocarbons (PAHs) and 6 phthalate diesters. Twenty-two of the chemicals of interest were found on at least one clothing swatch. Only di-(2-ethylhexyl) phthalate (DEHP), a plasticizer, added to polyvinyl chloride (PVC) to increase flexibility, was found on every swatch. DEHP concentrations were the highest of any chemical measured, and were 52 to 875 times higher than any PAH concentration measured. DEHP was also detected on most items of unused firefighter personal protective clothing, although at much lower levels. These findings suggest that firefighters are exposed to high levels of DEHP, a probable human carcinogen, and at levels much higher than PAHs, the semivolatile toxic combustion products most extensively studied historically. Firefighter exposure to DEHP and other phthalate diesters therefore merits further study.
NASA Astrophysics Data System (ADS)
Sun, Y.-L.; Zhang, Q.; Schwab, J. J.; Demerjian, K. L.; Chen, W.-N.; Bae, M.-S.; Hung, H.-M.; Hogrefe, O.; Frank, B.; Rattigan, O. V.; Lin, Y.-C.
2010-10-01
Submicron aerosol particles (PM1) were measured in-situ using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) during the summer 2009 Field Intensive Study at Queens College in New York City. Organic aerosol (OA) and sulfate are the two dominant species, accounting for 54% and 24%, respectively, of total PM1 mass on average. The average mass size distribution of OA presents a small mode peaking at ~150 nm (Dva) in addition to an accumulation mode (~550 nm) that is internally mixed with sulfate, nitrate, and ammonium. The diurnal cycles of sulfate and OA both show pronounced peaks between 01:00-02:00 p.m. EST due to photochemical production. The average (±1σ) oxygen-to-carbon (O/C), hydrogen-to-carbon (H/C), and nitrogen-to-carbon (N/C) ratios of OA in NYC are 0.36 (±0.09), 1.49 (±0.08), and 0.012(±0.005), respectively, corresponding to an average organic mass-to-carbon (OM/OC) ratio of 1.62(±0.11). Positive matrix factorization (PMF) of the high resolution mass spectra identified five OA components: a hydrocarbon-like OA (HOA), two types of oxygenated OA (OOA) including a low-volatility OOA (LV-OOA) and a semi-volatile OOA (SV-OOA), a cooking-emission related OA (COA), and a unique nitrogen-enriched OA (NOA). HOA appears to represent primary OA (POA) from urban traffic emissions. It comprises primarily of reduced species (H/C=1.83; O/C=0.06) and shows a mass spectral pattern very similar to those of POA from fossil fuel combustion, and correlates tightly with traffic emission tracers including elemental carbon and NOx. LV-OOA, which is highly oxidized (O/C=0.63) and correlates well with sulfate, appears to be representative for regional, aged secondary OA (SOA). SV-OOA, which is less oxidized (O/C=0.38) and correlates well with non-refractory chloride, likely represents less photo-chemically aged, semi-volatile SOA. COA shows a similar spectral pattern to the reference spectra of POA from cooking emissions and a distinct diurnal pattern peaking around local lunch and dinner times. In addition, NOA is characterized with prominent CxH2x+2N+ peaks likely from amine compounds. Our results indicate that cooking-related activities are a major source of POA in NYC, releasing comparable amounts of POA as traffic emissions. POA=HOA+COA) on average accounts for ~30% of the total OA mass during this study while SOA dominates the OA composition with SV-OOA and LV-OOA on average accounting for 34% and 30%, respectively, of the total OA mass. The chemical evolution of SOA in NYC involves a~continuous oxidation from SV-OOA to LV-OOA, which is further supported by a gradual increase of O/C ratio and a simultaneous decrease of H/C ratio in total OOA. Detailed analysis of NOA (5.8% of OA) presents evidence that nitrogen-containing organic species such as amines might have played an important role in the atmospheric processing of OA in NYC, likely involving acid-base chemistry. Analysis of air mass trajectories and satellite imagery of aerosol optical depth (AOD) indicates that the high potential source regions of secondary sulfate and aged OA are mainly located in regions to the west and southwest of the city.
Olfactory specialization for perfume collection in male orchid bees.
Mitko, Lukasz; Weber, Marjorie G; Ramirez, Santiago R; Hedenström, Erik; Wcislo, William T; Eltz, Thomas
2016-05-15
Insects rely on the olfactory system to detect a vast diversity of airborne molecules in their environment. Highly sensitive olfactory tuning is expected to evolve when detection of a particular chemical with great precision is required in the context of foraging and/or finding mates. Male neotropical orchid bees (Euglossini) collect odoriferous substances from multiple sources, store them in specialized tibial pouches and later expose them at display sites, presumably as mating signals to females. Previous analysis of tibial compounds among sympatric species revealed substantial chemical disparity in chemical composition among lineages with outstanding divergence between closely related species. Here, we tested whether specific perfume phenotypes coevolve with matching olfactory adaptations in male orchid bees to facilitate the location and harvest of species-specific perfume compounds. We conducted electroantennographic (EAG) measurements on males of 15 sympatric species in the genus Euglossa that were stimulated with 18 compounds present in variable proportions in male hind tibiae. Antennal response profiles were species-specific across all 15 species, but there was no conspicuous differentiation between closely related species. Instead, we found that the observed variation in EAG activity follows a Brownian motion model of trait evolution, where the probability of differentiation increases proportionally with lineage divergence time. However, we identified strong antennal responses for some chemicals that are present as major compounds in the perfume of the same species, thus suggesting that sensory specialization has occurred within multiple lineages. This sensory specialization was particularly apparent for semi-volatile molecules ('base note' compounds), thus supporting the idea that such compounds play an important role in chemical signaling of euglossine bees. Overall, our study found no close correspondence between antennal responses and behavioral preferences/tibial contents, but confirms the utility of EAG profiling for discovering certain behaviorally active compounds. © 2016. Published by The Company of Biologists Ltd.
NASA Astrophysics Data System (ADS)
Melymuk, Lisa; Bohlin-Nizzetto, Pernilla; Prokeš, Roman; Kukučka, Petr; Přibylová, Petra; Vojta, Šimon; Kohoutek, Jiří; Lammel, Gerhard; Klánová, Jana
2017-10-01
Degradation of semivolatile organic compounds (SVOCs) occurs naturally in ambient air due to reactions with reactive trace gases (e.g., ozone, NOx). During air sampling there is also the possibility for degradation of SVOCs within the air sampler, leading to underestimates of ambient air concentrations. We investigated the possibility of this sampling artifact in commonly used active and passive air samplers for seven classes of SVOCs, including persistent organic pollutants (POPs) typically covered by air monitoring programs, as well as SVOCs of emerging concern. Two active air samplers were used, one equipped with an ozone denuder and one without, to compare relative differences in mass of collected compounds. Two sets of passive samplers were also deployed to determine the influence of degradation during longer deployment times in passive sampling. In active air samplers, comparison of the two sampling configurations suggested degradation of particle-bound polycyclic aromatic hydrocarbons (PAHs), with concentrations up to 2× higher in the denuder-equipped sampler, while halogenated POPs did not have clear evidence of degradation. In contrast, more polar, reactive compounds (e.g., organophosphate esters and current use pesticides) had evidence of losses in the sampler with denuder. This may be caused by the denuder itself, suggesting sampling bias for these compounds can be created when typical air sampling apparatuses are adapted to limit degradation. Passive air samplers recorded up to 4× higher concentrations when deployed for shorter consecutive sampling periods, suggesting that within-sampler degradation may also be relevant in passive air monitoring programs.
Liagkouridis, Ioannis; Cousins, Ian T; Cousins, Anna Palm
2014-09-01
This review explores the existing understanding and the available approaches to estimating the emissions and fate of semi-volatile organic compounds (SVOCs) and in particular focuses on the brominated flame retardants (BFRs). Volatilisation, an important emission mechanism for the more volatile compounds can be well described using current emission models. More research is needed, however, to better characterise alternative release mechanisms such as direct material-particle partitioning and material abrasion. These two particle-mediated emissions are likely to result in an increased chemical release from the source than can be accounted for by volatilisation, especially for low volatile compounds, and emission models need to be updated in order to account for these. Air-surface partitioning is an important fate process for SVOCs such as BFRs however it is still not well characterised indoors. In addition, the assumption of an instantaneous air-particle equilibrium adopted by current indoor fate models might not be valid for high-molecular weight, strongly sorbing compounds. A better description of indoor particle dynamics is required to assess the effect of particle-associated transport as this will control the fate of low volatile BFRs. We suggest further research steps that will improve modelling precision and increase our understanding of the factors that govern the indoor fate of a wide range of SVOCs. It is also considered that the appropriateness of the selected model for a given study relies on the individual characteristics of the study environment and scope of the study. Copyright © 2014 Elsevier B.V. All rights reserved.
Xinling, Li; Zhen, Huang
2009-03-15
A study of engine performance characteristics and both of regulated (CO, HC, NO(x), and smoke) and unregulated (ultrafine particle number, mass concentrations and size distribution) emissions for a turbocharged diesel engine fueled with conventional diesel, gas-to-liquid (GTL) and dimethyl ether (DME) fuels respectively at different engine loads and speeds have been carried out. The results indicated that fuel components significantly affected the engine performance and regulated/unregulated emissions. GTL exhibited almost the same power and torque output as diesel, while improved fuel economy. GTL significantly reduced regulated emissions with average reductions of 21.2% in CO, 15.7% in HC, 15.6% in NO(x) and 22.1% in smoke in comparison to diesel, as well as average reductions in unregulated emissions of total ultrafine particle number (N(tot)) and mass (M(tot)) emissions by 85.3% and 43.9%. DME can significantly increase torque and power, compared with the original diesel engine, as well as significantly reduced regulated emissions of 40.1% in HC, 48.2% in NO(x) and smoke free throughout all the engine conditions. However, N(tot) for DME is close to that for diesel. The reason is that the accumulation mode particle number emissions for DME are very low due to the characteristics of oxygen content and no C-C bond, which promotes the processes of nucleation and condensation of the semi-volatile compounds in the exhaust gas, as a result, a lot of nucleation mode particles produce.
Nonequilibrium atmospheric secondary organic aerosol formation and growth
Perraud, Véronique; Bruns, Emily A.; Ezell, Michael J.; Johnson, Stanley N.; Yu, Yong; Alexander, M. Lizabeth; Zelenyuk, Alla; Imre, Dan; Chang, Wayne L.; Dabdub, Donald; Pankow, James F.; Finlayson-Pitts, Barbara J.
2012-01-01
Airborne particles play critical roles in air quality, health effects, visibility, and climate. Secondary organic aerosols (SOA) formed from oxidation of organic gases such as α-pinene account for a significant portion of total airborne particle mass. Current atmospheric models typically incorporate the assumption that SOA mass is a liquid into which semivolatile organic compounds undergo instantaneous equilibrium partitioning to grow the particles into the size range important for light scattering and cloud condensation nuclei activity. We report studies of particles from the oxidation of α-pinene by ozone and NO3 radicals at room temperature. SOA is primarily formed from low-volatility ozonolysis products, with a small contribution from higher volatility organic nitrates from the NO3 reaction. Contrary to expectations, the particulate nitrate concentration is not consistent with equilibrium partitioning between the gas phase and a liquid particle. Rather the fraction of organic nitrates in the particles is only explained by irreversible, kinetically determined uptake of the nitrates on existing particles, with an uptake coefficient that is 1.6% of that for the ozonolysis products. If the nonequilibrium particle formation and growth observed in this atmospherically important system is a general phenomenon in the atmosphere, aerosol models may need to be reformulated. The reformulation of aerosol models could impact the predicted evolution of SOA in the atmosphere both outdoors and indoors, its role in heterogeneous chemistry, its projected impacts on air quality, visibility, and climate, and hence the development of reliable control strategies. PMID:22308444
Emission of polycyclic aromatic hydrocarbons from diesel engine in a bus station, Londrina, Brazil
NASA Astrophysics Data System (ADS)
Tavares, Moacir; Pinto, Jurandir P.; Souza, Alexandre L.; Scarmínio, Ieda S.; Cristina Solci, Maria
2004-09-01
The concentrations of vapor phase polycyclic aromatic hydrocarbons (PAHs) were measured at the Central Bus Station of Londrina, where only diesel-powered vehicles circulate. The samples were collected within a period of 24 h for 14 consecutive days in January 2002. The semi-volatile PAHs were collected using a cartridge packed with XAD-2 resin, extracted under sonication and subsequently analyzed by gas chromatograph equipped with the flame ionization and mass spectrometer detectors (GC-FID and GC/MS). Ten PAH compounds were found (naphthalene, acenapthylene, acenapthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo(a)anthracene and chrysene). The average concentrations ranged from 1.4±0.3 ng m-3 for benzo(a)anthracene to 348.0±32.7 ng m-3 for phenanthrene. The species that presented higher concentration were phenanthrene (348.0±32.7 ng m-3), fluorene (140.2±17.3 ng m-3) and naphthalene (97.7±10.3 ng m-3). The PAHs with two and three rings were responsible by 90.2% of the total concentration among 10 PAHs. The concentrations of PAHs were lower on Sunday in comparison with the workdays, due to the reduction of bus traffic in the station. Correlations and principal component analysis with Varimax rotation were used to estimate the local PAH emission source profile originating from the diesel exhaust. The ratio PHEN/FLU of 2.5 calculated from the results is suggested as indication from diesel combustion exhaust.
McDonald, Jacob D.; Harrod, Kevin S.; Seagrave, JeanClare; Seilkop, Steven K.; Mauderly, Joe L.
2004-01-01
In this study we compared a “baseline” condition of uncontrolled diesel engine exhaust (DEE) emissions generated with current (circa 2003) certification fuel to an emissions-reduction (ER) case with low sulfur fuel and a catalyzed particle trap. Lung toxicity assessments (resistance to respiratory viral infection, lung inflammation, and oxidative stress) were performed on mice (C57Bl/6) exposed by inhalation (6 hr/day for 7 days). The engine was operated identically (same engine load) in both cases, and the inhalation exposures were conducted at the same exhaust dilution rate. For baseline DEE, this dilution resulted in a particle mass (PM) concentration of approximately 200 μg/m3 PM, whereas the ER reduced the PM and almost every other measured constituent [except nitrogen oxides (NOx)] to near background levels in the exposure atmospheres. These measurements included PM, PM size distribution, PM composition (carbon, ions, elements), NOx, carbon monoxide, speciated/total volatile hydrocarbons, and several classes of semi-volatile organic compounds. After exposure concluded, one group of mice was immediately sacrificed and assessed for inflammation and oxidative stress in lung homogenate. Another group of mice were intratracheally instilled with respiratory syncytial virus (RSV), and RSV lung clearance and inflammation was assessed 4 days later. Baseline DEE produced statistically significant biological effects for all measured parameters. The use of low sulfur fuel and a catalyzed trap either completely or nearly eliminated the effects. PMID:15345344
DOE Office of Scientific and Technical Information (OSTI.GOV)
Buonanno, Giorgio, E-mail: buonanno@unicas.it; Stabile, Luca; Avino, Pasquale
2011-11-15
Highlights: > Particle size distributions and total concentrations measurement at the stack and before the fabric filter of an incinerator. > Chemical characterization of UFPs in terms of heavy metal concentration through a nuclear method. > Mineralogical investigation through a Transmission Electron Microscope equipped with an Energy Dispersive Spectrometer. > Heavy metal concentrations on UFPs as function of the boiling temperature. > Different mineralogical and morphological composition amongst samples collected before the fabric filter and at the stack. - Abstract: Waste combustion processes are responsible of particles and gaseous emissions. Referring to the particle emission, in the last years specificmore » attention was paid to ultrafine particles (UFPs, diameter less than 0.1 {mu}m), mainly emitted by combustion processes. In fact, recent findings of toxicological and epidemiological studies indicate that fine and ultrafine particles could represent a risk for health and environment. Therefore, it is necessary to quantify particle emissions from incinerators also to perform an exposure assessment for the human populations living in their surrounding areas. To these purposes, in the present work an experimental campaign aimed to monitor UFPs was carried out at the incineration plant in San Vittore del Lazio (Italy). Particle size distributions and total concentrations were measured both at the stack and before the fabric filter inlet in order to evaluate the removal efficiency of the filter in terms of UFPs. A chemical characterization of UFPs in terms of heavy metal concentration was performed through a nuclear method, i.e. Instrumental Neutron Activation Analysis (INAA), as well as a mineralogical investigation was carried out through a Transmission Electron Microscope (TEM) equipped with an Energy Dispersive Spectrometer (EDS) in order to evaluate shape, crystalline state and mineral compound of sampled particles. Maximum values of 2.7 x 10{sup 7} part. cm{sup -3} and 2.0 x 10{sup 3} part. cm{sup -3} were found, respectively, for number concentration before and after the fabric filter showing a very high efficiency in particle removing by the fabric filter. With regard to heavy metal concentrations, the elements with higher boiling temperature present higher concentrations at lower diameters showing a not complete evaporation in the combustion section and the consequent condensation of semi-volatile compounds on solid nuclei. In terms of mineralogical and morphological analysis, the most abundant compounds found in samples collected before the fabric filter are Na-K-Pb oxides followed by phyllosilicates, otherwise, different oxides of comparable abundance were detected in the samples collected at the stack.« less
Modeling Gas-Particle Partitioning of SOA: Effects of Aerosol Physical State and RH
NASA Astrophysics Data System (ADS)
Zuend, A.; Seinfeld, J.
2011-12-01
Aged tropospheric aerosol particles contain mixtures of inorganic salts, acids, water, and a large variety of organic compounds. In liquid aerosol particles non-ideal mixing of all species determines whether the condensed phase undergoes liquid-liquid phase separation or whether it is stable in a single mixed phase, and whether it contains solid salts in equilibrium with their saturated solution. The extended thermodynamic model AIOMFAC is able to predict such phase states by representing the variety of organic components using functional groups within a group-contribution concept. The number and composition of different condensed phases impacts the diversity of reaction media for multiphase chemistry and the gas-particle partitioning of semivolatile species. Recent studies show that under certain conditions biogenic and other organic-rich particles can be present in a highly viscous, semisolid or amorphous solid physical state, with consequences regarding reaction kinetics and mass transfer limitations. We present results of new gas-particle partitioning computations for aerosol chamber data using a model based on AIOMFAC activity coefficients and state-of-the-art vapor pressure estimation methods. Different environmental conditions in terms of temperature, relative humidity (RH), salt content, amount of precursor VOCs, and physical state of the particles are considered. We show how modifications of absorptive and adsorptive gas-particle mass transfer affects the total aerosol mass in the calculations and how the results of these modeling approaches compare to data of aerosol chamber experiments, such as alpha-pinene oxidation SOA. For a condensed phase in a mixed liquid state containing ammonium sulfate, the model predicts liquid-liquid phase separation up to high RH in case of, on average, moderately hydrophilic organic compounds, such as first generation oxidation products of alpha-pinene. The computations also reveal that treating liquid phases as ideal mixtures substantially overestimates the SOA mass, especially at high relative humidity.
Bartrons, Mireia; Grimalt, Joan O.; de Mendoza, Guillermo; Catalan, Jordi
2012-01-01
Organohalogen compounds are some of the most notorious persistent pollutants disturbing the Earth biosphere. Although human-made, these chemicals are not completely alien to living systems. A large number of natural organohalogens, part of the secondary metabolism, are involved in chemical trophic interactions. Surprisingly, the relationship between organisms’ trophic position and synthetic organohalogen biotransformation capability has not been investigated. We studied the case for polybromodiphenyl ethers (PBDE), a group of flame-retardants of widespread use in the recent years, in aquatic food webs from remote mountain lakes. These relatively simple ecosystems only receive pollution by atmospheric transport. A large predominance of the PBDE congener currently in use in Europe, BDE-209, largely dominated the PBDE composition of the basal resources of the food web. In contrast, primary consumers (herbivores and detritivores) showed a low proportion of BDE-209, and dominance of several less brominated congeners (e.g. BDE-100, BDE47). Secondary consumers (predators) showed large biomagnification of BDE-209 compare to other congeners. Finally, top predator fish characterized by low total PBDE concentrations. Examination of the bromine stable isotopic composition indicates that primary consumers showed higher PBDE biotransformation capability than secondary consumers. We suggest that the evolutionary response of primary consumers to feeding deterrents would have pre-adapted them for PBDE biotransformation. The observed few exceptions, some insect taxa, can be interpreted in the light of the trophic history of the evolutionary lineage of the organisms. Bromine isotopic composition in fish indicates that low PBDE values are due to not only biotransformation but also to some other process likely related to transport. Our finding illustrates that organohalogen compounds may strongly disturb ecosystems even at low concentrations, since the species lacking or having scarce biotransformation capability may be selectively more exposed to these halogenated hydrophobic semi-volatile organic pollutants due to their high bioaccumulation potential. PMID:22848624
Observational Constraints on Modeling Growth and Evaporation Kinetics of Isoprene SOA
NASA Astrophysics Data System (ADS)
Zaveri, R. A.; Shilling, J. E.; Zelenyuk, A.; Liu, J.; Wilson, J. M.; Laskin, A.; Wang, B.; Fast, J. D.; Easter, R. C.; Wang, J.; Kuang, C.; Thornton, J. A.; Setyan, A.; Zhang, Q.; Onasch, T. B.; Worsnop, D. R.
2014-12-01
Isoprene is thought to be a major contributor to the global secondary organic aerosol (SOA) budget, and therefore has the potential to exert a significant influence on earth's climate via aerosol direct and indirect radiative effects. Both aerosol optical and cloud condensation nuclei properties are quite sensitive to aerosol number size distribution, as opposed to the total aerosol mass concentration. Recent studies suggest that SOA particles can be highly viscous, which can affect the kinetics of SOA partitioning and size distribution evolution when the condensing organic vapors are semi-volatile. In this study, we examine the growth kinetics of SOA formed from isoprene photooxidation in the presence of pre-existing Aitken and accumulation mode aerosols in: (a) the ambient atmosphere during the CARES field campaign, and (b) the environmental chamber at PNNL. Each growth episode is analyzed and interpreted with the updated MOSAIC aerosol box model, which performs kinetic gas-particle partitioning of SOA and takes into account diffusion and chemical reaction within the particle phase. The model is initialized with the observed aerosol size distribution and composition at the beginning of the experiment, and the total amount of SOA formed in the model at any given time is constrained by the observed total amount of SOA formed. The variable model parameters include the number of condensing organic species, their gas-phase formation rates, their effective volatilities, and their bulk diffusivities in the Aitken and accumulation modes. The objective of the constrained modeling exercise is then to determine which model configuration is able to best reproduce the observed size distribution evolution, thus providing valuable insights into the possible mechanism of SOA formation. We also examine the evaporation kinetics of size-selected particles formed in the environmental chamber to provide additional constraints on the effective volatility and bulk diffusivity of the organic species. Our results suggest that SOA formed from isoprene photooxidation is semi-volatile, and the resulting size distribution evolution is highly sensitive to the phase state (bulk diffusivity) of the pre-existing aerosol. Implications of these findings on further SOA model development and evaluation strategy will be discussed.
Barro, Ruth; Ares, Sergio; Garcia-Jares, Carmen; Llompart, Maria; Cela, Rafael
2004-08-06
In this study, a combination of solid-phase extraction (SPE) and solid-phase microextraction (SPME) has been used to determine chlorobenzenes in air. Analytes were sampled by pumping a known volume of air through a porous polymer (Tenax TA). Then, the adsorbent was transferred into a glass vial and SPME was performed. The quantification was carried out using gas chromatography (GC)-electron-capture detection or GC-MS. Several SPME coatings (100 microm poly(dimethylsiloxane) (PDMS), 75 microm Carboxen (CAR)-PDMS, 65 microm PDMS-divinylbenzene (DVB), 65 microm PDMS-DVB and 85 microm polyacrylate (PA) were evaluated, obtaining the highest responses with Carbowax (CW)- PDMS for the most volatile chlorobenzenes, and with PDMS-DVB or CW-DVB fibers for the semivolatile compounds. To optimize some other factors that could affect the SPME step, a factorial design was used. Kinetic studies of the SPME process were also performed. Concerning the SPE step, breakthrough was studied, showing that 2.5 m3 of air could be processed without losses of the most volatile compounds. The performance of the method was evaluated. External calibration, which does not require the complete sampling process, demonstrated to be suitable, obtaining good linearity (R2 > 0.99) for all chlorobenzenes. Recovery studies were performed at two concentration levels (4 and 40 ng/m3), obtaining quantitative recoveries (>80%). Limits of detection at the sub ng/m3 were achieved for all the target compounds.
Lorah, Michelle M.; Clark, Jeffrey S.
1996-01-01
Chemical manufacturing, munitions filling, and other military-support activities have resulted in the contamination of ground water, surface water, and soil in the Canal Creek area of Aberdeen Proving Ground, Maryland. Chlorinated volatile organic compounds, including 1,1,2,2-tetrachloroethane and trichloroethylene, are widespread ground-water contaminants in two aquifers that are composed of unconsolidated sand and gravel. Distribution and fate of chlorinated organic compounds in the ground water has been affected by the movement and dissolution of solvents in their dense immiscible phase and by microbial degradation under anaerobic conditions. Detection of volatile organic contaminants in adjacent surface water indicates that shallow contaminated ground water discharges to surface water. Semivolatile organic compounds, especially polycyclic aromatic hydrocarbons, are the most prevalent organic contaminants in soils. Various trace elements, such as arsenic, cadmium, lead, and zinc, were found in elevated concentrations in ground water, surface water, and soil. Simulations with a ground-water-flow model and particle tracker postprocessor show that, without remedial pumpage, the contaminants will eventually migrate to Canal Creek and Gunpowder River. Simulations indicate that remedial pumpage of 2.0 million gallons per day from existing wells is needed to capture all particles originating in the contaminant plumes. Simulated pumpage from offsite wells screened in a lower confined aquifer does not affect the flow of contaminated ground water in the Canal Creek area.
NASA Astrophysics Data System (ADS)
Busca, R.; Saccon, M.; Moukhtar, S.; Rudolph, J.
2009-05-01
Atmospheric particulate organic matter (POM) adversely affects health and climate. One of the still poorly understood sources of secondary organic matter (SOM) is the formation of secondary POM from the photo- oxidation of atmospheric volatile organic compounds (VOC). Nitrophenols, which are toxic semi-volatile compounds, are formed in the atmosphere by OH-radical initiated photo-oxidation of aromatic hydrocarbons, such as toluene. A method was developed to determine concentrations and stable carbon isotope ratios of particulate methyl nitrophenols in the atmosphere. This method has been used to quantify methyl nitrophenols, specifically 2-methyl-4-nitrophenol and 4-methyl-2-nitrophenol, found in atmospheric PM samples in trace quantities. Using this method, we conducted measurements of methyl nitrophenols in atmospheric PM in rural and suburban areas in Southern Ontario. The results of these measurements showed that the concentration of methyl nitrophenols in atmospheric PM is much lower than expected from the extrapolation of laboratory experiments and measured atmospheric toluene concentrations. In order to better understand the reasons for these findings, an analytical method for the analysis of nitrophenols in the gas phase is currently being developed. Similarly, the measurement technique is modified to allow analysis of other phenolic products of the oxidation of aromatic hydrocarbons in PM as well as in the gas phase. In this poster, sampling techniques for collection and GC-MS analysis of nitrophenols in gas phase and PM will be presented along with preliminary results from summer 2008 and spring 2009 studies.
Midander, Klara; Elihn, Karine; Wallén, Anna; Belova, Lyuba; Karlsson, Anna-Karin Borg; Wallinder, Inger Odnevall
2012-06-15
Continuous daily measurements of airborne particles were conducted during specific periods at an underground platform within the subway system of the city center of Stockholm, Sweden. Main emphasis was placed on number concentration, particle size distribution, soot content (analyzed as elemental and black carbon) and surface area concentration. Conventional measurements of mass concentrations were conducted in parallel as well as analysis of particle morphology, bulk- and surface composition. In addition, the presence of volatile and semi volatile organic compounds within freshly collected particle fractions of PM(10) and PM(2.5) were investigated and grouped according to functional groups. Similar periodic measurements were conducted at street level for comparison. The investigation clearly demonstrates a large dominance in number concentration of airborne nano-sized particles compared to coarse particles in the subway. Out of a mean particle number concentration of 12000 particles/cm(3) (7500 to 20000 particles/cm(3)), only 190 particles/cm(3) were larger than 250 nm. Soot particles from diesel exhaust, and metal-containing particles, primarily iron, were observed in the subway aerosol. Unique measurements on freshly collected subway particle size fractions of PM(10) and PM(2.5) identified several volatile and semi-volatile organic compounds, the presence of carcinogenic aromatic compounds and traces of flame retardants. This interdisciplinary and multi-analytical investigation aims to provide an improved understanding of reported adverse health effects induced by subway aerosols. Copyright © 2012 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Khare, P.; Marcotte, A.; Sheu, R.; Ditto, J.; Gentner, D. R.
2017-12-01
Intermediate- and semi-volatile organic compounds (IVOCs and SVOCs) have high secondary organic aerosol (SOA) yields, as well as significant ozone formation potentials. Yet, their emission sources and oxidation pathways remain largely understudied due to limitations in current analytical capabilities. Online mass spectrometers are able to collect real time data but their limited mass resolving power renders molecular level characterization of IVOCs and SVOCs from the unresolved complex mixture unfeasible. With proper sampling techniques and powerful analytical instrumentation, our offline tandem mass spectrometry (i.e. MS×MS) techniques provide molecular-level and structural identification over wide polarity and volatility ranges. We have designed a novel analytical system for offline analysis of gas-phase SOA precursors collected on custom-made multi-bed adsorbent tubes. Samples are desorbed into helium via a gradual temperature ramp and sample flow is split equally for direct-MS×MS analysis and separation via gas chromatography (GC). The effluent from GC separation is split again for analysis via atmospheric pressure chemical ionization quadrupole time-of-flight mass spectrometry (APCI-Q×TOF) and traditional electron ionization mass spectrometry (EI-MS). The compounds for direct-MS×MS analysis are delivered via a transfer line maintained at 70ºC directly to APCI-Q×TOF, thus preserving the molecular integrity of thermally-labile, or other highly-reactive, organic compounds. Both our GC-MS×MS and direct-MS×MS analyses report high accuracy parent ion masses as well as information on molecular structure via MS×MS, which together increase the resolution of unidentified complex mixtures. We demonstrate instrument performance and present preliminary results from urban atmospheric samples collected from New York City with a wide range of compounds including highly-functionalized organic compounds previously understudied in outdoor air. Our work offers new insights into emerging emission sources in urban environments that can have a major impact on public health and also improves understanding of anthropogenic SOA precursor emissions.
NASA Astrophysics Data System (ADS)
Chuang, Jane C.; Mack, Gregory A.; Kuhlman, Michael R.; Wilson, Nancy K.
A pilot field study was performed in Columbus, OH, during the winter of 1986/1987. The objectives were to determine the feasibility of the use of a newly developed quiet sampler in indoor air sampling for particles and semivolatile organic compounds (SVOC) and to measure the concentrations of polycyclic aromatic hydrocarbons (PAH), PAH derivatives, and nicotine in air in selected residences. Eight homes were chosen for sampling on the basis of these characteristics: electric/gas heating system, electric/gas cooking appliances, and the absence/presence of environmental tobacco smoke (ETS). The indoor sampler was equipped with a quartz-fiber filter to collect particles followed by XAD-4 resin to trap SVOC. A PS-1 sampler with a similar sampling module was used outdoors. The indoor air was sampled in the kitchen and living room areas over two consecutive 8-h periods. The outdoor air was sampled concurrently with the indoor samples over a 16-h period. Fifteen PAH, five nitro-PAH, five oxygenated PAH, and three nitrogen heterocyclic compounds were determined in these samples. The most abundant PAH found indoors was naphthalene. The indoor concentrations of PAH derivatives were lower than those of their parent compounds. Average concentrations of all but three target compounds (naphthalene dicarboxylic acid anhydride, pyrene dicarboxylic acid anhydride, and 2-nitrofluoranthene) were higher indoors than outdoors. Environmental tobacco smoke was the most significant influence on indoor pollutant levels. Homes with gas heating systems had higher indoor pollutant levels than homes with electric heating systems. However, the true effects of heating and cooking systems were not characterized as accurately as the effects of ETS because of the small sample sizes and the lack of statistical significance for most pollutant differences in the absence of ETS. The concentrations of PAH marker compounds (phenanthrene, fluoranthene, and pyrene) correlated well with the concentrations of other target compounds. Quinoline and isoquinoline can be used to indicate indoor levels of ETS.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Mumford, J.L.; Burton, R.M.; Svendsgaard, D.J.
1991-10-01
This study assessed human exposure to air pollutants from unvented kerosene heaters in mobile homes. Eight electric homes with no smokers were monitored for airborne particles of < 10 {mu}m in diameter (PM{sub 10}), semivolatile organics, and carbon monoxide with the kerosene heaters on and off. The organic emissions were assayed for polycyclic aromatic hydrocarbon (PAH), nitro-PAH, and for mutagenicity in a Salmonella typhimurium reverse mutation assay. Usage of kerosene heaters resulted in (a) a significant increase in CO and organic levels (including carcinogenic PAH and nitro-PAH), (b) no significant effect on PM{sub 10} levels, except in two homes, (c)more » the presence of unburned kerosene fuel, (d) an increase in mutagenicity (in TA98) of particle-phase organics in five homes, and (e) little mutagenicity in the semivolatile organics in TA98 and TA100. Four of the eight heaters investigated emitted pollutants that exceeded the US ambient air standards for the 24-h PM{sub 10} standard and/or CO standards (the 1-h peak or 8-h average standard). This study showed that kerosene heater emissions can significantly impact indoor air quality in mobile homes.« less
NASA Astrophysics Data System (ADS)
Feng, Jialiang
For the first time, the dependency of the characteristics of organic matter in PM2.5 on geographical and climatic zones in three metropolitan cities of China was studied. Seasonal samples were collected at suburban and urban sites in Beijing, Shanghai and Guangzhou in 2002 and 2003. To further support the above study, seasonal samples were also collected at Changdao Island, a remote island, in Bohai Sea/Yellow Sea. Concentrations of organic carbon (OC), elemental carbon (EC), water-soluble organic carbon (WSOC), and solvent-extractable organic compounds (SEOC) were analyzed. The characteristics of the n-alkanes, polycyclic aromatic hydrocarbons, n-fatty acids, n-alkanols and molecular markers such as triterpanes were determined and used for source identification. Source apportionment was complemented by Chemical Mass Balance (CMB) modeling using the measured organic species as tracers. The impact of wind speed and wind direction on air quality was studied by back trajectory calculations and analysis. In general, traffic emissions were the largest contributors of OC followed by coal burning, kitchen emissions, vegetative detritus and biomass burning. However, in the space-heating season in Northern China, coal burning was the most important contributor of OC in the suburban areas of Beijing and at Changdao. Beijing had the highest concentration of organic aerosol followed by Guangzhou and Shanghai, while seasonal variation was in reverse order. Dispersion conditions determined by local topographies and meteorology were responsible for this trend. Contrary to common understanding, pollutant concentrations at the suburban sites were higher than the urban sites in all three cities. The main reason was the rapid urbanization of the suburban areas in the immediate vicinity of urban centers since China opened up for economic development, in addition, large numbers of manufacturing plants were relocated from the cities to the countryside in an attempt to clean up the urban environment. WSOC/TC ratios were comparable in all three cities at 0.2-0.3 and this value can be considered typical for urban aerosols from Chinese cities. Similar PAH/ALK ratios were found in the three cities, and PAHs were from a mixed contribution of coal burning and engine exhaust. More than half of the resolved SEOC was found to be n-fatty acids and they were mainly from kitchen emissions based on source profile comparisons and CMB analysis. The increase of contribution from coal burning in Beijing due to space heating was identified by the different distribution of triterpanes in summer and winter. The relative concentrations of semivolatile fossil fuel residue n-alkanes (<=C26) were inversely dependent on the ambient temperature. Similar trend was found in the concentrations of the semivolatile PAHs (molecular weight <=228). This was mainly caused by the gas/particle partitioning of semivolatile species in the different climatic zones. The enrichment of higher molecular weight plant wax compounds from Beijing to Shanghai to Guangzhou was a reflection of the variations of the vegetation in the different climatic zones. The seasonal variations in the concentrations and compositions of organic matter at Changdao were similar to the three cities, especially to Beijing. The remote island was also impacted by anthropogenic pollutants, and transported particles played a significant role in the contribution of the organic matter exemplified by the high WSOC/TC, low C18:1/C18 fatty acid, and high BeP/(BeP+BaP) ratios.
REGULATORY PERSPECTIVE ON MANAGING RISKS AT ...
Over 700 sites in the United States have been identified where wood preserving operations have been conducted. The most common types of wood preservatives found at these sites are creosote, pentachlorophenol (PCP), and copper chromated arsenate (CCA). When properly used and disposed of, these preservatives do not impose a significant health risk. However, due to operating procedures (many of which were accepted industry practices at the time), wood treating operations have contributed to soil and groundwater contamination. Primary sources of pollution at these sites are lagoons, waste ponds, drip raacki areas and chemical storage and treatment tanks. To better understand the risks associated with the use of wood preserving compounds, it is important to identify the constituents of concern. Creosote is produced as a distillate from coal tar and hence, is a variable mixture of hundreds of compounds, mostly semivolatile organics (SVOCs). Polynuclear Aromatic Hydrocarbons (PAHs) generally, account for up to 85%, by weight, of the chemical constituents found in undiluted creosote. Genetic toxicity if individual PAHs increase with m,olecular weight. USEPA has determined that 7 PAHs are probable human carcinogens and has set forth order-of-magnitue relative potency factors for these constituents, Pentachlorophenol (PCP0 is another preservative used in wood preserving processes and is prepared by dissolving technical grade PCP in oil to produce a solution that
DEVELOPMENT OF A SYSTEMATIC APPROACH TO ...
Risk assessment is a crucial component of the site remediation decision-making process. Some current EPA methods do not have detection limits low enough for risk assessment of many VOCs (e.g., EPA Region 3 Risk Based Concentration levels, EPA Region 9 Preliminary Remediation Goals, state-specified concentration levels). The magnitude of this problem was described in a paper recently presented at a University of Massachusetts Remediation Conference with the conclusion that the resolution of this issue is critical for valid human health and ecological risk assessments. Likewise, the difficulty of obtaining complete extraction of water-soluble VOCs and semi-volatile organic compounds (SVOCs) makes the generation of reliable and reproducible data a serious concern in site characterization and risk assessment programs.This poster presents findings of the development of an analytical method which uses thermal desorption combined with dual gas chromatography/mass spectrometry (GC/MS) to extract and accurately measure low levels of VOCs and SVOCs in soil and sediment samples with medium to high moisture content. Thermal extraction was selected for examination because the technique is simpler and more efficient than the present EPA purge-and-trap methods, and all water-soluble compounds are amenable to the procedure. Efforts were made to modify commonly used instrumentation (e.g., Archon
Xiong, Jianyin; Huang, Shaodan; Zhang, Yinping
2012-01-01
The diffusion coefficient (D m) and material/air partition coefficient (K) are two key parameters characterizing the formaldehyde and volatile organic compounds (VOC) sorption behavior in building materials. By virtue of the sorption process in airtight chamber, this paper proposes a novel method to measure the two key parameters, as well as the convective mass transfer coefficient (h m). Compared to traditional methods, it has the following merits: (1) the K, D m and h m can be simultaneously obtained, thus is convenient to use; (2) it is time-saving, just one sorption process in airtight chamber is required; (3) the determination of h m is based on the formaldehyde and VOC concentration data in the test chamber rather than the generally used empirical correlations obtained from the heat and mass transfer analogy, thus is more accurate and can be regarded as a significant improvement. The present method is applied to measure the three parameters by treating the experimental data in the literature, and good results are obtained, which validates the effectiveness of the method. Our new method also provides a potential pathway for measuring h m of semi-volatile organic compounds (SVOC) by using that of VOC. PMID:23145156
Volatile Organic Compound Emissions by Agricultural Crops
NASA Astrophysics Data System (ADS)
Ormeno, E.; Farres, S.; Gentner, D.; Park, J.; McKay, M.; Karlik, J.; Goldstein, A.
2008-12-01
Biogenic Volatile Organic Compounds (BVOCs) participate in ozone and aerosol formation, and comprise a substantial fraction of reactive VOC emission inventories. In the agriculturally intensive Central Valley of California, emissions from crops may substantially influence regional air quality, but emission potentials have not been extensively studied with advanced instrumentation for many important crops. Because crop emissions may vary according to the species, and California emission inventories are constructed via a bottom-up approach, a better knowledge of the emission rate at the species-specific level is critical for reducing uncertainties in emission inventories and evaluating emission model performance. In the present study we identified and quantified the BVOCs released by dominant agricultural crops in California. A screening study to investigate both volatile and semivolatile BVOC fractions (oxygenated VOCs, isoprene, monoterepenes, sesquiterpenes, etc.) was performed for 25 crop species (at least 3 replicates plants each), including branch enclosures of woody species (e.g. peach, mandarin, grape, pistachio) and whole plant enclosures for herbaceous species (e.g. onion, alfalfa, carrot), through a dynamic cuvette system with detection by PTRMS, in-situ GCMS/FID, and collection on carbon-based adsorbents followed by extraction and GCMS analysis. Emission data obtained in this study will allow inclusion of these crops in BVOC emission inventories and air quality simulations.
NASA Astrophysics Data System (ADS)
Qin, Momei; Hu, Yongtao; Wang, Xuesong; Vasilakos, Petros; Boyd, Christopher M.; Xu, Lu; Song, Yu; Ng, Nga Lee; Nenes, Athanasios; Russell, Armistead G.
2018-07-01
Monoterpenes react with nitrate radicals (NO3), contributing substantially to nighttime organic aerosol (OA) production. In this study, the role of reactions of monoterpenes + NO3 in forming biogenic secondary organic aerosol (BSOA) was examined using the Community Multiscale Air Quality (CMAQ) model, with extended emission profiles of biogenic volatile organic compounds (BVOCs), species-specific representations of BSOA production from individual monoterpenes and updated aerosol yields for monoterpene + NO3. The model results were compared to detailed measurements from the Southern Oxidants and Aerosol Study (SOAS) at Centreville, Alabama. With the more detailed model, monoterpene-derived BSOA increased by ∼1 μg m-3 at night, accounting for one-third of observed less-oxidized oxygenated OA (LO-OOA), more closely agreeing with observations (lower error, stronger correlation). Implementation of a multigenerational oxidation approach resulted in the model capturing elevated OA episodes. With the aging model, aged semi-volatile organic compounds (ASVOCs) contributed over 60% of the monoterpene-derived BSOA, followed by SOA formation via nitrate radical chemistry, making up to 34% of that formed at night. Among individual monoterpenes, β-pinene and limonene contributed most to the monoterpene-derived BSOA from nighttime reactions.
A critical review of reported air concentrations of organic compounds in aircraft cabins.
Nagda, N L; Rector, H E
2003-09-01
This paper presents a review and assessment of aircraft cabin air quality studies with measured levels of volatile and semivolatile organic compounds (VOCs and SVOCs). VOC and SVOC concentrations reported for aircraft cabins are compared with those reported for residential and office buildings and for passenger compartments of other types of transportation. An assessment of measurement technologies and quality assurance procedures is included. The six studies reviewed in the paper range in coverage from two to about 30 flights per study. None of the monitored flights included any unusual or episodic events that could affect cabin air quality. Most studies have used scientifically sound methods for measurements. Study results indicate that under routine aircraft operations, contaminant levels in aircraft cabins are similar to those in residential and office buildings, with two exceptions: (1). levels of ethanol and acetone, indicators of bioeffluents and chemicals from consumer products are higher in aircraft than in home or office environments, and (2). levels of certain chlorinated hydrocarbons and fuel-related contaminants are higher in residential/office buildings than in aircraft. Similarly, ethanol and acetone levels are higher in aircraft than in other transportation modes but the levels of some pollutants, such as m-/p-xylenes, tend to be lower in aircraft.
NASA Astrophysics Data System (ADS)
Krieger, Ulrich; Marcolli, Claudia; Siegrist, Franziska
2015-04-01
The production of secondary organic aerosol (SOA) by gas-to-particle partitioning is generally represented by an equilibrium partitioning model. A key physical parameter which governs gas-particle partitioning is the pure component vapor pressure, which is difficult to measure for low- and semivolatile compounds. For typical atmospheric compounds like e.g. citric acid or tartaric acid, vapor pressures have been reported in the literature which differ by up to six orders of magnitude [Huisman et al., 2013]. Here, we report vapor pressures of a homologous series of polyethylene glycols (triethylene glycol to octaethylene glycol) determined by measuring the evaporation rate of single, levitated aerosol particles in an electrodynamic balance. We propose to use those as a reference data set for validating different vapor pressure measurement techniques. With each addition of a (O-CH2-CH2)-group the vapor pressure is lowered by about one order of magnitude which makes it easy to detect the lower limit of vapor pressures accessible with a particular technique down to a pressure of 10-8 Pa at room temperature. Reference: Huisman, A. J., Krieger, U. K., Zuend, A., Marcolli, C., and Peter, T., Atmos. Chem. Phys., 13, 6647-6662, 2013.
Saini, Amandeep; Thaysen, Clara; Jantunen, Liisa; McQueen, Rachel H; Diamond, Miriam L
2016-09-06
The accumulation of phthalate esters, brominated flame retardants (BFRs) and organophosphate esters (OPEs) by clothing from indoor air and transfer via laundering to outdoors were investigated. Over 30 days cotton and polyester fabrics accumulated 3475 and 1950 ng/dm(2) ∑5phthalates, 65 and 78 ng/dm(2) ∑10BFRs, and 1200 and 310 ng/dm(2) ∑8OPEs, respectively. Planar surface area concentrations of OPEs and low molecular weight phthalates were significantly greater in cotton than polyester and similar for BFRs and high molecular weight phthalates. This difference was significantly and inversely correlated with KOW, suggesting greater sorption of polar compounds to polar cotton. Chemical release from cotton and polyester to laundry water was >80% of aliphatic OPEs (log KOW < 4), < 50% of OPEs with an aromatic structure, 50-100% of low molecular weight phthalates (log KOW 4-6), and < detection-35% of higher molecular weight phthalates (log KOW > 8) and BFRs (log KOW > 6). These results support the hypothesis that clothing acts an efficient conveyer of soluble semivolatile organic compounds (SVOCs) from indoors to outdoors through accumulation from air and then release during laundering. Clothes drying could as well contribute to the release of chemicals emitted by electric dryers. The results also have implications for dermal exposure.
Yang, Cui; Zhao, Jinhua; Wang, Juan; Yu, Hongling; Piao, Xiangfan; Li, Donghao
2013-07-26
A novel organic solvent-free mode of gas purge microsyringe extraction, termed water-based gas purge microsyringe extraction, was developed. This technique can directly extract target compounds in wet samples without any drying process. Parameters affecting the extraction efficiency were investigated. Under optimal extraction conditions, the recoveries of alkylphenols were between 87.6 and 105.8%, and reproducibility was between 5.2 and 12.1%. The technique was also used to determine six kinds of alkylphenols (APs) from samples of Laminaria japonica Aresh. The OP and NP were detected in all the samples, and concentrations ranged from 26.0 to 54.5ngg(-1) and 45.0-180.4ngg(-1), respectively. The 4-n-butylphenol was detected in only one sample and its concentration was very low. Other APs were not detected in L. japonica Aresh samples. The experimental results demonstrated that the technique is fast, simple, non-polluting, allows for quantitative extraction, and a drying process was not required for wet samples. Since only aqueous solution and a conventional microsyringe were used, this technique proved affordable, efficient, and convenient for the extraction of volatile and semivolatile ionizable compounds. Copyright © 2013 Elsevier B.V. All rights reserved.
Synthetic musk fragrances in urban and rural air of Iowa and the Great Lakes
NASA Astrophysics Data System (ADS)
Peck, Aaron M.; Hornbuckle, Keri C.
Synthetic musk fragrances are semivolatile organic compounds used to scent a variety of household and personal care products. In this study, six polycyclic musk fragrances (HHCB, AHTN, ATII, AHMI, ADBI, and DPMI) and two nitro musk fragrances (musk xylene and musk ketone) were evaluated in 181 air samples collected at urban, suburban, and rural sites in Iowa and the Great Lakes. This is the largest reported study of the compounds in ambient air and reveals the ubiquitous nature of these environmental contaminants. HHCB and AHTN were detected most frequently and at the highest concentrations at all sites. Synthetic musk fragrance concentrations were highest in urban locations, including Milwaukee, WI (previously reported) and an urban location in Cedar Rapids, IA. Urban concentrations of HHCB and AHTN are on the order of 1-5 ng m -3 and background terrestrial concentrations are about an order of magnitude less. In rural Iowa, the concentrations and frequency of detection of the synthetic musk fragrances are comparable to (and often greater than) gas-phase pesticide concentrations. The concentrations measured at the suburban location in Iowa City, IA and over the Lakes Erie, Ontario, and Michigan were generally intermediate of those measured at the rural and urban locations. Concentrations of HHCB and AHTN were correlated with temperature at the sampling sites in Iowa.
Woolfenden, Elizabeth
2010-04-16
Sorbent tubes/traps are widely used in combination with gas chromatographic (GC) analytical methods to monitor the vapour-phase fraction of organic compounds in air. Applications range from atmospheric research and ambient air monitoring (indoor and outdoor) to occupational hygiene (personal exposure assessment) and measuring chemical emission levels. Part 1 of this paper reviewed the main sorbent-based air sampling strategies including active (pumped) tube monitoring, diffusive (passive) sampling onto sorbent tubes/cartridges plus sorbent trapping/focusing of whole air samples that are either collected in containers (such as canisters or bags) or monitored online. Options for subsequent extraction and transfer to GC(MS) analysis were also summarised and the trend to thermal desorption (TD)-based methods and away from solvent extraction was explained. As a result of this trend, demand for TD-compatible sorbents (alternatives to traditional charcoal) is growing. Part 2 of this paper therefore continues with a summary of TD-compatible sorbents, their respective advantages and limitations and considerations for sorbent selection. Other analytical considerations for optimizing sorbent-based air monitoring methods are also discussed together with recent technical developments and sampling accessories which have extended the application range of sorbent trapping technology generally. Copyright 2010 Elsevier B.V. All rights reserved.
Frenzel, Steven A.
2000-01-01
Organochlorines, semivolatile organic compounds (SVOCs), and trace elements were investigated in streambed sediments and fish tissues at selected sites in the Cook Inlet Basin, Alaska, during 1998. At most sites, SVOCs and organochlorine compounds were either not detected or detected at very low concentrations. Chester Creek at Arctic Boulevard at Anchorage, which was the only site sampled with a significant degree of development in the watershed, had elevated levels of many SVOCs in streambed sediment. Coring of sediments from two ponds on Chester Creek confirmed the presence of elevated concentrations of a variety of organic compounds. Moose Creek, a stream with extensive coal deposits in its watershed, had low concentrations of numerous SVOCs in streambed sediment. Three sites located in national parks or in a national wildlife refuge had no detectable concentrations of SVOCs. Trace elements were analyzed in both streambed sediments and tissues of slimy sculpin. The two media provided similar evidence for elevated concentrations of cadmium, lead, and zinc at Chester Creek. In this study, 'probable effect levels '(PELs) were determined from sediments finer than 0.063 millimeters, where concentrations tend to be greatest. Arsenic and chromium concentrations exceeded the PEL at eight and six sites respectively. Zinc exceeded the PEL at one site. Cadmium and copper concentrations were smaller than the PEL at all sites. Mercury concentrations in streambed sediments from the Deshka River were near the PEL, and selenium concentrations at that site also appear to be elevated above background levels. At half the sites where slimy sculpin were sampled, selenium concentrations were at levels that may cause adverse effects in some species.
Qin, Yan; Pang, Yingming; Cheng, Zhihong
2016-11-01
The needle trap device (NTD) technique is a new microextraction method for sampling and preconcentration of volatile organic compounds (VOCs). Previous NTD studies predominantly focused on analysis of environmental volatile compounds in the gaseous and liquid phases. Little work has been done on its potential application in biological samples and no work has been reported on analysis of bioactive compounds in essential oils from herbal medicines. The main purpose of the present study is to develop a NTD sampling method for profiling VOCs in biological samples using herbal medicines as a case study. A combined method of NTD sample preparation and gas chromatography-mass spectrometry was developed for qualitative analysis of VOCs in Viola tianschanica. A 22-gauge stainless steel, triple-bed needle packed with Tenax, Carbopack X and Carboxen 1000 sorbents was used for analysis of VOCs in the herb. Furthermore, different parameters affecting the extraction efficiency and capacity were studied. The peak capacity obtained by NTDs was 104, more efficient than those of the static headspace (46) and hydrodistillation (93). This NTD method shows potential to trap a wide range of VOCs including the lower and higher volatile components, while the static headspace and hydrodistillation only detects lower volatile components, and semi-volatile and higher volatile components, respectively. The developed NTD sample preparation method is a more rapid, simpler, convenient, and sensitive extraction/desorption technique for analysis of VOCs in herbal medicines than the conventional methods such as static headspace and hydrodistillation. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.
Particle growth kinetics over the Amazon rainforest
NASA Astrophysics Data System (ADS)
Pinterich, T.; Andreae, M. O.; Artaxo, P.; Kuang, C.; Longo, K.; Machado, L.; Manzi, A. O.; Martin, S. T.; Mei, F.; Pöhlker, C.; Pöhlker, M. L.; Poeschl, U.; Shilling, J. E.; Shiraiwa, M.; Tomlinson, J. M.; Zaveri, R. A.; Wang, J.
2016-12-01
Aerosol particles larger than 100 nm play a key role in global climate by acting as cloud condensation nuclei (CCN). Most of these particles, originated from new particle formation or directly emitted into the atmospheric, are initially too small to serve as CCN. These small particles grow to CCN size mainly through condensation of secondary species. In one extreme, the growth is dictated by kinetic condensation of very low-volatility compounds, favoring the growth of the smallest particles; in the other extreme, the process is driven by Raoult's law-based equilibrium partitioning of semi-volatile organic compound, favoring the growth of larger particles. These two mechanisms can lead to very different production rates of CCN. The growth of particles depends on a number of parameters, including the volatility of condensing species, particle phase, and diffusivity inside the particles, and this process is not well understood in part due to lack of ambient data. Here we examine atmospheric particle growth using high-resolution size distributions measured onboard the DOE G-1 aircraft during GoAmazon campaign, which took place from January 2014 to December 2015 near Manaus, Brazil, a city surrounded by natural forest for over 1000 km in every direction. City plumes are clearly identified by the strong enhancement of nucleation and Aitken mode particle concentrations over the clean background. As the plume traveled downwind, particle growth was observed, and is attributed to condensation of secondary species and coagulation (Fig.1). Observed aerosol growth is modeled using MOSAIC (Model for Simulating Aerosol Interactions and Chemistry), which dynamically partitions multiple compounds to all particle size bins by taking into account compound volatility, gas-phase diffusion, interfacial mass accommodation, particle-phase diffusion, and particle-phase reaction. The results from both wet and dry seasons will be discussed.
Heating of solid earthen material, measuring moisture and resistivity
Heath, W.O.; Richardson, R.L.; Goheen, S.C.
1994-07-19
The present invention includes a method of treating solid earthen material having volatile, semi-volatile, and non-volatile contaminants. Six electrodes are inserted into a region of earthen material to be treated in a substantially equilateral hexagonal arrangement. Six phases of voltages are applied to corresponding electrodes. The voltages are adjusted within a first range of voltages to create multiple current paths between pairs of the electrodes. The current paths are evenly distributed throughout the region defined by the electrodes and therefore uniformly heat the region. The region of earthen material is heated to a temperature sufficient to substantially remove volatile and semi-volatile contaminants by promoting microbial action. This temperature is less than a melting temperature of the earthen material. 13 figs.
Heating of solid earthen material, measuring moisture and resistivity
Heath, William O.; Richardson, Richard L.; Goheen, Steven C.
1994-01-01
The present invention includes a method of treating solid earthen material having volatile, semi-volatile, and non-volatile contaminants. Six electrodes are inserted into a region of earthen material to be treated in a substantially equilateral hexagonal arrangement. Six phases of voltages are applied to corresponding electrodes. The voltages are adjusted within a first range of voltages to create multiple current paths between pairs of the electrodes. The current paths are evenly distributed throughout the region defined by the electrodes and therefore uniformly heat the region. The region of earthen material is heated to a temperature sufficient to substantially remove volatile and semi-volatile contaminants by promoting microbial action. This temperature is less than a melting temperature of the earthen material.
Covay, K.J.; Beck, D.A.
2001-01-01
In May 1998 the U.S. Geological Survey, in cooperation with the University of Nevada, Las Vegas, investigated rates of sediment deposition and concentrations of selected synthetic organic compounds at four sites in Lake Mead. Sediment cores were extracted from two sites (one shallow and one deep) in Las Vegas Bay, from one site in the Overton Arm, and from one site near the historic confluence of the Colorado and Virgin Rivers. The sediment cores were age-dated using cesium-137 and were analyzed for the presence of organochlorine compounds (pesticides and degradation products, polychlorinated biphenyls, dioxins, and furans) and for semivolatile organic compounds (polycyclic aromatic hydrocarbons and phenols). Sediment-deposition rates after impoundment of the Colorado River by Hoover Dam were determined by measuring the accumulation of mass during three different periods: (1) from the approximate impoundment date for each site (1935-37) to the initial occurrence of cesium-137 in the atmosphere (1952); (2) from 1952 to the maximum concentration of cesium-137 in the atmosphere (1964); and (3) from 1964 to the collection date of the sample (1998). Sediment-deposition rates for the entire post-impoundment period (1935-98) averaged 1.45 (g/cm2)/yr (grams per square centimeter per year) at the Las Vegas Bay shallow site, 1.25 (g/cm2)/yr at the Las Vegas Bay deep site, 0.80 (g/cm2)/yr at the Overton Arm site, and 0.65 (g/cm2)/yr at the Colorado and Virgin Rivers confluence site. Sediment-deposition rates after impoundment of the Colorado River by Hoover Dam were determined by measuring the accumulation of mass during three different periods: (1) from the approximate impoundment date for each site (1935-37) to the initial occurrence of cesium-137 in the atmosphere (1952); (2) from 1952 to the maximum concentration of cesium-137 in the atmosphere (1964); and (3) from 1964 to the collection date of the sample (1998). Sediment-deposition rates for the entire post-impoundment period (1935-98) averaged 1.45 (g/cm2)/yr (grams per square centimeter per year) at the Las Vegas Bay shallow site, 1.25 (g/cm2)/yr at the Las Vegas Bay deep site, 0.80 (g/cm2)/yr at the Overton Arm site, and 0.65 (g/cm2)/yr at the Colorado and Virgin Rivers confluence site. Total numbers of synthetic organic compounds detected in sediment samples were 48 at the Las Vegas Bay shallow site, 57 at the Las Vegas Bay deep site, 26 at the Overton Arm site, and 31 at the Colorado and Virgin Rivers confluence site. The most commonly detected organochlorine pesticide and polychlorinated biphenyl compounds were dichlorodiphenyldichloroethane and dichlorodiphenyldichloroethylene. The most commonly detected dioxin compounds were tetrachlorodibenzo-p-dioxin and octochlorodibenzo-p-dioxin. The most commonly detected furan compounds were tetrachlorodibenzofuran and octochlorodibenzofuran. The most commonly detected polycyclic aromatic hydrocarbons included perylene, benzo[g,h,i]perylene, 2,6-dimethylnaphthalene, and indeno[1,2,3-c,d]pyrene. The most commonly detected phenol compound was phenol.
NASA Astrophysics Data System (ADS)
Tasoglou, A.; Ramachandran, S.; Khlystov, A.; Saha, P.; Grieshop, A. P.; Pandis, S. N.
2015-12-01
Secondary organic aerosol (SOA) is a major contributor to the global aerosol burden. Black carbon (BC) is a significant climate warming agent, while light-absorbing organic carbon (brown carbon, BrC), also impacts the atmospheric radiative balance. The optical properties of ambient aerosols can be affected by biogenic SOA through the lensing effect (coating of BC cores by semivolatile SOA), and by the potential formation of BrC from biogenic sources influenced by anthropogenic sources. To evaluate these effects, measurements of ambient aerosol optical properties and BC concentrations were made in rural Centreville, AL (a remote site with little anthropogenic influence) in summer 2013 and at Duke Forest in Chapel Hill, NC (a site close to high density vehicular traffic and industrial sources), during summer 2015. Photoacoustic extinctiometers (PAX, 405 nm and 532 nm) measured particulate light absorption and a single particle soot photometer (SP2) measured BC mass at both locations. A seven-wavelength Aethalometer and a three-wavelength nephelometer were also deployed at Duke Forest. A third PAX (870 nm) was deployed at Centreville. For absorption and BC measurements, the sample was cycled between a dry line and a dry/thermally-denuded line. Hourly samples were collected with a steam jet aerosol collector (SJAC) for online (2013) and offline (2015) chemical composition analysis. BC concentrations were generally higher at Duke Forest compared to the rural Centreville site. The Aethalometer readings at Duke Forest show greater absorption at the shorter wavelengths (370 nm and 470 nm) than expected from the absorption at 880 nm coupled with an inverse wavelength dependence, suggesting the presence of brown carbon. This presentation will examine the evidence for brown carbon at the two sites, as well as the effect of non-BC coatings on BC light absorption (the lensing effect.)