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Sample records for organic compounds measured

  1. Breath measurements as volatile organic compound biomarkers.

    PubMed Central

    Wallace, L; Buckley, T; Pellizzari, E; Gordon, S

    1996-01-01

    A brief review of the uses of breath analysis in studies of environmental exposure to volatile organic compounds (VOCs) is provided. The U.S. Environmental Protection Agency's large-scale Total Exposure Assessment Methodology Studies have measured concentrations of 32 target VOCs in the exhaled breath of about 800 residents of various U.S. cities. Since the previous 12-hr integrated personal air exposures to the same chemicals were also measured, the relation between exposure and body burden is illuminated. Another major use of the breath measurements has been to detect unmeasured pathways of exposure; the major impact of active smoking on exposure to benzene and styrene was detected in this way. Following the earlier field studies, a series of chamber studies have provided estimates of several important physiological parameters. Among these are the fraction, f, of the inhaled chemical that is exhaled under steady-state conditions and the residence times. tau i in several body compartments, which may be associated with the blood (or liver), organs, muscle, and fat. Most of the targeted VOCs appear to have similar residence times of a few minutes, 30 min, several hours, and several days in the respective tissue groups. Knowledge of these parameters can be helpful in estimating body burden from exposure or vice versa and in planning environmental studies, particularly in setting times to monitor breath in studies of the variation with time of body burden. Improvements in breath methods have made it possible to study short-term peak exposure situations such as filling a gas tank or taking a shower in contaminated water. PMID:8933027

  2. MEASUREMENT OF ORGANIC COMPOUND EMISSIONS USING SMALL TEST CHAMBERS

    EPA Science Inventory

    Organic compounds emitted from a variety of indoor materials have been measured using small (166 L) environmental test chambers. The paper discusses: a) factors to be considered in small chamber testing; b) parameters to be controlled; c) the types of results obtained. The follow...

  3. Measurement of organic compound emissions using small test chambers

    SciTech Connect

    Tichenor, B.A.

    1989-01-01

    The paper discusses the measurement of organic emissions from a variety of indoor materials, using small (166 liter) environmental test chambers. The following materials were tested: adhesives, caulks, pressed wood products, floor waxes, paints, and solid insecticides. For each material, chamber concentration of organics has been determined for a range of environmental conditions (e.g., air exchange rate, temperature, and relative humidity). Various product loading ratios (area of sample/volume of chamber) have also been investigated. Emission rates for individual organic compounds, as well as total measured organics, were calculated. The effects of environmental variables on emission rates have been evaluated. Models are used to evaluate the effect of chamber walls and concentration on emission rates.

  4. Measurements of halogenated organic compounds near the tropical tropopause

    NASA Technical Reports Server (NTRS)

    Schauffler, S. M.; Heidt, L. E.; Pollock, W. H.; Gilpin, T. M.; Vedder, J. F.; Solomon, S.; Lueb, R. A.; Atlas, E. L.

    1993-01-01

    The amount of organic chlorine and bromine entering the stratosphere have a direct influence on the magnitude of chlorine and bromine catalyzed ozone losses. Twelve organic chlorine species and five organic bromine species were measured from 12 samples collected near the tropopause between 23.8 deg N and 25.3 deg N during AASE 2. The average mixing ratios of total organic chlorine and total organic bromine were 3.50 +/- 0.06 ppbv and 21.1 +/- 0.8 pptv, respectively. CH3Cl represented 15.1% of the total organic chlorine, with CFC 11 (CCl3F) and CFC 12 (CCl2F2) accounting for 22.6% and 28.2%, respectively, with the remaining 34.1% primarily from CCl4, CH3CCl3, and CFC 113 (CCl2FCClF2). CH3Br represented 54% of the total organic bromine. The 95% confidence intervals of the mixing ratios of all but four of the individual compounds were within the range observed in low and mid-latitude mid-troposphere samples. The four compounds with significantly lower mixing ratios at the tropopause were CHCl3, CH2Cl2, CH2Br2, and CH3CCl3. The lower mixing ratios may be due to entrainment of southern hemisphere air during vertical transport in the tropical region and/or to exchange of air across the tropopause between the lower stratosphere and upper troposphere.

  5. Measurements of Halogenated Organic Compounds near the Tropical Tropopause

    NASA Technical Reports Server (NTRS)

    Schauffler, S. M.; Heidt, L. E.; Pollock, W. H.; Gilpin, T. M.; Vedder, J. F.; Solomon, S.; Leub, R. A.; Atlas, E. L.

    1993-01-01

    The amount of organic chlorine and bromine entering the stratosphere have a direct influence on the magnitude of chlorine and bromine catalyzed ozone losses. Twelve organic chlorine species and five organic bromine species were measured from 12 samples collected near the tropopause between 23.8 deg N and 25.3 deg N during AASE 2. The average mixing ratios of total organic chlorine and total organic bromine were 3.50 +/- 0.06 ppbv and 21.1 +/- 0.8 pptv, respectively. CH3Cl represented 15.1% of the total organic chlorine, with CFC 11 (CCl3F) and CFC 12 (CCl2F2) accounting for 22.6% and 28.2%, respectively, with the remaining 34.1% primarily from CCl4, CH3CCl3, and CFC 113 (CCl2FCClF2). CH3Br represented 54% of the total organic bromine. The 95% confidence intervals of the mixing ratios of all but four of the individual compounds were within the range observed in low and mid-latitude midtroposphere samples. The four compounds with significantly lower mixing ratios at the tropopause were CHCl3, CH2Cl2, CH2Br2, and CH3CCl3. The lower mixing ratios may be due to entrainment of southern hemisphere air during vertical transport in the tropical region and/or to exchange of air across the tropopause between the lower stratosphere and upper troposphere.

  6. MEASUREMENT OF VAPOR PHASE ORGANIC COMPOUNDS AT HIGH CONCENTRATIONS

    EPA Science Inventory

    Laboratory, industrial, chemical, or other waste products may have constituents that evolve volatile organic compounds (VOCS) at very high concentrations. hese could pose human health risks during handling, storage, and disposal of the waste through inhalation, dermal exposure, o...

  7. VOLATILE ORGANIC COMPOUNDS MEASURED IN DEARS PASSIVE SAMPLERS

    EPA Science Inventory

    A suite of 27 volatile organic compounds (VOCs) were monitored in personal exposures, indoors and outdoors of participant's residences, and at a central community site during the DEARS summer 2004 monitoring season. The list of VOCs focused on compounds typically associated with ...

  8. Measuring concentrations of volatile organic compounds in vinyl flooring.

    PubMed

    Cox, S S; Little, J C; Hodgson, A T

    2001-08-01

    The initial solid-phase concentration of volatile organic compounds (VOCs) is a key parameter influencing the emission characteristics of many indoor materials. Solid-phase measurements are typically made using solvent extraction or thermal headspace analysis. The high temperatures and chemical solvents associated with these methods can modify the physical structure of polymeric materials and, consequently, affect mass transfer characteristics. To measure solid-phase concentrations under conditions resembling those in which the material would be installed in an indoor environment, a new technique was developed for measuring VOC concentrations in vinyl flooring (VF) and similar materials. A 0.09-m2 section of new VF was punched randomly to produce -200 0.78-cm2 disks. The disks were milled to a powder at -140 degrees C to simultaneously homogenize the material and reduce the diffusion path length without loss of VOCs. VOCs were extracted from the VF particles at room temperature by fluidized-bed desorption (FBD) and by direct thermal desorption (DTD) at elevated temperatures. The VOCs in the extraction gas from FBD and DTD were collected on sorbent tubes and analyzed by gas chromatography/mass spectrometry (GC/MS). Seven VOCs emitted by VF were quantified. Concentration measurements by FBD ranged from 5.1 microg/g VF for n-hexadecane to 130 microg/g VF for phenol. Concentrations measured by DTD were higher than concentrations measured by FBD. Differences between FBD and DTD results may be explained using free-volume and dual-mobility sorption theory, but further research is necessary to more completely characterize the complex nature of a diffusant in a polymer matrix. PMID:11518293

  9. Measurements of volatile organic compounds over West Africa

    NASA Astrophysics Data System (ADS)

    Murphy, J. G.; Oram, D. E.; Reeves, C. E.

    2010-06-01

    In this paper we describe measurements of volatile organic compounds (VOC) made using a Proton Transfer Reaction Mass Spectrometer (PTR-MS) aboard the UK Facility for Atmospheric Airborne Measurements during the African Monsoon Multidisciplinary Analyses (AMMA) campaign. Observations were made during approximately 85 h of flying time between 17 July and 17 August 2006, above an area between 4° N and 18° N and 3° W and 4° E, encompassing ocean, mosaic forest, and the Sahel desert. High time resolution observations of counts at mass to charge (m/z) ratios of 42, 59, 69, 71, and 79 were used to calculate mixing ratios of acetonitrile, acetone, isoprene, the sum of methyl vinyl ketone and methacrolein, and benzene respectively using laboratory-derived humidity-dependent calibration factors. Strong spatial associations between vegetation and isoprene and its oxidation products were observed in the boundary layer, consistent with biogenic emissions followed by rapid atmospheric oxidation. Acetonitrile, benzene, and acetone were all enhanced in airmasses which had been heavily influenced by biomass burning. Benzene and acetone were also elevated in airmasses with urban influence from cities such as Lagos, Cotonou, and Niamey. The observations provide evidence that both deep convection and mixing associated with fair-weather cumulus were responsible for vertical redistribution of VOC emitted from the surface. Profiles over the ocean showed a depletion of acetone in the marine boundary layer, but no significant decrease for acetonitrile.

  10. Measurements of volatile organic compounds over West Africa

    NASA Astrophysics Data System (ADS)

    Murphy, J. G.; Oram, D. E.; Reeves, C. E.

    2010-02-01

    In this paper we describe measurements of volatile organic compounds (VOCs) made using a Proton Transfer Reaction Mass Spectrometer (PTR-MS) aboard the UK Facility for Atmospheric Airborne Measurements during the African Monsoon Multidisciplinary Analyses (AMMA) campaign. Observations were made during approximately 85 h of flying time between 17 July and 17 August 2006, above an area between 4° N and 18° N and 3° W and 4° E, encompassing ocean, mosaic forest, and the Sahel desert. High time resolution observations of counts at mass to charge (m/z) ratios of 42, 59, 69, 71, and 79 were used to calculate mixing ratios of acetonitrile, acetone, isoprene, the sum of methyl vinyl ketone and methacrolein, and benzene, respectively using laboratory-derived humidity-dependent calibration factors. Strong spatial associations between vegetation and isoprene and its oxidation products were observed in the boundary layer, consistent with biogenic emissions followed by rapid atmospheric oxidation. Acetonitrile, benzene, and acetone were all enhanced in airmasses which had been heavily influenced by biomass burning. Benzene and acetone were also elevated in airmasses with urban influence from cities such as Lagos, Cotonou, and Niamey. The observations provide evidence that both deep convection and mixing associated with fair-weather cumulus were responsible for vertical redistribution of VOCs emitted from the surface. Profiles over the ocean showed a depletion of acetone in the marine boundary layer, but no significant decrease for acetonitrile.

  11. Measuring Emissions of Volatile Organic Compounds from Silage

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Volatile organic compound (VOC) emissions are considered to be important precursors to smog and ozone production. An experimental protocol was developed to obtain undisturbed silage samples from silage storages. Samples were placed in a wind tunnel where temperature, humidity, and air flow were cont...

  12. Airborne flux measurements of biogenic volatile organic compounds over California

    NASA Astrophysics Data System (ADS)

    Misztal, P. K.; Karl, T.; Weber, R.; Jonsson, H. H.; Guenther, A. B.; Goldstein, A. H.

    2014-03-01

    Biogenic Volatile Organic Compound (BVOC) fluxes were measured onboard the CIRPAS Twin Otter aircraft as part of the California Airborne BVOC Emission Research in Natural Ecosystem Transects (CABERNET) campaign during June 2011. The airborne virtual disjunct eddy covariance (AvDEC) approach used measurements from a PTR-MS and a wind radome probe to directly determine fluxes of isoprene, MVK + MAC, methanol, monoterpenes, and MBO over ∼10 000 km of flight paths focusing on areas of California predicted to have the largest emissions of isoprene. The Fast Fourier Transform (FFT) approach was used to calculate fluxes over long transects of more than 15 km, most commonly between 50 and 150 km. The Continuous Wavelet Transformation (CWT) approach was used over the same transects to also calculate "instantaneous" fluxes with localization of both frequency and time independent of non-stationarities. Vertical flux divergence of isoprene is expected due to its relatively short lifetime and was measured directly using "racetrack" profiles at multiple altitudes. It was found to be linear and in the range 5% to 30% depending on the ratio of aircraft altitude to PBL height (z / zi). Fluxes were generally measured by flying consistently at 400 ± 50 m (a.g.l.) altitude, and extrapolated to the surface according to the determined flux divergence. The wavelet-derived surface fluxes of isoprene averaged to 2 km spatial resolution showed good correspondence to Basal Emission Factor (BEF) landcover datasets used to drive biogenic VOC (BVOC) emission models. The surface flux of isoprene was close to zero over Central Valley crops and desert shrublands, but was very high (up to 15 mg m-2 h-1) above oak woodlands, with clear dependence of emissions on temperature and oak density. Isoprene concentrations of up to 8 ppb were observed at aircraft height on the hottest days and over the dominant source regions. While isoprene emissions from agricultural crop regions, shrublands, and

  13. MEASUREMENT OF ORGANIC COMPOUND EMISSIONS USING SMALL TEST CHAMBERS

    EPA Science Inventory

    The paper discusses the measurement of organic emissions from a variety of indoor materials, using small (166 liter) environmental test chambers. he following materials were tested: adhesives, caulks, pressed wood products, floor waxes, paints, and solid insecticides. or each mat...

  14. Maximizing Information from Residential Measurements of Volatile Organic Compounds

    SciTech Connect

    Maddalena, Randy; Li, Na; Hodgson, Alfred; Offermann, Francis; Singer, Brett

    2013-02-01

    Continually changing materials used in home construction and finishing can introduce new chemicals or changes in the VOC profile in residential air and the trend towards tighter homes can lead to higher exposure concentrations for many indoor sources. However, the complex mixture of VOCs in residential air makes it difficult to discover emerging contaminants and/or trends in pollutant profiles. The purpose of this study is to prepare a comprehensive library of chemicals found in homes, along with a semi-quantitative approach to maximize the information gained from VOC measurements. We carefully reviewed data from 108 new California homes and identified 238 individual compounds. The majority of the identified VOCs originated indoors. Only 31% were found to have relevant health based exposure guidelines and less than 10% had a chronic reference exposure level (CREL). The finding highlights the importance of extending IAQ studies to include a wider range of VOCs

  15. ORGANIC COMPOUNDS MEASURED IN PM2.5 DURING NEOPS

    EPA Science Inventory

    Secondary formation of submicron ambient particulate matter occurs when organic and inorganic constituents having sufficiently low volatility condense onto preexisting particles in the atmosphere. The presence of the resulting submicron particles has led to three important env...

  16. MEASUREMENT OF POLYCYCLIC ORGANIC MATERIALS AND OTHER HAZARDOUS ORGANIC COMPOUNDS IN STACK GASES - STATE OF THE ART

    EPA Science Inventory

    This report documents and reviews state-of-the-art methods for the measurement of polycyclic organic matter (POM) and other hazardous organic materials which are present in industrial stack emissions. Measurement methods for many hazardous compounds, such as POM and nitrosamines,...

  17. Laboratory and field screening strategies for measuring volatile organic compounds in landfill gas

    SciTech Connect

    Emerson, C.W.

    1999-11-01

    Distinct patterns often exist in the presence and absence of hazardous contaminants in the environment. These patterns can be used to select efficient screening tools, or groups of compounds that provide the most information on overall occurrences of a larger target group of compounds. By using these screens to indicate whether a sample is contaminated with detectable amounts of the compounds of interest, attention can be focused on those samples considered most likely to contain measurable concentrations of targeted compounds. The cost savings that result from eliminating samples that are most likely uncontaminated can be applied to obtaining additional samples that more accurately characterize the spatial or temporal variability of the environmental problem. In a retrospective application of screening techniques to the State of California's database of volatile organic compounds in landfill gas, two laboratory screening compounds, perchloroethylene and methylene chloride, represent over 95% of the total number of positive detections of a target group of 10 volatile organic compounds. Benzene and vinyl chloride, two field screening compounds that were selected using the characteristics of commercially available colorimetric detector tubes, recorded 74% of the total contaminant detections and a 52% savings in analytical costs as compared to an exhaustive analysis of every sample for all 10 volatile organic compounds. The number of detections recorded could have been improved if more sensitive and less selective field screening devices were available.

  18. LEAF, BRANCH, STAND & LANDSCAPE SCALE MEASUREMENTS OF VOLATILE ORGANIC COMPOUND FLUXES FROM U.S. WOODLANDS

    EPA Science Inventory

    Natural volatile organic compounds (VOC) fluxes were measured in three U.S. woodlands in summer 1993. Fluxes from individual leaves and branches were estimated with enclosure techniques and used to initialize and evaluate VOC emission model estimates. Ambient measurements were us...

  19. MEASUREMENTS OF VOLATILE ORGANIC COMPOUNDS AND PARTICLES DURING APPLICATION OF LATEX PAINT WITH AN AIRLESS SPRAYER

    EPA Science Inventory

    The paper discusses experiments, conducted at EPA's Indoor Air Quality Research House, to measure airborne concentrations of volatile organic compounds (VOCs) and particles during and following the spray-application of latex wall paint. (NOTE: Paint may be applied indoors by a v...

  20. LONG-PATH FTIR MEASUREMENTS OF VOLATILE ORGANIC COMPOUNDS IN AN INDUSTRIAL SETTING

    EPA Science Inventory

    As part of a Superfund Innovative Technology Evaluation (SITE) field program, a Fourier transform infrared (FTIR) spectrometer vas used to make open path measurements of volatile organic compounds in the New Castle, Delaware, area. he SITE program requires that new technologies b...

  1. RT-MATRIX: Measuring Total Organic Carbon by Photocatalytic Oxidation of Volatile Organic Compounds

    NASA Technical Reports Server (NTRS)

    2008-01-01

    Volatile organic compounds (VOCs) inevitably accumulate in enclosed habitats such as the International Space Station and the Crew Exploration Vehicle (CEV) as a result of human metabolism, material off-gassing, and leaking equipment. Some VOCs can negatively affect the quality of the crew's life, health, and performance; and consequently, the success of the mission. Air quality must be closely monitored to ensure a safe living and working environment. Currently, there is no reliable air quality monitoring system that meets NASA's stringent requirements for power, mass, volume, or performance. The ultimate objective of the project -- the development of a Real-Time, Miniaturized, Autonomous Total Risk Indicator System (RT.MATRIX).is to provide a portable, dual-function sensing system that simultaneously determines total organic carbon (TOC) and individual contaminants in air streams.

  2. Performance audits and laboratory comparisons for SCOS97-NARSTO measurements of speciated volatile organic compounds

    NASA Astrophysics Data System (ADS)

    Fujita, Eric M.; Harshfield, Gregory; Sheetz, Laurence

    Performance audits and laboratory comparisons were conducted as part of the quality assurance program for the 1997 Southern California Ozone Study (SCOS97-NARSTO) to document potential measurement biases among laboratories measuring speciated nonmethane hydrocarbons (NMHC), carbonyl compounds, halogenated compounds, and biogenic hydrocarbons. The results show that measurements of volatile organic compounds (VOC) made during SCOS97-NARSTO are generally consistent with specified data quality objectives. The hydrocarbon comparison involved nine laboratories and consisted of two sets of collocated ambient samples. The coefficients of variation among laboratories for the sum of the 55 PAM target compounds and total NMHC ranged from ±5 to 15 percent for ambient samples from Los Angeles and Azusa. Abundant hydrocarbons are consistently identified by all laboratories, but discrepancies occur for olefins greater than C 4 and for hydrocarbons greater than C 8. Laboratory comparisons for halogenated compounds and biogenic hydrocarbons consisted of both concurrent ambient sampling by different laboratories and round-robin analysis of ambient samples. The coefficients of variation among participating laboratories were about 10-20 percent. Performance audits were conducted for measurement of carbonyl compounds involving sampling from a standard mixture of carbonyl compounds. The values reported by most of the laboratories were within 10-20 percent of those of the reference laboratory. Results of field measurement comparisons showed larger variations among the laboratories ranging from 20 to 40 percent for C 1-C 3 carbonyl compounds. The greater variations observed in the field measurement comparison may reflect potential sampling artifacts, which the performance audits did not address.

  3. Volatile organic compound measurements in the California/Mexico border region during SCOS97

    SciTech Connect

    Zielinska, B.; Sagebiel, J.; Uberna, E.; Harshfield, G.; Pasek, R.

    1999-07-01

    Measurements of volatile organic compounds (VOC) were carried out in the California/Mexico border region during the Southern California Ozone study in the Summer of 1997 (SCOS97). Integrated 3-hr samples were collected in Rosarito (south of Tijuana, Mexico) and in Mexicali during Intensive Operational Periods (IOP), twice per IOP day. VOC were collected using stainless-steel 6 L canisters; carbonyl compounds were collected using 2,4-dinitrophenylhydrazine (DNPH) impregnated C{sub 18} SepPak cartridges. The canister samples were analyzed for speciated volatile hydrocarbons (C{sub 2}-C{sub 12}), CO, CO{sub 2}, CH{sub 4}, MTBE, and halogenated hydrocarbons. DNPH-impregnated cartridges were analyzed for fourteen C{sub 1}-C{sub 7} carbonyl compounds. The results of these measurements will be discussed.

  4. Polarimeter with linear response for measuring optical activity in organic compounds

    NASA Astrophysics Data System (ADS)

    Flores, Jorge L.; Montoya, Marcial; Garcia-Torales, G.; Gonzalez Alvarez, Alejandro

    2005-08-01

    A polarimeter designed for measuring small rotation angles on the polarization plane of light is described. The experimental device employs one fixed polarizer and a rotating analyzer. The system generates a periodical intensity signal, which is then Fourier analyzed. The coefficients of Fourier Transform contain information about rotation angles produced by organic compounds that exhibited optical activity. The experimental device can be used to determine the sugar concentration in agave juice.

  5. Solid phase microextraction: measurement of volatile organic compounds (VOCs) in Dhaka City air pollution.

    PubMed

    Hussam, A; Alauddin, M; Khan, A H; Chowdhury, D; Bibi, H; Bhattacharjee, M; Sultana, S

    2002-08-01

    A solid phase microextraction (SPME) technique was applied for the sampling of volatile organic compounds (VOCs) in ambient air polluted by two stroke autorickshaw engines and automobile exhausts in Dhaka city, Bangladesh. Analysis was carried out by capillary gas chromatography (GC) and GC-mass spectrometry (MS). The methodology was tested by insitu sampling of an aromatic hydrocarbon mixture gas standard with a precision of +/-5% and an average accuracy of 1-20%. The accuracy for total VOCs concentration measurement was about 7%. VOC's in ambient air were collected by exposing the SPME fiber at four locations in Dhaka city. The chromatograms showed signature similar to that of unburned gasoline (petrol) and weathered diesel containing more than 200 organic compounds; some of these compounds were positively identified. These are normal hydrocarbons pentane (n-C5H2) through nonacosane (n-C29H60), aromatic hydrocarbons: benzene, toluene, ethylbenzene, n-propylbenzene, n-butylbenzene, 1,3,5-trimethylbenzene, xylenes, and 1-isocyanato-3-methoxybenzene. Two samples collected near an autorickshaw station contained 783000 and 1479000 microg/m3 of VOCs. In particular, the concentration of toluene was 50-100 times higher than the threshold limiting value of 2000 microg/m3. Two other samples collected on street median showed 135000 microg/m3 and 180000 microg/m3 of total VOCs. The method detection limit of the technique for most semi-volatile organic compounds was 1 microg/m3. PMID:15328688

  6. Evaluation of NO+ reagent ion chemistry for online measurements of atmospheric volatile organic compounds

    NASA Astrophysics Data System (ADS)

    Koss, Abigail R.; Warneke, Carsten; Yuan, Bin; Coggon, Matthew M.; Veres, Patrick R.; de Gouw, Joost A.

    2016-07-01

    NO+ chemical ionization mass spectrometry (NO+ CIMS) can achieve fast (1 Hz and faster) online measurement of trace atmospheric volatile organic compounds (VOCs) that cannot be ionized with H3O+ ions (e.g., in a PTR-MS or H3O+ CIMS instrument). Here we describe the adaptation of a high-resolution time-of-flight H3O+ CIMS instrument to use NO+ primary ion chemistry. We evaluate the NO+ technique with respect to compound specificity, sensitivity, and VOC species measured compared to H3O+. The evaluation is established by a series of experiments including laboratory investigation using a gas-chromatography (GC) interface, in situ measurement of urban air using a GC interface, and direct in situ measurement of urban air. The main findings are that (1) NO+ is useful for isomerically resolved measurements of carbonyl species; (2) NO+ can achieve sensitive detection of small (C4-C8) branched alkanes but is not unambiguous for most; and (3) compound-specific measurement of some alkanes, especially isopentane, methylpentane, and high-mass (C12-C15) n-alkanes, is possible with NO+. We also demonstrate fast in situ chemically specific measurements of C12 to C15 alkanes in ambient air.

  7. Volatile organic compounds in the marine troposphere and surface oceans: methods, measurements and biogeochemical implications

    NASA Astrophysics Data System (ADS)

    Hudson, Edward

    2010-09-01

    Volatile organic compounds (VOCs), among them non-methane hydrocarbons (NMHCs) and low molecular weight carbonyl compounds (aldehydes and ketones), affect the oxidative capacity of the atmosphere and thus pollutant lifetimes and global climate. VOCs in the surface oceans may be transported into, or derived from, the atmosphere. This thesis describes the development and optimization of chromatographic and preconcentration methods to determine volatile organic compounds (VOCs) in surface seawater and marine air, and their use to explore VOC distribution and fluxes at the seaair interface. It includes the first measurements of many carbonyl compounds in temperate and subarctic marine waters and the first estimates of fluxes of several aldehydes from the ocean surface into the marine atmosphere. Sea surface air, size-fractionated marine aerosols, and surface ocean water dissolved organic matter were simultaneously sampled in the Nordic seas. Nineteen C2-C7 NMHCs were quantified in the air samples. Site-to-site variability in NMHC concentrations was high, suggesting variable, local sources. The aerosols consisted mainly of inorganic marine material, but a culturable bacterium identified as Micrococcus luteus was also isolated from the 9.9 -- 18 mum fraction, suggesting organic matter may be transferred from the surface oceans to the atmosphere by marine aerosols. Lastly, a number of VOCs, including acetone, were detected in the seawater samples using solid-phase microextraction (SPME), leading to the subsequent development of an SPME application for carbonyl compounds in seawater. A mobile, economical and solventless method for the detection and quantification of carbonyl compounds in seawater, a matrix of global importance, was developed. The compounds were derivatized using O-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine (PFBHA)and then pre-concentrated by SPME for gas chromatography with mass spectrometric (GC/MS) or flame ionization (GC-FID) detection. The method was

  8. Determining Source Strength of Semivolatile Organic Compounds using Measured Concentrations in Indoor Dust

    PubMed Central

    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

  9. Measurements of biogenic non-methane organic compound emissions from grasslands

    SciTech Connect

    Fukui, Yoshiko

    1994-12-31

    Non-methane organic compounds (NMOCs) play an important role in the formation of photochemical oxidants in the troposphere. NMOCs originate from both anthropogenic and biogenic sources. Many organic compounds of biogenic origins are more reactive than those of anthropogenic origin because of the presence of internal double bonds within their molecular structure. The objective of this investigation was to examine the seasonal variation of NMOC emissions from grasslands and determine the environmental factors that control the emissions. An enclosure system was chosen as the most appropriate sampling technique for measuring emissions from herbaceous vegetation, and an analysis method using cryogenic preconcentration/high resolution gas chromatography was established. Emission rates were measured at a fixed location in a natural grassland during 1992 and 1993. Measurements were also made at various locations within the same site where the vegetation was harvested after the emission rates were determined. Emission rates of NMOCs for grasslands are not as large as those reported for forests. However the emissions of oxygenated hydrocarbons exceeded the emissions of monoterpenes and have not previously been identified as important forest-type emissions. A framework for parameterizing the NMOC emissions from grasslands based on seasonal and instantaneous variations of the emission rate measurements was developed. Temperature, hypoxia induced by water saturated soil, and frost were key environmental factors affecting both the composition and magnitude of NMOC emissions.

  10. Measurements of semi-volatile organic compounds in settled dust: influence of storage temperature and duration.

    PubMed

    Blanchard, O; Mercier, F; Ramalho, O; Mandin, C; Le Bot, B; Glorennec, P

    2014-04-01

    Indoor dust samples cannot always be analyzed immediately after collection. However, little information is currently available on how storage conditions may affect measurements. This study was designed to determine how sample storage conditions may affect the concentration of semi-volatile organic compounds (SVOCs) in the dust. A composite dust was prepared using a Standard Reference Material (SRM 2585) with real indoor dust samples. The composite dust was stored in various types of packaging, at different temperatures (-18°C, 5°C, 20°C, and 35°C), and in different light conditions. The concentration of SVOCs was measured after various storage durations. No effect on SVOC concentrations was observed for the composite dust stored in an amber glass vial at -18°C for 36 months. At 5°C, 20°C, and 35°C, losses occurred for the more volatile compounds. The experimental storage conditions clearly showed that temperature and duration affected the concentrations of SVOCs in the composite dust. The type of packaging material (polyethylene zip bag or polyethylene garbage bag) did not seem to have a systematic effect on the preservation of SVOCs in the composite dust. Maximum storage duration times are proposed for each compound at various temperatures. For most compounds, samples can be stored for 2 months at 20°C. For samples that cannot be analyzed immediately, we recommend to store them in the dark at -18°C to ensure a good recovery of all tested compounds. PMID:24033516

  11. Flux of organic compounds from grass measured by relaxed eddy accumulation technique.

    PubMed

    Olofsson, Marcus; Ek-Olausson, Birgitta; Ljungström, Evert; Langer, Sarka

    2003-12-01

    Fluxes of some Volatile Organic Compounds (VOC) from grass were measured at a golf course in western Sweden, using the Relaxed Eddy Accumulation (REA) technique. The sampling was done by collecting VOC onto adsorbent tubes and the analysis was performed by thermal desorption followed by GC/MS. High emissions were observed after cutting. Transient fluxes of (Z)-3-hexenyl acetate (0.51 microg m(-2) s(-1)), (Z)-3-hexen-1-ol (0.14 microg m(-2) s(-1)) and (Z)-3-hexenal (0.40 microg m(-2) s(-1)) were measured, even at low temperatures. The REA technique requires a relatively large fetch area that is sometimes not available. Therefore, a procedure for correcting measured fluxes from a limited fetch is suggested. PMID:14710940

  12. Emissions of volatile organic compounds inferred from airborne flux measurements over a megacity

    NASA Astrophysics Data System (ADS)

    Karl, T.; Apel, E.; Hodzic, A.; Riemer, D. D.; Blake, D. R.; Wiedinmyer, C.

    2009-01-01

    Toluene and benzene are used for assessing the ability to measure disjunct eddy covariance (DEC) fluxes of Volatile Organic Compounds (VOC) using Proton Transfer Reaction Mass Spectrometry (PTR-MS) on aircraft. Statistically significant correlation between vertical wind speed and mixing ratios suggests that airborne VOC eddy covariance (EC) flux measurements using PTR-MS are feasible. City-median midday toluene and benzene fluxes are calculated to be on the order of 14.1±4.0 mg/m2/h and 4.7±2.3 mg/m2/h, respectively. For comparison the adjusted CAM2004 emission inventory estimates toluene fluxes of 10 mg/m2/h along the footprint of the flight-track. Wavelet analysis of instantaneous toluene and benzene measurements during city overpasses is tested as a tool to assess surface emission heterogeneity. High toluene to benzene flux ratios above an industrial district (e.g. 10-15 g/g) including the International airport (e.g. 3-5 g/g) and a mean flux (concentration) ratio of 3.2±0.5 g/g (3.9±0.3 g/g) across Mexico City indicate that evaporative fuel and industrial emissions play an important role for the prevalence of aromatic compounds. Based on a tracer model, which was constrained by BTEX (BTEX- Benzene/Toluene/Ethylbenzene/m, p, o-Xylenes) compound concentration ratios, the fuel marker methyl-tertiary-butyl-ether (MTBE) and the biomass burning marker acetonitrile (CH3CN), we show that a combination of industrial, evaporative fuel, and exhaust emissions account for >87% of all BTEX sources. Our observations suggest that biomass burning emissions play a minor role for the abundance of BTEX compounds in the MCMA (2-13%).

  13. Emissions of volatile organic compounds inferred from airborne flux measurements over a megacity

    NASA Astrophysics Data System (ADS)

    Karl, T.; Apel, E.; Hodzic, A.; Riemer, D.; Blake, D.; Wiedinmyer, C.

    2008-07-01

    Toluene and benzene are used for assessing the ability to measure disjunct eddy covariance (DEC) fluxes of Volatile Organic Compounds (VOC) using Proton Transfer Reaction Mass Spectrometry (PTR-MS) on aircraft. Statistically significant correlation between vertical wind speed and mixing ratios suggests that airborne VOC eddy covariance (EC) flux measurements using PTR-MS are feasible. City-average midday toluene and benzene fluxes are calculated to be on the order of 15.5±4.0 mg/m2/h and 4.7±2.3 mg/m2/h respectively. These values argue for an underestimation of toluene and benzene emissions in current inventories used for the Mexico City Metropolitan Area (MCMA). Wavelet analysis of instantaneous toluene and benzene measurements during city overpasses is tested as a tool to assess surface emission heterogeneity. High toluene to benzene flux ratios above an industrial district (e.g. 10 15) including the International airport (e.g. 3 5) and a mean flux (concentration) ratio of 3.2±0.5 (3.9±0.3) across Mexico City indicate that evaporative fuel and industrial emissions play an important role for the prevalence of aromatic compounds. Based on a tracer model, which was constrained by BTEX (Benzene/Toluene/Ethylbenzene/m,p,o-Xylenes) compound concentration ratios, the fuel marker methyl-tertiary-butyl-ether (MTBE) and the biomass burning marker acetonitrile (CH3CN), we show that a combination of industrial, evaporative fuel, and exhaust emissions account for >90% of all BTEX sources. Our observations suggest that biomass burning emissions play a minor role for the abundance of BTEX compounds (0 10%) in the MCMA.

  14. Measurements of Volatile Organic Compounds in a Newly Built Daycare Center

    PubMed Central

    Noguchi, Miyuki; Mizukoshi, Atsushi; Yanagisawa, Yukio; Yamasaki, Akihiro

    2016-01-01

    We measured temporal changes in concentrations of total volatile organic compounds (TVOCs) and individual volatile organic compounds in a newly built daycare center. The temporal changes of the TVOC concentrations were monitored with a photo ionization detector (PID), and indoor air was sampled and analyzed by Gas Chromatography/Mass Spectrometry (GC/MS) and high performance liquid chromatography (HPLC) to determine the concentrations of the constituent VOCs. The measurements were performed just after completion of the building and again 3 months after completion. The TVOC concentration exceeded 1000 µg·m−3 for all the sampling locations just after completion of building, and decreased almost one tenth after 3 months, to below the guideline values of the TVOC in Japan at 400 µg·m−3. The concentrations of the target VOCs of which the indoor concentrations are regulated in Japan were below the guideline values for all the cases. The air-exchange rates were determined based on the temporal changes of the TVOC concentrations, and it was found that the countermeasure to increase the air exchange rate successfully decrease the TVOC concentration level in the rooms. PMID:27455290

  15. Measurements of Volatile Organic Compounds in a Newly Built Daycare Center.

    PubMed

    Noguchi, Miyuki; Mizukoshi, Atsushi; Yanagisawa, Yukio; Yamasaki, Akihiro

    2016-01-01

    We measured temporal changes in concentrations of total volatile organic compounds (TVOCs) and individual volatile organic compounds in a newly built daycare center. The temporal changes of the TVOC concentrations were monitored with a photo ionization detector (PID), and indoor air was sampled and analyzed by Gas Chromatography/Mass Spectrometry (GC/MS) and high performance liquid chromatography (HPLC) to determine the concentrations of the constituent VOCs. The measurements were performed just after completion of the building and again 3 months after completion. The TVOC concentration exceeded 1000 µg·m(-3) for all the sampling locations just after completion of building, and decreased almost one tenth after 3 months, to below the guideline values of the TVOC in Japan at 400 µg·m(-3). The concentrations of the target VOCs of which the indoor concentrations are regulated in Japan were below the guideline values for all the cases. The air-exchange rates were determined based on the temporal changes of the TVOC concentrations, and it was found that the countermeasure to increase the air exchange rate successfully decrease the TVOC concentration level in the rooms. PMID:27455290

  16. Development of a fast GC/MS-system for airborne measurements of Volatile Organic Compounds

    NASA Astrophysics Data System (ADS)

    Wenk, Ann-Kathrin; Wegener, Robert; Hofzumahaus, Andreas; Wahner, Andreas

    2010-05-01

    Volatile Organic Compounds (VOC) determine the radical chemistry of the atmosphere. They can serve both as sources, or sinks for radicals. Mass spectrometry linked to gas chromatography (GC/MS) is a widespread technique in environmental analysis since it can be used to separate and analyze any compound which can be evaporated and pass the analytical column with very high precision and a good sensitivity. The use of special chromatographic phases and long capillary columns enables the quantification of a wide range of compounds with little interference from other sample constituents. An in situ GC/MS consists in principle of three compartments, 1) a preconcentration unit where the sample is extracted from the air, focussed onto a small volume and volatilized, 2) a chromatographic system where the analytes are separated on the analytical column and 3) a mass spectrometer where the compounds are ionized and detected. VOC have to be preconcentrated due to their low concentration level and in order to get enough sensitivity for analysis. The aim of this project was to develop an in situ GC/MS system to analyze volatile Nonmethane Hydrocarbons (NMHC) and Oxygenated Volatile Organic Compounds (OVOC) for the High Altitude and LOng Range Research Aircraft (HALO). In contrast to other analytical instruments a GC/MS works discontinuously. The preconcentration unit is either heated up when the compounds are volatilized or cooled down when substances are adsorbed. The same is true for the GC oven. It is heated up when the compounds are separated or it is cooled down to be ready for the next injection. On a system with a single GC oven, these processes will inevitably lengthen the whole analytical procedure. To speed up the analytical process the GC/MS system described here was equipped with two GC ovens and two adsorption units. While the components are adsorbed in one adsorption unit, in the other unit the components are desorbed and transferred to the GC unit. The second GC

  17. Continuous Underway Seawater Measurements of Biogenic Volatile Organic Compounds in the Western Atlantic Ocean

    NASA Astrophysics Data System (ADS)

    Zoerb, M.; Kim, M.; Bertram, T. H.

    2014-12-01

    The products of isoprene and terpene oxidation have been shown to contribute significantly to secondary aerosol production rates over continental regions, where the emission rates have been well characterized. Significantly less is known about the emission of isoprene and monoterpenes from marine sources. We discuss the development of a chemical ionization mass spectrometer (CIMS) employing benzene reagent ion chemistry for the selective detection of biogenic volatile organic compounds. The CIMS was coupled to a seawater equilibrator for the measurement of dissolved gases in surface seawater. This system was deployed aboard the R/V Knorr during the Western Atlantic Climate Study II in Spring 2014. Here, we report surface seawater (5 m depth) concentrations of dimethyl sulfide, isoprene, and alpha-pinene. The concentration measurements are discussed in terms of surface seawater temperature, nutrient availability, and primary productivity.

  18. Measurements of oxygenated volatile organic compounds in the oil sands region of Alberta

    NASA Astrophysics Data System (ADS)

    Moussa, S. G.; Leithead, A.; Li, S. M.; Gordon, M.; Hayden, K. L.; Wang, D. K.; Staebler, R. M.; Liu, P.; O'Brien, J.; Mittermeier, R.; Liggio, J.

    2014-12-01

    Oxygenated volatile organic compounds (OVOCs) are ubiquitous in the atmosphere, and represent an important fraction of volatile organic compounds. Additionally some OVOC species may pose health risks. OVOCs can affect the oxidative and radiative budget of the atmosphere since they are precursors to ground level ozone, hydroxyl radicals and secondary organic aerosols (SOA). OVOCs such as methanol, formaldehyde, acetaldehyde, acetone, crotonaldehyde, methylvinylketone (MVK), methylethylketone (MEK) and acrolein can be emitted from anthropogenic and biogenic sources. Additionally, they are the secondary products of the photo-oxidation of hydrocarbons (biogenic and anthropogenic). Understanding the magnitude of these sources is a prerequisite for accurate representations of radical cycling, ozone production and SOA formation in air quality models. The sources of OVOCs in the Alberta Oil Sands (OS) region have not previously been well characterized. In the summer of 2013, airborne measurements of various OVOCs were made in the Athabasca oil sands region between August 13 and September 7, 2013. Proton Transfer Reaction-Time of Flight-Mass Spectrometry (PTR-ToF-MS) was used to measure methanol, formaldehyde, acetaldehyde, acetone, crotonaldehyde, MVK, MEK, acrolein as well as other hydrocarbons. Emission ratios (ER) for several OVOCs (relative to carbon monoxide; CO) were used to estimate direct anthropogenic emissions from OS industrial sources, while the calculated OH radical exposures were used to estimate the production and removal of secondary anthropogenic OVOCs. The results indicate that OVOCs such as acetaldehyde, crotonaldehyde and MVK have both primary and secondary anthropogenic and biogenic sources. However, species such as methanol and acrolein are from biogenic and anthropogenic sources, respectively. The results of this work will help to characterize sources of OVOCs and the factors influencing their atmospheric fate in the Oil Sands region.

  19. Measurement of volatile organic compounds in the urban atmosphere of Harris County, Texas, USA.

    PubMed

    Conley, Felicia L; Thomas, Renard L; Wilson, Bobby L

    2005-01-01

    Volatile organic compounds (VOCs) are a major component of urban air pollution. It is well documented that exposure to certain types of VOCs can cause adverse health effects such as cancer, immune and neurological damage, and reproductive and endocrine disorders. Urban air samples were collected at five locations in Harris County, Texas to determine the measurement of VOCs in the ambient air of residential areas in close proximity to industrial facilities that emit toxic air pollutants into the air. Three locations used in this study were located along the Houston Ship Channel (HSC), in the heart of one of the largest petrochemical complexes in the nation. Two other sampling locations were located many miles away from the ship channel and any industrial facilities that are required to report toxic air emissions. Air samples were collected daily over an 8-h period from December 2002 to March 2003. The samples were collected in 6-L stainless steel Silonite-coated canisters and analyzed using a modified version of EPA Method TO-15. A total of 53 compounds was quantitated using a gas chromatograph mass spectrometer system coupled to a cryogenic preconcentrator. Eighteen alkanes and oxygenated compounds were identified, along with 7 alkenes and 5 aromatic compounds. Several alkanes such as butane, isobutane, 2-methyl butane, and pentane were detected at all five sites. The total VOC concentrations determined were highest at two of the industrial sites and lowest at the site farthest away from the ship channel and any industrial facilities. This study concluded that the atmosphere near Harris County's industrial complex had higher concentrations of VOCs than the atmosphere in areas farther away from the HSC. The atmosphere of areas downwind from emission sources were found to be directly affected by toxic air emissions from industrial process but not at the levels seen in areas closer to the HSC. PMID:16134361

  20. IN SITU MEASUREMENTS OF C2-C10 VOLATILE ORGANIC COMPOUNDS ABOVE A SIERRA NEVADA PONDEROSA PINE PLANTATION

    EPA Science Inventory

    A fully automated GC-FID system was designed and built to measure ambient concentrations of C2-C10 volatile organic compounds, including many oxygenated compounds, without using liquid cryogen. It was deployed at Blodgett Forest Research Station in Georgetown, CA USA, 38 deg 53' ...

  1. Diffusive sampling and measurement of microbial volatile organic compounds in indoor air.

    PubMed

    Araki, A; Eitaki, Y; Kawai, T; Kanazawa, A; Takeda, M; Kishi, R

    2009-10-01

    Microbial volatile organic compounds (MVOC), chemicals emitted from various microorganisms, in indoor air have been of concern in recent years. For large field studies, diffusive samplers are widely used to measure indoor environments. Since the sampling rate of a sampler is a fundamental parameter to calculate concentration, the sampling rates of eight MVOC with diffusive samplers were determined experimentally using a newly developed water-bubbling method: air was supplied to the MVOC-solutions and the vapor collected in an exposure bag, where diffusive and active samplers were placed in parallel for comparison. Correlations between the diffusive and active samplings gave good linear regressions. The sampling rates were 30-35 ml/min and the detection limits were 0.044-0.178 microg/m(3), as determined by GC/MS analysis. Application of the sampling rates in indoor air was validated by parallel sampling of the diffusive and active sampling method. 5% Propan-2-ol/CS(2) was the best solvent to desorb the compounds from absorbents. The procedure was applied to a field study in 41 dwellings. The most frequently detected compounds were hexan-2-one and heptan-2-one, with 97.5% detection rates and geometric mean values of 0.470 and 0.302 microg/m(3), respectively. This study shows that diffusive samplers are applicable to measure indoor MVOC levels. Practical Implications At present, there are still limited reports on indoor Microbial Volatile Organic Compounds (MVOC) levels in general dwellings and occupants' health. Compared with active sampling methods, air sampling using a diffusive sampler is particularly advantageous for use in large field studies due to its smallness, light-size, easy-handling, and cost-effectiveness. In this study, sampling rates of selected MVOC of the diffusive sampler were determined using the water-bubbling method: generating gases by water-bubbling and exposing the diffusive and active samplers at the same time. The obtained sampling rates

  2. Volatile organic compounds in indoor air: A review ofconcentrations measured in North America since 1990

    SciTech Connect

    ATHodgson@lbl.gov

    2003-04-01

    Central tendency and upper limit concentrations of volatile organic compounds (VOCs) measured in indoor air are summarized and reviewed. Data were obtained from published cross-sectional studies of residential and office buildings conducted in North America from 1990through the present. VOC concentrations in existing residences reported in 12 studies comprise the majority of the data set. Central tendency and maximum concentrations are compared between new and existing residences and between existing residences and office buildings. Historical changes in indoor VOC concentrations since the Clean Air Act Amendments of 1990 are explored by comparing the current data set with two published reviews of previous data obtained primarily in the 1980s. These historical comparisons suggest average indoor concentrations of some toxic air contaminants, such as 1,1,1-trichloroethane have decreased.

  3. Measurement of Organic Compounds in Diesel and Gasoline Engine Exhaust using Thermal Desorption PTR-MS

    NASA Astrophysics Data System (ADS)

    Jobson, B. T.; Gueneron, M.; Erickson, M. H.; Vanderschelden, G. S.

    2013-12-01

    A proton transfer reaction mass spectrometer modified with a thermal desorption sampler was used to measure organic compounds in diesel and gasoline engine exhaust in a laboratory setting. The drift tube was operated at 80 Td, providing an M+1 and M-1 mass spectrum for the most abundant constituents of the exhaust including alkenes, cycloalkanes, bicycloalkanes, monoaromatics, and naphthenic monoaromatic compounds. Alkanes were observed to fragment to a common set of ions. Use of the thermal desorption sampler enabled the total concentration of C10-C17 alkanes to be determined. The abundance of higher molecular weight cycloalkanes, bicycloalkanes, napthenic monoaromatics, and larger C10-C17 alkanes was much greater in diesel exhaust, allowing for a distinct source fingerprint pattern to distinguish diesel from gasoline exhaust. Use of the finger print source profiles allowed us to quantify the relative amounts of diesel and gasoline exhaust in mixtures, suggesting its utility to determine the relative contributions of gasoline and diesel engine exhaust to hydrocarbon concentrations in urban areas.

  4. Measurement and Comparison of Organic Compound Concentrations in Plasma, Whole Blood, and Dried Blood Spot Samples

    PubMed Central

    Batterman, Stuart A.; Chernyak, Sergey; Su, Feng-Chiao

    2016-01-01

    The preferred sampling medium for measuring human exposures of persistent organic compounds (POPs) is blood, and relevant sample types include whole blood, plasma, and dried blood spots (DBS). Because information regarding the performance and comparability of measurements across these sample types is limited, it is difficult to compare across studies. This study evaluates the performance of POP measurements in plasma, whole blood and DBS, and presents the distribution coefficients needed to convert concentrations among the three sample types. Blood samples were collected from adult volunteers, along with demographic and smoking information, and analyzed by GC/MS for organochlorine pesticides (OCPs), chlorinated hydrocarbons (CHCs), polychlorinated biphenyls (PCBs), and brominated diphenyl ethers (PBDEs). Regression models were used to evaluate the relationships between the sample types and possible effects of personal covariates. Distribution coefficients also were calculated using physically-based models. Across all compounds, concentrations in plasma were consistently the highest; concentrations in whole blood and DBS samples were comparable. Distribution coefficients for plasma to whole blood concentrations ranged from 1.74 to 2.26 for pesticides/CHCs, averaged 1.69 ± 0.06 for the PCBs, and averaged 1.65 ± 0.03 for the PBDEs. Regression models closely fit most chemicals (R2 > 0.80), and whole blood and DBS samples generally showed very good agreement. Distribution coefficients estimated using biologically-based models were near one and did not explain the observed distribution. Among the study population, median concentrations of several pesticides/CHCs and PBDEs exceeded levels reported in the 2007–2008 National Health and Nutrition Examination Survey, while levels of other OCPs and PBDEs were comparable or lower. Race and smoking status appeared to slightly affect plasma/blood concentration ratios for several POPs. The experimentally

  5. Measurements of Methane Emissions and Volatile Organic Compounds from Shale Gas Operations in the Marcellus Shale

    NASA Astrophysics Data System (ADS)

    Omara, M.; Subramanian, R.; Sullivan, M.; Robinson, A. L.; Presto, A. A.

    2014-12-01

    The Marcellus Shale is the most expansive shale gas reserve in play in the United States, representing an estimated 17 to 29 % of the total domestic shale gas reserves. The rapid and extensive development of this shale gas reserve in the past decade has stimulated significant interest and debate over the climate and environmental impacts associated with fugitive releases of methane and other pollutants, including volatile organic compounds. However, the nature and magnitude of these pollutant emissions remain poorly characterized. This study utilizes the tracer release technique to characterize total fugitive methane release rates from natural gas facilities in southwestern Pennsylvania and West Virginia that are at different stages of development, including well completion flowbacks and active production. Real-time downwind concentrations of methane and two tracer gases (acetylene and nitrous oxide) released onsite at known flow rates were measured using a quantum cascade tunable infrared laser differential absorption spectrometer (QC-TILDAS, Aerodyne, Billerica, MA) and a cavity ring down spectrometer (Model G2203, Picarro, Santa Clara, CA). Evacuated Silonite canisters were used to sample ambient air during downwind transects of methane and tracer plumes to assess volatile organic compounds (VOCs). A gas chromatograph with a flame ionization detector was used to quantify VOCs following the EPA Method TO-14A. A preliminary assessment of fugitive emissions from actively producing sites indicated that methane leak rates ranged from approximately 1.8 to 6.2 SCFM, possibly reflecting differences in facility age and installed emissions control technology. A detailed comparison of methane leak rates and VOCs emissions with recent published literature for other US shale gas plays will also be discussed.

  6. Measurement of personal exposure to volatile organic compounds and particle associated PAH in three UK regions.

    PubMed

    Saborit, Juana Mari Delgado; Aquilina, Noel J; Meddings, Claire; Baker, Stephen; Vardoulakis, Sotiris; Harrison, Roy M

    2009-06-15

    Personal exposures to 15 volatile organic compounds (VOC) and 16 polycyclic aromatic hydrocarbons (PAH) of 100 adult nonsmokers living in three UK areas, namely London, West Midlands, and rural South Wales, were measured using an actively pumped sampler carried around by the volunteers for 5/1 (VOC/PAH) consecutive 24-h periods, following their normal lifestyle. Results from personal exposure measurements categorized by geographical location, type of dwelling, and exposure to environmental tobacco smoke (ETS) are presented. The average personal exposure concentration to benzene, 1,3-butadiene, and benzo(a)pyrene representing the main carcinogenic components of the VOC and PAH mixture were 2.2 +/- 2.5 microg/m3, 0.4 +/- 0.7 microg/m3, and 0.3 +/- 0.7 ng/m3 respectively. The association of a number of generic factors with personal exposure concentrations was investigated, including first-line property, traffic, the presence of an integral garage, and ETS. Only living in houses with integral garages and being exposed to ETS were identified as unequivocal contributors to VOC personal exposure, while only ETS had a clear effect upon PAH personal exposures. The measurements of personal exposures were compared with health-based European and UK air quality guidelines, with some exceedences occurring. Activities contributing to high personal exposures included the use of a fireplace in the home, ETS exposure, DIY (i.e., construction and craftwork activities), and photocopying, among others. PMID:19603680

  7. Volatile organic compounds in the New England troposphere: Atmospheric chemistry and measurement techniques

    NASA Astrophysics Data System (ADS)

    Ambrose, Jesse L.

    Atmospheric measurements made at Appledore Island, Maine were used to investigate nighttime nitrate radical (NO3) chemistry and its significance for the nitrogen oxides (NOx = NO + NO2) budget in the Gulf of Maine region during the summer of 2004 International Consortium for Atmospheric Research on Transport and Transformation field campaign. Removal of NOx was strongly dependent on reactions of NO3 with biogenic volatile organic compounds and the fate of dinitrogen pentoxide (N 2O5). For three case studies, temporal profiles of NO 3 were calculated from measured parameters. Comparisons between measured and calculated NO3 mixing ratios highlighted significant uncertainties in the kinetic parameters governing gas-phase and heterogeneous N2O 5 hydrolysis. Removal of NOx was estimated to be ˜11 ppbv day-1, with nighttime chemical pathways contributing ˜50%. Atmospheric measurements made at the AIRMAP atmospheric monitoring station Thompson Farm (THF) during summer, 2004 were used to test the specificity of a proton transfer reaction-mass spectrometer (PTA-MS) for atmospheric toluene measurements under conditions often dominated by biogenic emissions. Quantitative estimates were made of potential interferences in the PTR-MS toluene measurements related to sampling and analysis of monoterpenes, including fragmentation of the monoterpenes and some of their primary carbonyl oxidation products in the PTR-MS drift tube. The analysis supported only minor interferences from the investigated fragmentation sources, suggesting that toluene can be reliably quantified by PTR-MS with the operating parameters used, under the ambient compositions probed. This work extends the range of field conditions under which PTR-MS validation studies have been conducted. A GC instrument was developed for measurement of hydrogen cyanide (HCN) in the lower atmosphere. Its major features include a cold temperature analyte enrichment system, a robust porous polymer stationary phase capillary

  8. Insights into secondary organic aerosol formation mechanisms from measured gas/particle partitioning of specific organic tracer compounds.

    PubMed

    Zhao, Yunliang; Kreisberg, Nathan M; Worton, David R; Isaacman, Gabriel; Weber, Robin J; Liu, Shang; Day, Douglas A; Russell, Lynn M; Markovic, Milos Z; VandenBoer, Trevor C; Murphy, Jennifer G; Hering, Susanne V; Goldstein, Allen H

    2013-04-16

    In situ measurements of organic compounds in both gas and particle phases were made with a thermal desorption aerosol gas chromatography (TAG) instrument. The gas/particle partitioning of phthalic acid, pinonaldehyde, and 6,10,14-trimethyl-2-pentadecanone is discussed in detail to explore secondary organic aerosol (SOA) formation mechanisms. Measured fractions in the particle phase (f(part)) of 6,10,14-trimethyl-2-pentadecanone were similar to those expected from the absorptive gas/particle partitioning theory, suggesting that its partitioning is dominated by absorption processes. However, f(part) of phthalic acid and pinonaldehyde were substantially higher than predicted. The formation of low-volatility products from reactions of phthalic acid with ammonia is proposed as one possible mechanism to explain the high f(part) of phthalic acid. The observations of particle-phase pinonaldehyde when inorganic acids were fully neutralized indicate that inorganic acids are not required for the occurrence of reactive uptake of pinonaldehyde on particles. The observed relationship between f(part) of pinonaldehyde and relative humidity suggests that the aerosol water plays a significant role in the formation of particle-phase pinonaldehyde. Our results clearly show it is necessary to include multiple gas/particle partitioning pathways in models to predict SOA and multiple SOA tracers in source apportionment models to reconstruct SOA. PMID:23448102

  9. Characteristics of Ambient Volatile Organic Compounds (VOCs) Measured in Shanghai, China

    PubMed Central

    Cai, Chang-Jie; Geng, Fu-Hai; Tie, Xue-Xi; Yu, Qiong; Peng, Li; Zhou, Guang-Qiang

    2010-01-01

    To better understand the characteristics of ambient abundance of volatile organic compounds (VOCs) in Shanghai, one of the biggest metropolis of China, VOCs were measured with a gas chromatography system equipped with a mass-selective detector (GC/MSD) from July 2006 to February 2010. An intensive measurement campaign was conducted (eight samples per day with a 3 hour interval) during May 2009. The comparison of ambient VOCs collected in different regions of Shanghai shows that the concentrations are slightly higher in the busy commercial area (28.9 ppbv at Xujiaui) than in the urban administrative area (24.3 ppbv at Pudong). However, during the intensive measurement period, the concentrations in the large steel industrial area (28.7 ppbv at Baoshan) were much higher than in the urban administrative area (18 ppbv at Pudong), especially for alkanes, alkenes, and toluene. The seasonal variations of ambient VOC concentrations measured at the Xujiahui sampling site indicate that the VOC concentrations are significantly affected by meteorological conditions (such as wind direction and precipitation). In addition, although alkanes are the most abundant VOCs at the Xujiahui measurement site, the most important VOCs contributing to ozone formation potential (OFP) are aromatics, accounting for 57% of the total OFP. The diurnal variations of VOC concentrations show that VOC concentrations are higher on weekdays than in weekends at the Xujiahui sampling site, suggesting that traffic condition and human activities have important impacts on VOC emissions in Shanghai. The evidence also shows that the major sources of isoprene are mainly resulted from gasoline evaporation at a particular time (06:00–09:00) in the busy commercial area. The results gained from this study provide useful information for better understanding the characteristics of ambient VOCs and the sources of VOCs in Shanghai. PMID:22163629

  10. Production of extremely low volatile organic compounds from biogenic emissions: Measured yields and atmospheric implications

    SciTech Connect

    Jokinen, Tuija; Berndt, Torsten; Makkonen, Risto; Kerminen, Veli-Matti; Junninen, Heikki; Paasonen, Pauli; Stratmann, Frank; Herrmann, Hartmut; Guenther, Alex B.; Worsnop, Douglas R.; Kulmala, M.; Ehn, Mikael K.; Sipila, Mikko

    2015-06-09

    Extremely low volatility organic compounds (ELVOC) are suggested to promote aerosol particle formation and cloud condensation nuclei (CCN) production in the atmosphere. We show that the capability of biogenic VOC (BVOC) to produce ELVOC depends strongly on their chemical structure and relative oxidant levels. BVOC with an endocyclic double bond, representative emissions from, e.g., boreal forests, efficiently produce ELVOC from ozonolysis. Compounds with exocyclic double bonds or acyclic compounds including isoprene, emission representative of the tropics, produce minor quantities of ELVOC, and the role of OH radical oxidation is relatively larger. Implementing these findings into a global modeling framework shows that detailed assessment of ELVOC production pathways is crucial for understanding biogenic secondary organic aerosol and atmospheric CCN formation.

  11. EXPOSURE TO VOLATILE ORGANIC COMPOUNDS MEASURED IN A SOURCE IMPACTED AIRSHED

    EPA Science Inventory

    A three-year exposure monitoring study is being conducted in a large city in the Midwestern U.S. The study is aimed at determining the factors influencing exposures to air pollutants of outdoor origin, including volatile organic compounds (VOCs) and particulate matter.

  12. 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)

  13. Measurements of volatile organic compounds in rural area of Yangtze River Delta region: Measurement comparison and source characterization

    NASA Astrophysics Data System (ADS)

    Kudo, S.; Saito, S.; Tanimoto, H.; Inomata, S.; Kanaya, Y.; Yamaji, K.; Xiaole, P.; Wang, Z.

    2012-12-01

    Concentrations of non-methane volatile organic compounds (NMVOCs) in ambient air were measured by three different methods in a city of Rudong in May and June 2010. Intercomparison of VOCs measurements was made among in-situ measurements and canister analyses with a gas chromatography/flame ionization detection/mass spectrometry (GC/FID/MS) and proton transfer reaction-mass spectrometry (PTR-MS). For 18 VOCs measured by GC/FID/MS, canister analyses and in-situ measurements were in reasonably good agreement (R2 > 0.90). However, alkenes and aromatics in canister samples were found to be lower than in-situ measurements likely due to adsorption of low volatile compounds onto the wall surface inside canisters. For comparison of GC/MS with PTR-MS, the correlations for isoprene, benzene, C8 aromatics, and C9 aromatics were highly significant (R2 ≥ 0.93) with each other. However, there were quantitative differences between GC/MS and PTR-MS. For example, isoprene measured by PTR-MS indicates existence of interferences from C5 alcohols, C5 aldehydes, and furan. During the latter part of the field campaign, elevated concentrations of VOCs and CO were observed when intensive burning of crop residues took place near the sampling site. The concentrations of ethane, propane, ethane, isoprene, acetone, acetaldehyde, and aromatics varied in the range between 0 and 30 ppbv. The observed VOCs concentrations are compared to model results by a regional chemistry-transport model for Asia. The modeled concentrations underestimated the observed concentrations by a factor of 10 for NMHCs, 100 for aromatics, 10 for oxygenated VOCs, implying that current emissions inventories miss a number of sources for these VOCs.

  14. D/H Isotope Ratio Measurements of Atmospheric Volatile Organic Compounds

    NASA Astrophysics Data System (ADS)

    Meisehen, Thomas; Bühler, Fred; Koppmann, Ralf; Krebsbach, Marc

    2015-04-01

    Analysis of isotope ratios in atmospheric volatile organic compounds (VOC) is a reliable method to allocate their sources, to estimate atmospheric residence times and investigate physical and chemical processes on various temporal and spatial scales. Most investigations yet focus on carbon isotope ratios. Certainly more detailed information can be gained by the ratio of deuterium (D) to hydrogen (H) in VOC, especially due to the high mass ratio. Combining measurements of carbon and hydrogen isotopes could lead to considerable improvement in our understanding of atmospheric processes. For this purpose we set up and thoroughly characterised a gas chromatograph pyrolysis isotope ratio mass spectrometer to measure the D/H ratio in atmospheric VOC. From a custom-made gas standard mixture VOC were adsorbed on Tenax®TA which has the advantage that CO2 is not preconcentrated when measuring ambient air samples. Our results show that the pyrolysis method has significant impact on the D/H ratios. A pyrolysis temperature of at least 1723 K and conditioning of the ceramic tube on a regular basis is essential to obtain reproducible D/H isotope ratios. For an independent comparison D/H ratios of the pure VOC used in the gas standard were determined using elemental analysis by Agroisolab (Jülich, Germany). Comparisons of 10 VOC show perfect agreement within the standard deviations of our measurements and the errors given by Agroisolab, e.g. for n-pentane, toluene, 4-methyl-2-pentanone and n-octane. A slight mean difference of 5.1 o was obtained for n-heptane while significant mean differences of 15.5 o and 20.3 o arose for 1,2,4-trimethylbenzene and isoprene, respectively. We further demonstrate the stability of our system and show that the sample preparation does not affect the isotope ratios. Moreover the applicability of our system to ambient air samples is demonstrated.

  15. Airborne Flux Measurements of Volatile Organic Compounds and NOx over a European megacity

    NASA Astrophysics Data System (ADS)

    Shaw, Marvin; Lee, James; Davison, Brian; Misztal, Pawel; Karl, Thomas; Hewitt, Nick; Lewis, Alistair

    2014-05-01

    Ground level ozone (O3) and nitrogen dioxide (NO2) are priority pollutants whose concentrations are closely regulated by European Union Air Quality Directive 2008/50/EC. O3 is a secondary pollutant, produced from a complex chemical interplay between oxides of nitrogen (NOx = NO + NO2) and volatile organic compounds (VOCs). Whilst the basic atmospheric chemistry leading to O3 formation is generally well understood, there are substantial uncertainties associated with the magnitude of emissions of both VOCs and NOx. At present our knowledge of O3 precursor emissions in the UK is primarily derived from National Atmospheric Emission inventories (NAEI) that provide spatially disaggregated estimates at 1x1km resolution, and these are not routinely tested at city or regional scales. Uncertainties in emissions propagate through into uncertainties in predictions of air quality in the future, and hence the likely effectiveness of control policies on both background and peak O3 and NO2 concentrations in the UK. The Ozone Precursor Fluxes in the Urban Environment (OPFUE) project aims to quantify emission rates for NOx and selected VOCs in and around the megacity of London using airborne eddy covariance (AEC). The mathematical foundation for AEC has been extensively reviewed and AEC measurements of ozone, dimethyl sulphide, CO2 and VOCs have been previously reported. During the summer of 2013, approximately 30 hours of airborne flux measurements of toluene, benzene, NO and NO2 were obtained from the NERC Airborne Research and Survey Facility's (ARSF) Dornier-228 aircraft. Over SE England, flights involved repeated south west to north east transects of ~50 km each over Greater London and it's surrounding suburbs and rural areas, flying at the aircraft's minimum operating flight altitude and airspeed (~300m, 80m/s). Mixing ratios of benzene and toluene were acquired at 2Hz using a proton transfer reaction mass spectrometer (PTR-MS) and compared to twice hourly whole air canister

  16. Measurements of volatile organic compounds in Southeastern Mexico City, 1998 - 2007

    NASA Astrophysics Data System (ADS)

    Wöhrnschimmel, H.; Magaña, M.; Bueno, E.; Pérez, J. M.; González, S.; Blanco, S.; Cárdenas, B.

    2009-04-01

    Air pollution is one of the principal environmental problems in Megacities. In Mexico City, very high ozone concentrations, a result of precursors like nitrogen oxides (NOx) and volatile organic compounds (VOCs), are thought to cause severe health effects on a population of about 20 million. In addition, there are several air toxics among VOCs that threaten public health. Therefore, measuring VOCs is crucial for the definition of air quality management control strategies. In this paper we report a time series of VOC measurements, carried out in Southeastern Mexico City from 1998 to 2007. Over 26,000 grab samples were taken at different hours of the day and stations of the year, which permits a detailed analysis of changes and tendencies of VOC species, in particular the air toxics benzene, toluene and xylene (BTX). Totally, 13 species have been quantified by GC-FID. A significant decreasing tendency has been observed in VOC species, especially in BTX. The reductions were 0.1 ppbV per year for benzene and toluene. o-xylene decreased with an average rate of 0.3 ppbV per year. For the morning hours, when emissions are strongest, the reductions were even more notable (0.2, 1.3 and 0.5 ppbV per year, respectively). With this, the annual average for benzene concentrations is below the standard of 1.5 ppbV established by the European Community. The observed reductions can be attributed to an improving vehicle technology, in spite of an increasing vehicular fleet. Furthermore, in this paper we discuss total VOC data in comparison with simultaneous NOx measurements, and its implications on photochemical air pollution and validation of the emissions inventory.

  17. Fluxes of biogenic volatile organic compounds measured and modelled above a Norway spruce forest

    NASA Astrophysics Data System (ADS)

    Juráň, Stanislav; Fares, Silvano; Pallozzi, Emanuele; Guidolotti, Gabriele; Savi, Flavia; Alivernini, Alessandro; Calfapietra, Carlo; Večeřová, Kristýna; Křůmal, Kamil; Večeřa, Zbyněk; Cudlín, Pavel; Urban, Otmar

    2016-04-01

    Fluxes of biogenic volatile organic compounds (BVOCs) were investigated at Norway spruce forest at Bílý Kříž in Beskydy Mountains of the Czech Republic during the summer 2014. A proton-transfer-reaction-time-of-flight mass spectrometer (PTR-TOF-MS, Ionicon Analytik, Austria) has been coupled with eddy-covariance system. Additionally, Inverse Lagrangian Transport Model has been used to derive fluxes from concentration gradient of various monoterpenes previously absorbed into n-heptane by wet effluent diffusion denuder with consequent quantification by gas chromatography with mass spectrometry detection. Modelled data cover each one day of three years with different climatic conditions and previous precipitation patterns. Model MEGAN was run to cover all dataset with monoterpene fluxes and measured basal emission factor. Highest fluxes measured by eddy-covariance were recorded during the noon hours, represented particularly by monoterpenes and isoprene. Inverse Lagrangian Transport Model suggests most abundant monoterpene fluxes being α- and β-pinene. Principal component analysis revealed dependencies of individual monoterpene fluxes on air temperature and particularly global radiation; however, these dependencies were monoterpene specific. Relationships of monoterpene fluxes with CO2 flux and relative air humidity were found to be negative. MEGAN model correlated to eddy-covariance PTR-TOF-MS measurement evince particular differences, which will be shown and discussed. Bi-directional fluxes of oxygenated short-chain volatiles (methanol, formaldehyde, acetone, acetaldehyde, formic acid, acetic acid, methyl vinyl ketone, methacrolein, and methyl ethyl ketone) were recorded by PTR-TOF-MS. Volatiles of anthropogenic origin as benzene and toluene were likely transported from the most benzene polluted region in Europe - Ostrava city and adjacent part of Poland around Katowice, where metallurgical and coal mining industries are located. Those were accumulated during

  18. Measurements of Volatile Organic Compounds and Gaseous Sulfuric Acid During the 2008 CAREBEIJING Campaign

    NASA Astrophysics Data System (ADS)

    Zhang, R.; Zheng, J.; Hu, M.; Zhu, T.

    2009-05-01

    Air quality in Beijing has been a hot topic recently, because Beijing hosted the 2008 summer Olympics. To combat the problem, China ordered numerous factories shut down or used only sporadically during the games to limit air pollution in the area. Another major step involved ordering about one-half of the city's 3.3 million vehicles off the road during the games, allowing only cars on roads with odd or even-numbered license plates on alternate days until the games were over. In addition, China has implemented new auto emission standards since March 2009 with regulations that are similar to those used throughout Europe. Our team at the Texas A&M participated in the 2008 CAREBEIJING campaign, with the objectives of studying the complex chemistry of the air in Beijing, looking at emission controls and their effectiveness, studying the surrounding air from other regions and how it can affect Beijing's air, and comparing all of our findings with air quality in other cities we have examined, such as Mexico City and Houston. In this talk, preliminary results of measurements of volatile organic compounds (VOCs) and gaseous sulfuric acid will be presented to discuss the trends of VOCs and new particle formation associated with the traffic control.

  19. Elemental ratio measurements of organic compounds using aerosol mass spectrometry: characterization, improved calibration, and implications

    DOE PAGESBeta

    Canagaratna, M. R.; Jimenez, J. L.; Kroll, J. H.; Chen, Q.; Kessler, S. H.; Massoli, P.; Hildebrandt Ruiz, L.; Fortner, E.; Williams, L. R.; Wilson, K. R.; et al

    2014-07-31

    Elemental compositions of organic aerosol (OA) particles provide useful constraints on OA sources, chemical evolution, and effects. The Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) is widely used to measure OA elemental composition. This study evaluates AMS measurements of atomic oxygen-to-carbon (O : C), hydrogen-to-carbon (H : C), organic mass-to-organic carbon (OM : OC), and carbon oxidation state (OSC) for a vastly expanded laboratory dataset of multifunctional oxidized OA standards. For the expanded standard dataset, the "Aiken-Explicit" method (Aiken et al., 2008), which uses experimentally measured ion intensities at all ions to determine elemental ratios, reproduces known molecular O :more » C and H : C ratio values within 20% (average absolute value of relative errors) and 12% respectively. The more commonly used "Aiken-Ambient" method, which uses empirically estimated H2O+ and CO+ ion intensities to avoid gas phase air interferences at these ions, reproduces O : C and H : C of multifunctional oxidized species within 28% and 14% of known values. These values are systematically biased low, however, with larger biases observed for alcohols and simple diacids. A detailed examination of the H2O+, CO+, and CO2+ fragments in the high-resolution mass spectra of the standard compounds indicates that the Aiken-Ambient method underestimates the CO+ and H2O+ produced from many oxidized species. Combined AMS-vacuum ultraviolet (VUV) ionization measurements indicate that these ions are produced by dehydration and decarboxylation on the AMS vaporizer (usually operated at 600 °C). Thermal decomposition is observed to be efficient at vaporizer temperatures down to 200 °C. These results are used together to develop an "Improved-Ambient" elemental analysis method for AMS spectra measured in air. The Improved-Ambient method reduces the systematic biases and reproduces O : C (H : C) ratios of individual oxidized standards within 28% (13

  20. Elemental ratio measurements of organic compounds using aerosol mass spectrometry: characterization, improved calibration, and implications

    DOE PAGESBeta

    Canagaratna, M. R.; Jimenez, J. L.; Kroll, J. H.; Chen, Q.; Kessler, S. H.; Massoli, P.; Hildebrandt Ruiz, L.; Fortner, E.; Williams, L. R.; Wilson, K. R.; et al

    2015-01-12

    Elemental compositions of organic aerosol (OA) particles provide useful constraints on OA sources, chemical evolution, and effects. The Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) is widely used to measure OA elemental composition. This study evaluates AMS measurements of atomic oxygen-to-carbon (O : C), hydrogen-to-carbon (H : C), and organic mass-to-organic carbon (OM : OC) ratios, and of carbon oxidation state (OS C) for a vastly expanded laboratory data set of multifunctional oxidized OA standards. For the expanded standard data set, the method introduced by Aiken et al. (2008), which uses experimentally measured ion intensities at all ions to determinemore » elemental ratios (referred to here as "Aiken-Explicit"), reproduces known O : C and H : C ratio values within 20% (average absolute value of relative errors) and 12%, respectively. The more commonly used method, which uses empirically estimated H2O+ and CO+ ion intensities to avoid gas phase air interferences at these ions (referred to here as "Aiken-Ambient"), reproduces O : C and H : C of multifunctional oxidized species within 28 and 14% of known values. The values from the latter method are systematically biased low, however, with larger biases observed for alcohols and simple diacids. A detailed examination of the H2O+, CO+, and CO2+ fragments in the high-resolution mass spectra of the standard compounds indicates that the Aiken-Ambient method underestimates the CO+ and especially H2O+ produced from many oxidized species. Combined AMS–vacuum ultraviolet (VUV) ionization measurements indicate that these ions are produced by dehydration and decarboxylation on the AMS vaporizer (usually operated at 600 °C). Thermal decomposition is observed to be efficient at vaporizer temperatures down to 200 °C. These results are used together to develop an "Improved-Ambient" elemental analysis method for AMS spectra measured in air. The Improved-Ambient method uses specific ion

  1. In situ measurements of C2-C10 volatile organic compounds above a Sierra Nevada ponderosa pine plantation

    NASA Astrophysics Data System (ADS)

    Lamanna, Mark S.; Goldstein, Allen H.

    1999-09-01

    A fully automated gas chromatograph-flame ionization detector system was designed and built to measure ambient concentrations of C2-C10 volatile organic compounds, including many oxygenated compounds, without using liquid cryogen. It was deployed at Blodgett Forest Research Station in Georgetown, California, 38°53'42.9″N, 120°37'57.9″W, 1315 m elevation. More than 900 in situ measurements were made above a ponderosa pine canopy at 40-min intervals, continuously from July 2 through August 1, 1997. Factor analysis and observed temporal patterns were used to categorize sources for measured compounds as biogenic or anthropogenic or both. Compounds that were clearly biogenic included methylbutenol, isoprene and its oxidation products (methacrolein and methyl vinyl ketone), and terpenes (α-pinene, 3-carene, d-limonene). Other compounds were partially biogenic, including acetone, ethene, propene, hexanal, acetaldehyde, and methanol. Hydroxyl radical (OH) loss rates were dominated by the clearly biogenic compounds, accounting for 70% of the loss under mean midday conditions. The most important single compounds were isoprene (33%) and methylbutenol (21%). These two compounds were dominant under all conditions, including the coldest and most polluted days. Under the most polluted conditions, acetaldehyde became very important, accounting for 13% of the total. Total OH loss rates were highly correlated with temperature because emissions of biogenic compounds, which dominate OH loss, are strongly temperature dependent. Much of the research on biogenic volatile organic compounds has focused on isoprene and terpenes. Our results suggest that quantifying and understanding factors controlling biogenic emissions of other compounds such as methylbutenol, acetone, hexanal, methanol, and acetaldehyde are critical for improving our understanding of regional photochemistry.

  2. Measurement of volatile organic compounds emitted in libraries and archives: an inferential indicator of paper decay?

    PubMed Central

    2012-01-01

    Background A sampling campaign of indoor air was conducted to assess the typical concentration of indoor air pollutants in 8 National Libraries and Archives across the U.K. and Ireland. At each site, two locations were chosen that contained various objects in the collection (paper, parchment, microfilm, photographic material etc.) and one location was chosen to act as a sampling reference location (placed in a corridor or entrance hallway). Results Of the locations surveyed, no measurable levels of sulfur dioxide were detected and low formaldehyde vapour (< 18 μg m-3) was measured throughout. Acetic and formic acids were measured in all locations with, for the most part, higher acetic acid levels in areas with objects compared to reference locations. A large variety of volatile organic compounds (VOCs) was measured in all locations, in variable concentrations, however furfural was the only VOC to be identified consistently at higher concentration in locations with paper-based collections, compared to those locations without objects. To cross-reference the sampling data with VOCs emitted directly from books, further studies were conducted to assess emissions from paper using solid phase microextraction (SPME) fibres and a newly developed method of analysis; collection of VOCs onto a polydimethylsiloxane (PDMS) elastomer strip. Conclusions In this study acetic acid and furfural levels were consistently higher in concentration when measured in locations which contained paper-based items. It is therefore suggested that both acetic acid and furfural (possibly also trimethylbenzenes, ethyltoluene, decane and camphor) may be present in the indoor atmosphere as a result of cellulose degradation and together may act as an inferential non-invasive marker for the deterioration of paper. Direct VOC sampling was successfully achieved using SPME fibres and analytes found in the indoor air were also identified as emissive by-products from paper. Finally a new non

  3. Analysis of Volatile Organic Compounds in a Controlled Environment: Ethylene Gas Measurement Studies on Radish

    NASA Technical Reports Server (NTRS)

    Kong, Suk Bin

    2001-01-01

    Volatile organic compound(VOC), ethylene gas, was characterized and quantified by GC/FID. 20-50 ppb levels were detected during the growth stages of radish. SPME could be a good analytical tool for the purpose. Low temperature trapping method using dry ice/diethyl ether and liquid nitrogen bath was recommended for the sampling process for GC/PID and GC/MS analysis.

  4. DEVELOPMENT AND VALIDATION OF A METHOD FOR MEASURING EXEMPT VOLATILE ORGANIC COMPOUNDS AND CARBON DIOXIDE IN CONSUMER PRODUCTS

    EPA Science Inventory

    The report describes the development and validation of a method for measuring exempt volatile organic compounds (VOCs) and carbon dioxide in consumer products. (NOTE: Ground-level ozone can cause a variety of adverse health effects as well as agricultural and ecological damage. C...

  5. A High Frequency Response Relaxed Eddy Accumulation Flux Measurement System for Sampling Short-Lived Biogenic Volatile Organic Compounds

    EPA Science Inventory

    A second-generation relaxed eddy accumulation system was built and tested with the capability to measure vertical biogenic volatile organic compound (VOC) fluxes at levels as low as 10 µg C m−2 hr−1. The system features a continuous, integrated gas-phase ozo...

  6. Monitoring the dynamic emission of biogenic volatile organic compounds from Cryptomeria japonica by enclosure measurement

    NASA Astrophysics Data System (ADS)

    Lin, Chun-Ya; Chang, Tzu-Cheng; Chen, Yu-Han; Chen, Ying-Ju; Cheng, Sen-Sung; Chang, Shang-Tzen

    2015-12-01

    Research on biogenic volatile organic compounds (BVOCs) emitted from trees is essential in the world since these BVOCs play an important role in the atmospheric process which may further influence on the air quality. However, little is known about BVOCs emitted from trees in the field in Taiwan. Hence, this study intends to establish an enclosure technique coupled with in situ sampling to facilitate the collection of BVOCs emitted from Cryptomeria japonica leaves. Furthermore, the emission model derived from the relationship between emission rate and temperature was applied to estimate the emission of BVOCs in the field. Results from GC-MS showed that the BVOCs emitted from intact leaves contain 14 monoterpenoids and 4 sesquiterpenoid. The emission rate of the major constituent, sabinene, was 0.42 μg h-1 g-1 around noon on September 11, 2013. Sabinene varies with the changing temperature inside the bag. These findings indicated that the enclosure technique can collect the BVOCs emitted from intact leaves and monitor the dynamic changes in emission. Two determinants, basal emission rate (at 30 °C) and β coefficient, of sabinene were further measured, and they were 1.29 μg h-1 g-1 and 0.18 °C-1, respectively. By using these two determinants and data of meteorology and forest resource, the emission of monoterpenes from C. japonica stand was estimated to be 1.13 mg m-2 h-1 in July in Xitou area. Taken together, the results provide valuable information for estimation of BVOCs from tree species in Taiwan for the first time.

  7. Volatile organic compounds in Tijuana during the Cal-Mex 2010 campaign: Measurements and source apportionment

    NASA Astrophysics Data System (ADS)

    Zheng, Jun; Garzón, Jessica P.; Huertas, María E.; Zhang, Renyi; Levy, Misti; Ma, Yan; Huertas, José I.; Jardón, Ricardo T.; Ruíz, Luis G.; Tan, Haobo; Molina, Luisa T.

    2013-05-01

    As part of the Cal-Mex 2010 air quality study, a proton transfer reaction-mass spectrometer (PTR-MS) was deployed at the San Diego-Tijuana border area to measure volatile organic compounds (VOCs) from 15 May to 30 June 2010. The major VOCs identified during the study included oxygenated VOCs (e.g., methanol, acetaldehyde, acetone, and methyl ethyl ketone) and aromatics (e.g., benzene, toluene, C8- and C9-aromatics). Biogenic VOCs (e.g., isoprene) were scarce in this region because of the lack of vegetation in this arid area. Using an U.S. EPA positive matrix factorization model, VOCs together with other trace gases (NOx, NOz and SO2) observed in this border region were attributed to four types of sources, i.e., local industrial solvent usage (58% in ppbC), gasoline vehicle exhaust (19% in ppbC), diesel vehicle exhaust (14% in ppbC), and aged plume (9% in ppbC) due to regional background and/or long-range transport. Diesel vehicle emission contributed to 87% of SO2 and 75% of NOx, and aged plume contributed to 92% of NOz. An independent conditional probability function analysis of VOCs, wind direction, and wind speed indicated that the industrial source did not show a significant tendency with wind direction. Both gasoline and diesel engine emissions were associated with air masses passing through two busy cross-border ports. Aged plumes were strongly associated with NW wind, which likely brought in aged air masses from the populated San Diego area.

  8. Production of extremely low volatile organic compounds from biogenic emissions: Measured yields and atmospheric implications

    PubMed Central

    Jokinen, Tuija; Berndt, Torsten; Makkonen, Risto; Kerminen, Veli-Matti; Junninen, Heikki; Stratmann, Frank; Herrmann, Hartmut; Guenther, Alex B.; Worsnop, Douglas R.; Kulmala, Markku; Ehn, Mikael; Sipilä, Mikko

    2015-01-01

    Oxidation products of monoterpenes and isoprene have a major influence on the global secondary organic aerosol (SOA) burden and the production of atmospheric nanoparticles and cloud condensation nuclei (CCN). Here, we investigate the formation of extremely low volatility organic compounds (ELVOC) from O3 and OH radical oxidation of several monoterpenes and isoprene in a series of laboratory experiments. We show that ELVOC from all precursors are formed within the first minute after the initial attack of an oxidant. We demonstrate that under atmospherically relevant concentrations, species with an endocyclic double bond efficiently produce ELVOC from ozonolysis, whereas the yields from OH radical-initiated reactions are smaller. If the double bond is exocyclic or the compound itself is acyclic, ozonolysis produces less ELVOC and the role of the OH radical-initiated ELVOC formation is increased. Isoprene oxidation produces marginal quantities of ELVOC regardless of the oxidant. Implementing our laboratory findings into a global modeling framework shows that biogenic SOA formation in general, and ELVOC in particular, play crucial roles in atmospheric CCN production. Monoterpene oxidation products enhance atmospheric new particle formation and growth in most continental regions, thereby increasing CCN concentrations, especially at high values of cloud supersaturation. Isoprene-derived SOA tends to suppress atmospheric new particle formation, yet it assists the growth of sub-CCN-size primary particles to CCN. Taking into account compound specific monoterpene emissions has a moderate effect on the modeled global CCN budget. PMID:26015574

  9. Production of extremely low volatile organic compounds from biogenic emissions: Measured yields and atmospheric implications.

    PubMed

    Jokinen, Tuija; Berndt, Torsten; Makkonen, Risto; Kerminen, Veli-Matti; Junninen, Heikki; Paasonen, Pauli; Stratmann, Frank; Herrmann, Hartmut; Guenther, Alex B; Worsnop, Douglas R; Kulmala, Markku; Ehn, Mikael; Sipilä, Mikko

    2015-06-01

    Oxidation products of monoterpenes and isoprene have a major influence on the global secondary organic aerosol (SOA) burden and the production of atmospheric nanoparticles and cloud condensation nuclei (CCN). Here, we investigate the formation of extremely low volatility organic compounds (ELVOC) from O3 and OH radical oxidation of several monoterpenes and isoprene in a series of laboratory experiments. We show that ELVOC from all precursors are formed within the first minute after the initial attack of an oxidant. We demonstrate that under atmospherically relevant concentrations, species with an endocyclic double bond efficiently produce ELVOC from ozonolysis, whereas the yields from OH radical-initiated reactions are smaller. If the double bond is exocyclic or the compound itself is acyclic, ozonolysis produces less ELVOC and the role of the OH radical-initiated ELVOC formation is increased. Isoprene oxidation produces marginal quantities of ELVOC regardless of the oxidant. Implementing our laboratory findings into a global modeling framework shows that biogenic SOA formation in general, and ELVOC in particular, play crucial roles in atmospheric CCN production. Monoterpene oxidation products enhance atmospheric new particle formation and growth in most continental regions, thereby increasing CCN concentrations, especially at high values of cloud supersaturation. Isoprene-derived SOA tends to suppress atmospheric new particle formation, yet it assists the growth of sub-CCN-size primary particles to CCN. Taking into account compound specific monoterpene emissions has a moderate effect on the modeled global CCN budget. PMID:26015574

  10. Volatile Organic Compounds source contributions in Paris: Measurement and modeling approaches. Focus on the traffic source

    NASA Astrophysics Data System (ADS)

    Gros, Valerie; Petetin, Hervé; Sarda-Estève, Roland; Kalogridis, Cerise; Baudic, Alexia; Bonnaire, Nicolas; Bonsang, Bernard; Xueref-Rémy, Irène; Ammoura, Lamia; Le Priol, Tiphaine; François Petit, Jean; Sanchez, Olivier; Rosso, Amandine; Perrussel, Olivier; Petit, Jean-Eudes; Sciare, Jean

    2013-04-01

    Paris is one of the few European megacities and with 11 Million inhabitants, almost 1/5 French population lives in Paris and its region. The EU-MEGAPOLI project allowed a detailed characterization of gaseous and particulate pollution in Paris in summer (July 2009) and winter (Jan-Feb 2010). Studies about VOCs source contributions performed for these periods have suggested the importance of traffic emissions, in contradiction with the local emission inventory, for which solvent source is the dominant VOC source in Paris. In order to examine the representativity of such conclusions, one-year (March 2010- March 2011) of continuous measurements of VOCs have been performed at the same urban site in Paris (as part of a French program PRIMEQUAL-FRANCIPOL). In addition, VOCs measurements (along with other gaseous and aerosol compounds) have been performed in a tunnel in order to better characterize the traffic source (October 2012, PRIMEQUAL -PREQUALIF project). Preliminary results will be presented here from this unique dataset, with a focus made on oxygenated compounds (methanol, acetaldehyde, acetone) and aromatic compounds (benzene, toluene, xylens...). We will show that the daily variability of oxygenated compounds is mainly linked to the local traffic source, as suggested by their co-variation with other compounds related to traffic emissions (CO, xylens...). In addition to this local source, we will show that oxygenated compounds baseline concentration levels are significantly enhanced during specific events (of a few day duration) characterized by continental air masses. Surprisingly other long-lived compounds (CO) appear to be much less affected by these events, providing evidences that the nature of these continental sources is not yet well established. Results from VOCs source contributions identification, quantification and geographical origin (Positive Matrix Factorization and Potential Source Contribution Function approaches) will be presented as well as

  11. Measurement and estimated health risks of volatile organic compounds and polychlorinated biphenyls in air at the Hanford Site

    SciTech Connect

    Patton, G.W.; Cooper, A.T.; Blanton, M.L.

    1994-10-01

    A variety of radioactive and nonradioactive chemicals have been released in effluent streams and discharged to waste disposal facilities during the nuclear materials production period at the Hanford Site. Extensive environmental surveillance for radioactive materials has occurred at Hanford; however, only limited information is available on the types and concentrations of organic pollutants potentially present. This report describes work performed to provide the Hanford Site Surface Environmental Surveillance Project with representative air concentration data for volatile organic compounds and polychlorinated biphenyls (PCBs). US Environmental Protection Agency (USEPA) volatile organic compound sampling methods evaluated for Hanford Site use were carbon-based adsorbent traps (TO-2) and Summa air canisters (TO-14). Polychlorinated biphenyls were sampled using USEPA method (TO-4), which uses glass fiber filters and polyurethane foam adsorbent beds to collect the PCBs. This report also presents results for environmental surveillance samples collected for volatile organic compound and PCB analyses from 1990 to 1993. All measured air concentrations of volatile organic compounds and PCBs were well below applicable maximum allowable concentration standards for air contaminants. Because of the lack of ambient air concentration standards, a conservative estimate is provided of the potential human health impacts from exposure to the ambient air concentrations measured on the Hanford Site.

  12. Volatile organic compound concentrations and emission rates measured over one year in a new manufactured house

    SciTech Connect

    Hodgson, Alfred T.; Nabinger, Steven J.; Persily, Andrew K.

    2004-09-01

    A study to measure indoor concentrations and emission rates of volatile organic compounds (VOCs), including formaldehyde, was conducted in a new, unoccupied manufactured house installed at the National Institute of Standards and Technology (NIST) campus. The house was instrumented to continuously monitor indoor temperature and relative humidity, heating and air conditioning system operation, and outdoor weather. It also was equipped with an automated tracer gas injection and detection system to estimate air change rates every 2 h. Another automated system measured indoor concentrations of total VOCs with a flame ionization detector every 30 min. Active samples for the analysis of VOCs and aldehydes were collected indoors and outdoors on 12 occasions from August 2002 through September 2003. Individual VOCs were quantified by thermal desorption to a gas chromatograph with a mass spectrometer detector (GC/MS). Formaldehyde and acetaldehyde were quantified by high performance liquid chromatography (HPLC). Weather conditions changed substantially across the twelve active sampling periods. Outdoor temperatures ranged from 7 C to 36 C. House air change rates ranged from 0.26 h{sup -1} to 0.60 h{sup -1}. Indoor temperature was relatively constant at 20 C to 24 C for all but one sampling event. Indoor relative humidity (RH) ranged from 21% to 70%. The predominant and persistent indoor VOCs included aldehydes (e.g., formaldehyde, acetaldehyde, pentanal, hexanal and nonanal) and terpene hydrocarbons (e.g., a-pinene, 3-carene and d-limonene), which are characteristic of wood product emissions. Other compounds of interest included phenol, naphthalene, and other aromatic hydrocarbons. VOC concentrations were generally typical of results reported for other new houses. Measurements of total VOCs were used to evaluate short-term changes in indoor VOC concentrations. Most of the VOCs probably derived from indoor sources. However, the wall cavity was an apparent source of

  13. Organic compounds in meteorites

    NASA Technical Reports Server (NTRS)

    Lawless, J. G.

    1980-01-01

    Recent studies of carbonaceous chondrites provide evidence that certain organic compounds are indigenous and the result of an abiotic, chemical synthesis. The results of several investigators have established the presence of amino acids and precursors, mono- and dicarboxylic acids, N-heterocycles, and hydrocarbons as well as other compounds. For example, studies of the Murchison and Murray meteorites have revealed the presence of at least 40 amino acids with nearly equal abundances of D and L isomers. The population consists of both protein and nonprotein amino acids including a wide variety of linear, cyclic, and polyfunctional types. Results show a trend of decreasing concentration with increasing carbon number, with the most abundant being glycine (41 n Moles/g). These and other results to be reviewed provide persuasive support for the theory of chemical evolution and provide the only natural evidence for the protobiological subset of molecules from which life on earth may have arisen.

  14. Breath Biomarkers to Measure Uptake of Volatile Organic Compounds by Bicyclists.

    PubMed

    Bigazzi, Alexander Y; Figliozzi, Miguel A; Luo, Wentai; Pankow, James F

    2016-05-17

    Breath biomarkers were used to study uptake of traffic-related volatile organic compounds (VOCs) from urban bicycling. Breath analysis was selected because it is one of the least invasive methods to assess urban traveler exposure. Research hurdles that were overcome included considering that factors other than on-road exposure can influence concentrations in the body, and absorbed doses during a trip can be small compared to baseline body burdens. Pre-trip, on-road, and post-trip breath concentrations and ambient air concentrations were determined for 26 VOCs for bicyclists traveling on different path types. Statistical analyses of the concentration data identified eight monoaromatic hydrocarbons potentially useful as breath biomarkers to compare differences in body levels brought about by urban travel choices. Breath concentrations of the biomarker compounds were significantly higher than background levels after riding on high-traffic arterial streets and on a path through a high-exposure industrial area, but not after riding on low-traffic local streets or on other off-street paths. Modeled effects of high-traffic streets on ambient concentrations were 100-200% larger than those of low-traffic streets; modeled effects of high-traffic streets on breath concentrations were 40-100% larger than those of low-traffic streets. Similar percentage increases in breath concentrations are expected for bicyclists in other cities. PMID:27097118

  15. In situ measurement of volatile organic compounds in groundwater by methods coupled to the cone penetrometer

    SciTech Connect

    Doskey, P.V.; Aldstadt, J.H.; Kuo, J.M.; Costanza, M.S.; Erickson, M.D.

    1995-03-01

    The objective of this investigation is to interface an in situ, on-line sparging system with a cone penetrometer to provide direct analysis of volatile organic compounds (VOCS) in groundwater by on-site analysis. Transfer line materials (15 m {times} 0.160--0.216 cm ID) composed of stainless steel, nickel, aluminum and Teflon{reg_sign}PFA, PTFE, and FEP were evaluated for their ability to quantitatively transfer chloroform, 1,1,1-trichloroethane, carbon tetrachloride, tetrachloroethylene, n-hexane, benzene, toluene, and o-xylene in the gas phase. The water content of the gas stream had an insignificant effect on the quantitative transfer of VOCs through Teflon{reg_sign} tubing but was critical to quantitative transfer of the compounds through metal tubing, particularly for nickel. Transfer efficiencies for all 7 analytes in moist gas streams through stainless steel tubing were greater than 95%. Toluene, tetrachloroethylene, and o-xylene were transferred with 93, 81 and 80% efficiency, respectively when drawn through Teflon{reg_sign}PFA tubing at 25 C. The sorption of these VOCs by Teflon{reg_sign} tubing was reversible and their transfer efficiencies improved to 94% when the tubing was flushed with 16 equivalent volumes of air. In general, the retention of the VOCs by Teflon{reg_sign} increased with decreasing aqueous solubility of the analyte. The efficiency at which VOCs were sparged from aqueous standards in Teflon{reg_sign}PFA, Type 304 stainless steel, and glass vessels were similar.

  16. Remote detection of volatile organic compounds by passive multispectral infrared imaging measurements.

    PubMed

    Wabomba, Mukire J; Sulub, Yusuf; Small, Gary W

    2007-04-01

    Automated pattern recognition methodology is described for the detection of signatures of volatile organic compounds from passive multispectral infrared imaging data collected from an aircraft platform. Data are acquired in an across-track scanning mode with a downward-looking line scanner based on 8 to 16 spectral channels in the 8-14 and 3-5 microm spectral ranges. Two controlled release experiments are performed in which plumes of ethanol are generated and detected from aircraft overflights at altitudes of 2200 to 2800 ft (671 to 853 m). In addition, a methanol release from a chemical manufacturing facility is monitored. Automated classifiers are developed by application of piecewise linear discriminant analysis to the calibrated, registered, and preprocessed radiance data acquired by the line scanner. Preprocessing steps evaluated include contrast enhancement, temperature-emissivity separation, feature selection, and feature extraction/noise reduction by the minimum noise fraction (MNF) transform. Successful classifiers are developed for both compounds and are tested with data not used in the classifier development. Separation of temperature and emissivity by use of the alpha residual calculation is found to reduce false positive detections to a negligible level, and the MNF transform is shown to enhance detection sensitivity. PMID:17456252

  17. Laboratory measurements of emissions of nonmethane volatile organic compounds from biomass burning in Chinese crop residues

    NASA Astrophysics Data System (ADS)

    Inomata, S.; Tanimoto, H.; PAN, X.; Taketani, F.; Komazaki, Y.; Miyakawa, T.; Kanaya, Y.; Wang, Z.

    2014-12-01

    The emission factors (EFs) of volatile organic compounds (VOCs) from the burning of Chinese crop residue were investigated as a function of modified combustion efficiency by the laboratory experiments. The VOCs including acetonitrile, aldehydes/ketones, furan, and aromatic hydrocarbons were monitored by proton-transfer-reaction mass spectrometry. Two samples, wheat straw and rape plant, were burned in dry conditions and for some experiments wheat straw was burned under wet conditions. We compared the present data to the field data reported by Kudo et al. [2014]. The agreement between the field and laboratory data was obtained for aromatics for relatively more smoldering data of dry samples but the field data were slightly underestimated compared with the laboratory data for oxygenated VOCs (OVOCs) and acetonitrile. When the EFs from the burning of wet samples were investigated, the underestimations for OVOCs and acetonitrile were improved compared with the data of dry samples. It may be a property of the burning of crop residue in the region of high temperature and high humidity that some inside parts of piled crop residue and/or the crop residue facing on the ground are still wet. But the ratios for acetic acid/glycolaldehyde was still lower than 1. This may suggest that strong loss processes of acetic acid/glycolaldehyde are present in the fresh plume.Kudo S., H. Tanimoto, S. Inomata, S. Saito, X. L. Pan, Y. Kanaya, F. Taketani, Z. F. Wang, H. Chen, H. Dong, M. Zhang, and K. Yamaji (2014), Emissions of nonmethane volatile organic compounds from open crop residue burning in Yangtze River Delta region, China, J. Geophys. Res. Atmos., 119, 7684-7698, doi: 10.1002/2013JD021044.

  18. Airborne measurements of organic bromine compounds in the Pacific tropical tropopause layer

    PubMed Central

    Navarro, Maria A.; Atlas, Elliot L.; Saiz-Lopez, Alfonso; Rodriguez-Lloveras, Xavier; Kinnison, Douglas E.; Lamarque, Jean-Francois; Tilmes, Simone; Filus, Michal; Harris, Neil R. P.; Meneguz, Elena; Ashfold, Matthew J.; Manning, Alistair J.; Cuevas, Carlos A.; Schauffler, Sue M.; Donets, Valeria

    2015-01-01

    Very short-lived brominated substances (VSLBr) are an important source of stratospheric bromine, an effective ozone destruction catalyst. However, the accurate estimation of the organic and inorganic partitioning of bromine and the input to the stratosphere remains uncertain. Here, we report near-tropopause measurements of organic brominated substances found over the tropical Pacific during the NASA Airborne Tropical Tropopause Experiment campaigns. We combine aircraft observations and a chemistry−climate model to quantify the total bromine loading injected to the stratosphere. Surprisingly, despite differences in vertical transport between the Eastern and Western Pacific, VSLBr (organic + inorganic) contribute approximately similar amounts of bromine [∼6 (4−9) parts per thousand] to the stratospheric input at the tropical tropopause. These levels of bromine cause substantial ozone depletion in the lower stratosphere, and any increases in future abundances (e.g., as a result of aquaculture) will lead to larger depletions. PMID:26504212

  19. Airborne measurements of organic bromine compounds in the Pacific tropical tropopause layer.

    PubMed

    Navarro, Maria A; Atlas, Elliot L; Saiz-Lopez, Alfonso; Rodriguez-Lloveras, Xavier; Kinnison, Douglas E; Lamarque, Jean-Francois; Tilmes, Simone; Filus, Michal; Harris, Neil R P; Meneguz, Elena; Ashfold, Matthew J; Manning, Alistair J; Cuevas, Carlos A; Schauffler, Sue M; Donets, Valeria

    2015-11-10

    Very short-lived brominated substances (VSLBr) are an important source of stratospheric bromine, an effective ozone destruction catalyst. However, the accurate estimation of the organic and inorganic partitioning of bromine and the input to the stratosphere remains uncertain. Here, we report near-tropopause measurements of organic brominated substances found over the tropical Pacific during the NASA Airborne Tropical Tropopause Experiment campaigns. We combine aircraft observations and a chemistry-climate model to quantify the total bromine loading injected to the stratosphere. Surprisingly, despite differences in vertical transport between the Eastern and Western Pacific, VSLBr (organic + inorganic) contribute approximately similar amounts of bromine [∼6 (4-9) parts per trillion] [corrected] to the stratospheric input at the tropical tropopause. These levels of bromine cause substantial ozone depletion in the lower stratosphere, and any increases in future abundances (e.g., as a result of aquaculture) will lead to larger depletions. PMID:26504212

  20. In situ measurements of volatile organic compounds in a boreal forest

    NASA Astrophysics Data System (ADS)

    Hakola, H.; Hellén, H.; Hemmilä, M.; Rinne, J.; Kulmala, M.

    2012-12-01

    We present biogenic VOC, including sesquiterpenes, measurements at the SMEAR II station (Station For Measuring Forest Ecosystem-Atmosphere Relations) in Finland using an in situ gas chromatograph mass-spectrometer with 2 h time resolution. The measurements were conducted over the period October 2010-October 2011, at least one week every month. To our knowledge there are no earlier species-speciated semi-continuous BVOC data also covering dormant periods. This was also the first time sesquiterpene mixing ratios were measured in a boreal forest. During the winter months, and still in March, the mixing ratios of all biogenic compounds were very low, most of the time below detection limits. The monoterpene mixing ratios increased in April and started to show diurnal variability, with maximum mixing ratio at night and minima during the day. The diurnal variability continued until October, after which the mixing ratios decreased and then only occasional episodes took place. The diurnal variation was affected by boundary layer height. Sesquiterpene mixing ratios were very low, only a few ppt. The main sesquiterpenes were longifolene and isolongifolene. The diurnal variation of isoprene was opposite to the mono- and sesquiterpene diurnal curve due to isoprene's light dependent emissions. Due to its daytime maximum mixing ratios, isoprene also dominated hydroxyl radical reactivity in summer even though our isoprene measurements are underestimates due to a breakthrough in a cold trap.

  1. Insights on Sources, Growth, and Phase Partitioning of Atmospheric Particles from Hourly Measurements of Organic Marker Compounds

    NASA Astrophysics Data System (ADS)

    Williams, B.; Goldstein, A.; Kreisberg, N.; Hering, S.; Docherty, K.; Jimenez, J.; Shields, L.; Qin, X.; Prather, K.; Ziemann, P.

    2007-12-01

    Atmospheric aerosols have adverse affects on human health and have direct and indirect affects on the global radiation balance. In order to implement particle concentration control strategies, we must first understand particle origins. Atmospheric aerosols have both primary sources such as combustion processes and secondary sources such as photochemically driven gas to particle phase partitioning. By monitoring changes in the molecular composition of the organic fraction of atmospheric aerosols, these various sources can be differentiated. Thermal desorption Aerosol Gas chromatography (TAG) is a new in-situ instrument capable of identifying and quantifying organic aerosol chemical composition with one hour time resolution. TAG is fully automated, offering around the clock measurements to determine diurnal, weekly, and seasonal patterns in organic aerosol composition, hence, determining aerosol sources and transformation processes. We report results from ambient measurements made in Southern California during the summer and fall of 2005 as part of the Study of Organic Aerosol at Riverside (SOAR). We use hourly measurements of over 300 individual organic compounds to define both primary and secondary particle sources. The particle sources defined include primary anthropogenic sources such as vehicle emissions, meat cooking, biomass burning, pesticide use, herbicide use, along with primary biogenic sources such as plant emissions and plant waxes. We also explore secondary particle sources (i.e. SOA) formed as a result of the oxidation of biogenic and anthropogenic precursor gases. Comparisons are made between TAG-defined sources and aerosol sources defined using Aerosol Time-Of-Flight Mass Spectrometer (ATOFMS) and Aerosol Mass Spectrometer (AMS) data. In addition to source apportionment results, we present seasonal changes in ambient phase partitioning of organic compounds as a function of carbon number for multiple compound classes.

  2. In situ measurements of volatile organic compounds in a boreal forest

    NASA Astrophysics Data System (ADS)

    Hakola, H.; Hellén, H.; Henriksson, M.; Rinne, J.; Kulmala, M.

    2012-06-01

    We present biogenic VOC, including sesquiterpenes, measurements at the SMEAR II station (Station For Measuring Forest Ecosystem-Atmosphere Relations) in Finland using an in situ gas chromatograph mass-spectrometer with 2 h time resolution. The measurements were conducted over the period October 2010-October 2011, at least one week every month. To our knowledge there are no earlier species-speciated semi-continuous BVOC data also covering dormant periods. During the winter months, and still in March, the concentrations of all biogenic compounds were very low, most of the time below detection limits. The monoterpene concentrations increased in April and started to show diurnal variability, with maximum concentrations at night and minima during the day. The diurnal variability continued until October, after which the concentrations decreased and then only occasional episodes took place. The diurnal variation was affected by boundary layer height. Sesquiterpene concentrations were very low, only a few ppt. The main sesquiterpenes were longifolene and isolongifolene. The diurnal variation of isoprene was opposite to the mono- and sesquiterpene diurnal curve due to isoprene's light dependent emissions. Due to its daytime maximum concentrations, isoprene also dominated hydroxyl radical reactivity in summer even though our isoprene measurements are underestimates due to a breakthrough in a cold trap.

  3. In situ measurement of volatile organic compounds in groundwater by methods coupled to the cone penetrometer

    SciTech Connect

    Doskey, P.V.; Aldstadt, J.H.; Kuo, J.M.; Costanza, M.S.; Erickson, M.D.

    1995-12-31

    The objective of this investigation was to interface an in situ, on-line sparging system with a cone penetrometer to provide direct analysis of volatile organic compounds (VOCS) in groundwater by on-site analysis. Transfer lines (15 m x 0.160- to 0.216-cm ID) composed of stainless steel, nickel, aluminum and Teflon{reg_sign} PFA, PTFE, and FEP were evaluated for their ability to quantitatively transfer chloroform, 1,1,1-trichloroethane, carbon tetrachloride, tetrachloroethylene, n-hexane, benzene, toluene, and o-xylene in the gas phase at 25 C. The water content of the gas stream had an insignificant effect on the quantitative transfer of VOCs through Teflon{reg_sign} tubing but was critical to efficiently transfer the compounds through metal tubing, particularly nickel. Transfer efficiencies for all eight analytes in moist gas streams through stainless steel tubing were greater than 95%. Toluene, tetrachloroethylene, and o-xylene were transferred with 93, 81, and 80% efficiency, respectively, when they were drawn through Teflon{reg_sign} PFA tubing at 25 C. The sorption of these VOCs by Teflon{reg_sign} tubing was reversible, and their transfer efficiencies improved to 94% when the tubing was flushed with 16 equivalent volumes of air. In general, the retention of the VOCs by Teflon{reg_sign} increased with decreasing aqueous solubility of the analyte. The efficiencies at which VOCs were sparged from aqueous standards in Teflon{reg_sign} PFA, Type 304 stainless steel, and glass vessels were similar.

  4. Measuring partition and diffusion coefficients for volatile organic compounds in vinyl flooring

    NASA Astrophysics Data System (ADS)

    Cox, Steven S.; Zhao, Dongye; Little, John C.

    Interactions between volatile organic compounds (VOCs) and vinyl flooring (VF), a relatively homogenous, diffusion-controlled building material, were characterized. The sorption/desorption behavior of VF was investigated using single-component and binary systems of seven common VOCs ranging in molecular weight from n-butanol to n-pentadecane. The simultaneous sorption of VOCs and water vapor by VF was also investigated. Rapid determination of the material/air partition coefficient ( K) and the material-phase diffusion coefficient ( D) for each VOC was achieved by placing thin VF slabs in a dynamic microbalance and subjecting them to controlled sorption/desorption cycles. K and D are shown to be independent of concentration for all of the VOCs and water vapor. For the four alkane VOCs studied, K correlates well with vapor pressure and D correlates well with molecular weight, providing a means to estimate these parameters for other alkane VOCs. While the simultaneous sorption of a binary mixture of VOCs is non-competitive, the presence of water vapor increases the uptake of VOCs by VF. This approach can be applied to other diffusion-controlled materials and should facilitate the prediction of their source/sink behavior using physically-based models.

  5. Laboratory measurements of emission factors of nonmethane volatile organic compounds from burning of Chinese crop residues

    NASA Astrophysics Data System (ADS)

    Inomata, Satoshi; Tanimoto, Hiroshi; Pan, Xiaole; Taketani, Fumikazu; Komazaki, Yuichi; Miyakawa, Takuma; Kanaya, Yugo; Wang, Zifa

    2015-05-01

    The emission factors (EFs) of nonmethane volatile organic compounds (NMVOCs) emitted during the burning of Chinese crop residue were investigated as a function of modified combustion efficiency in laboratory experiments. NMVOCs, including acetonitrile, aldehydes/ketones, furan, and aromatic hydrocarbons, were monitored by proton-transfer-reaction mass spectrometry. Rape plant was burned in dry conditions and wheat straw was burned in both wet and dry conditions to simulate the possible burning of damp crop residue in regions of high temperature and humidity. We compared the present data to field data reported by Kudo et al. (2014). Good agreement between field and laboratory data was obtained for aromatics under relatively more smoldering combustion of dry samples, but laboratory data were slightly overestimated compared to field data for oxygenated VOC (OVOC). When EFs from the burning of wet samples were investigated, the consistency between the field and laboratory data for OVOCs was stronger than for dry samples. This may be caused by residual moisture in crop residue that has been stockpiled in humid regions. Comparison of the wet laboratory data with field data suggests that Kudo et al. (2014) observed the biomass burning plumes under relatively more smoldering conditions in which approximately a few tens of percentages of burned fuel materials were wet.

  6. Measurement of emissions from air pollution sources. 4. C1-C27 organic compounds from cooking with seed oils.

    PubMed

    Schauer, James J; Kleeman, Michael J; Cass, Glen R; Simoneit, Bernd R T

    2002-02-15

    The emission rates of gas-phase, semivolatile, and particle-phase organic compounds ranging in carbon number from C1 to C27 were measured from institutional-scale food cooking operations that employ seed oils. Two cooking methods and three types of seed oils were examined: vegetables stir-fried in soybean oil, vegetables stir-fried in canola oil, and potatoes deep fried in hydrogenated soybean oil. The emission rates of 99 organic compounds were quantified, and these include n-alkanes, branched alkanes, alkenes, n-alkanoic acids, n-alkenoic acids, carbonyls, aromatics, polycyclic aromatic hydrocarbons (PAH), and lactones. Carbonyls and fatty acids (n-alkanoic and n-alkenoic acids) make up a significant portion of the organic compounds emitted from all three seed oil cooking procedures. The compositional differences in the organic compound emissions between the different cooking operations are consistent with the differences in the organic composition of the various cooking oils used. The distribution of the n-alkanoic acids between the gas and particle phases was found to be in good agreement with gas/particle partitioning theory. The relative importance of emissions from commercial deep frying operations to the total emissions of C16 and C18 n-alkanoic acids in the Los Angeles urban area was estimated using the available information and is estimated to account for approximately 7% of the total primary emissions of these acids. Additional emissions of these n-alkanoic acids from stir-frying and grill frying operations are expected. Estimates also indicate that seed oil cooking may make up a significant fraction of the emissions of lighter n-alkanoic acids such as nonanoic acid. PMID:11883419

  7. Compound Specific Concentration and Stable Isotope Ratio Measurements of Atmospheric Particulate Organic Matter and Gas Phase Nitrophenols

    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.

  8. OH Reactivity and Potential SOA Yields from Volatile Organic Compounds and Other Trace Gases Measured in Controlled Laboratory Biomass Burns

    NASA Astrophysics Data System (ADS)

    Gilman, J. B.; Warneke, C.; Kuster, W. C.; Goldan, P. D.; Veres, P. R.; Roberts, J. M.; de Gouw, J. A.; Burling, I. R.; Yokelson, R. J.

    2010-12-01

    A comprehensive suite of instruments were used to characterize volatile organic compounds (VOCs) and other trace gases (e.g., CO, CH4, NO2, etc.) emitted from controlled burns of various fuel types common to the Southeastern and Southwestern United States. These laboratory-based measurements were conducted in February 2009 at the U.S. Department of Agriculture’s Fire Sciences Laboratory in Missoula, Montana. An on-line GC-MS provided highly speciated VOC measurements of alkenes, alkanes, oxygenates, aromatics, biogenics, and nitrogen-containing compounds during the flaming or smoldering phases of replicate burns. The speciated GC-MS “grab” samples were integrated with fast-response gas-phase measurements (e.g., PTR-MS, PTR-IT-MS, NI-PT-CIMS, and FTIR) in order to determine VOC emission ratios and the fraction of identified vs. unidentifiable mass detected by PTR-MS. Emission ratios were used to calculate OH reactivity, which is a measure of potential ozone formation, as well as potential secondary organic aerosol (SOA) yields from the various fuel types. Small oxygenated VOCs had the highest emission ratios of the compounds observed. Alkenes dominated the VOC OH reactivity, which occasionally exceeded 1000 s-1. Calculated SOA yields from known precursors were dominated by aromatic VOCs, such as toluene, naphthalene (C10H8), and 1,3-benzenediol (C6H6O2, resorcinol). The contribution of several compounds not typically reported in ambient air measurements, such as substituted furans (C4H4O), pyrroles (C4H5N), and unsaturated C9 aromatics (C9H10), on OH reactivity and SOA yields will be discussed.

  9. On-line measurements of nitro organic compounds emitted from automobiles by proton transfer reaction mass spectrometry: Laboratory experiments and a field measurement

    NASA Astrophysics Data System (ADS)

    Inomata, S.; Tanimoto, H.; Fujitani, Y.; Fushimi, A.; Sato, K.; Sekimoto, K.; Yamada, H.; Hori, S.; Shimono, A.; Hikida, T.

    2011-12-01

    On-line measurements of nitro organic compounds in automobile exhaust were carried out by proton transfer reaction mass spectrometry (PTR-MS) with a chassis dynamometer. Diesel vehicles with oxidation catalyst system (diesel vehicle A) and with diesel PM-NOx reduction system ((diesel vehicle B) and a gasoline vehicle were used as a test vehicle. In the case of the diesel vehicle A, the emissions of nitromethane, nitrophenol (NPh), C7-, C8-, C9-, and C10-nitrophenols, and dihydroxynitrobenzenes (DHNB) were observed in the diesel exhaust from the experiment under the constant driving at 60 km hr-1. Temporal variations of mixing ratios for nitromethane, NPh, and DHNB along with related volatile organic compounds (VOCs) were measured during a transient driving cycle. The time-resolved measurement revealed that the nitromethane emission was strongly correlated with the emissions of CO, benzene, and acetone, which are relatively quickly produced in acceleration processes and appeared as sharp peaks. On the other hand, the NPh emission was moderately correlated with the emissions of acetic acid and phenol, which peaks were broad. The emission of nitromethane was observed from the exhaust of the diesel vehicle B but the emission of other nitro organic compounds was not observed. This suggests that the emission of nitro organic compounds besides nitromethane may depend on the diesel exhaust aftertreatment devices. The emission of nitromethane was also observed from the exhaust of the gasoline vehicle with cold start. An in-situ measurement of nitro organic compounds and their related VOCs was carried out at the crossing of an urban city, Kawasaki. Nitromethane was observed at the crossing and we found that the concentration of nitrometane varied rapidly. During the measurement, the maximum of the concentration of nitrometane reached 5 ppbv. Not only nitrophenols but also nitroaromatics were sometimes detected in the field measurement.

  10. Measurements of volatile organic compounds emitted from plants in the metropolitan area of São Paulo City , Brazil.

    NASA Astrophysics Data System (ADS)

    Carvalho, L.; Pisani, S.; Pool, C.; Vasconcellos, P.

    2003-04-01

    The presence of the biogenic hydrocarbons in an NO_x-containing atmosphere can enhance ozone generation and the impact of volatile organic compounds (VOCs) emitted from vegetation on atmospheric chemistry has been investigated. No study of VOC emission rates from plant species has been carried out in São Paulo City, Brazil, prior to this work. This study is part of a three-years project on biogenic volatile organic compounds emissions from species of plants found in the vegetation of the São Paulo metropolitan area. Typical plants (Alchornea sidifolia, Cupania oblongifolia, Cecropia pachystachia, Casearia sylvestris, Machaerium villosum, Croton floribundus, Myrcia rostrata, Solanum erianthum and Ficus insípida) were selected and identical species were studied in urban, sub-urban and forest regions. Biogenic hydrocarbons were determined placing branches of plants in enclosures and measuring the accumulation of emitted compounds in an all-Teflon chamber, the cuvette system. Measuring ambient VOC concentration adsorptive preconcentration, followed by GC-MS after thermal desorption of the sample, was employed to determine components heavier than C_5. Collection of carbonyl compounds on 2, 4-dinitrophenylhydrazine coated particles followed by HPLC-UV was used to analyze low molecular weight carbonyl compounds. Emissions rates of isoprene, a-pinene, camphene and limonene ranged from 0.01 to 2.16 μg C/h.g and emissions rates of aldehydes (C_1 - C_6), acrolein, methacrolein, 2-butanone and acetone ranged from 0.04 to 4.20 μg C/h.g. Ambient and chamber temperatures, relative humidity, light intensity, O_3 and NO_x were monitored during experiments.

  11. First PTRMS measurements of Volatile Organic Compounds from a Suburban site in India during the Monsoon Season

    NASA Astrophysics Data System (ADS)

    Sinha, V.

    2011-12-01

    Atmospheric levels of several important ozone precursor volatile organic compounds (VOCs) are reported in this study which were obtained by deploying a Proton transfer reaction mass spectrometer (PTR-MS) for the first time in India. The measurements were performed at a suburban site in Mohali, Punjab (30.78 N, 76.66 E) at circa 15 m above ground. Diel trends and seasonal averages of methanol, acetone, acetaldehyde, acetonitrile, isoprene, benzene, toluene and xylene are reported for the monsoon season, which is characterized by enhanced rates of wet deposition for various pollutants. Full mass scans of ambient air (upto 160 a.m.u ) are also shown indicating the presence of over 30 VOCs in ambient air comprising different organic classes of compounds such as alkenes, aromatics, alcohols, aldehydes, and ketones. In combination with measurements of Ozone, Nitrogen oxides and Carbon monoxide a comprehensive chemical characterization of the air masses and the factors driving the ozone chemistry has been carried out. This unique new dataset from a region known for scarcity of such measurements also reveals unique insights regarding the photochemical processing of primary emissions and potential implications for downwind ozone and secondary organic aerosol formation in the "wheat bowl" region of India.

  12. Measurement Protocols for In Situ Analysis of Organic Compounds at Mars and Comets

    NASA Technical Reports Server (NTRS)

    Mahaffy, P. R.; Brinckerhoff, W. B.; Buch, A.; Cabane, M.; Coll, P.; Demick, J.; Glavin, D. P.; Navarro-Gonzalez, R.

    2005-01-01

    The determination of the abundance and chemical and isotopic composition of organic molecules in comets and those that might be found in protected environments at Mars is a first step toward understanding prebiotic chemistries on these solar system bodies. While future sample return missions from Mars and comets will enable detailed chemical and isotopic analysis with a wide range of analytical techniques, precursor insitu investigations can complement these missions and facilitate the identification of optimal sites for sample return. Robust automated experiments that make efficient use of limited spacecraft power, mass, and data volume resources are required for use by insitu missions. Within these constraints we continue to explore a range of instrument techniques and measurement protocols that can maximize the return from such insitu investigations.

  13. Measurement Protocols for In situ Analysis of Organic Compounds at Mars and Comets

    NASA Technical Reports Server (NTRS)

    Mahaffy, P. R.; Brinckerhuff, W. B.; Buch, A.; Cabane, M.; Coll, P.; Demick, J.; Glavin, D. P.; Navarro-Gonzalez, R.

    2005-01-01

    The determination of the abundance and chemical and isotopic composition of organic molecules in comets and those that might be found in protected environments at Mars is a first step toward understanding prebiotic chemistries on these solar system bodies. While future sample return missions from Mars and comets will enable detailed chemical and isotopic analysis with a wide range of analytical techniques, precursor insitu investigations can complement these missions and facilitate the identification of optimal sites for sample return. Robust automated experiments that make efficient use of limited spacecraft power, mass, and data volume resources are required for use by insitu missions. Within these constraints we continue to explore a range of instrument techniques and measurement protocols that can maximize the return from such insitu investigations.

  14. Near-real-time measurement of trace volatile organic compounds from combustion processes using an on-line gas chromatography

    SciTech Connect

    Ryan, J.V.; Lemieux, P.M.; Preston, W.T.

    1998-12-31

    The US EPA`s current regulatory approach for combustion and incineration sources considers the use of real-time continuous emission monitors (CEMs) for particulate, metals, and organic compounds to monitor source emissions. Currently, the CEM technologies to support this approach have not been thoroughly developed and/or demonstrated. The EPA`s air Pollution Prevention and Control Division has developed a near-real-time volatile organic compound (VOC) CEM, using an on-line gas chromatograph (OLGC), capable of measuring over 20 VOCs at concentrations typically present in well-operated combustion systems. The OLGC system consists of a sample delivery system, a sample concentrator, and a GC equipped with both flame ionization and electron capture detectors. Application of the OLGC system was initially demonstrated through participation in the 1995 US EPA/DOE CEM demonstration program. Additional work has improved system performance, including increased automation and improved calibration technique. During pilot-scale incineration testing, measurement performance was examined in detail through comparisons to various CEM performance criteria. Specifically, calibration error, calibration drift error, and system bias were examined as a function of full scale and gas concentration. Although OLGC measurement performance was not able to meet standard EPA CEM measurement performance criteria, measurement performance was encouraging. The system demonstrated the ability to perform hourly trace level VOC measurements for as many as 23 different VOCs with boiling points ranging from {minus}23.7 to 180.5 C at a known level of measurement performance. This system is a suitable alternative to VOC reference method measurements which may be performed only intermittently.

  15. Measurement of trace gases and organic compounds in the smoke plume from a wildfire in Penedono (central Portugal)

    NASA Astrophysics Data System (ADS)

    Vicente, Ana; Alves, Célia; Monteiro, Cristina; Nunes, Teresa; Mirante, Fátima; Evtyugina, Margarita; Cerqueira, Mário; Pio, Casimiro

    2011-09-01

    Gas and particulate fractions were measured simultaneously from a wildfire in Penedono, central Portugal, which occurred in summer 2009. The total volatile hydrocarbons (THC) and carbon oxides (CO 2 and CO) collected in Tedlar bags were measured using automatic analysers with flame ionisation and non-dispersive infrared detectors, respectively. Carbonyls (formaldehyde and acetaldehyde) were sampled from the Tedlar bags in DNHP cartridges and analysed by high-performance liquid chromatography. Fine (PM 2.5) and coarse (PM 2.5-10) smoke particles were collected sequentially, on pre-fired quartz fibre filters, with a portable high-volume sampler. The detailed speciation of organic compounds in smoke samples was carried out by gas chromatography-mass spectrometry. The organic and elemental carbon content of particulate matter was analysed by a thermal-optical transmission technique. Average emission factors of 1.86 ± 0.80 and 0.063 ± 0.066 g kg -1 (dry basis) were obtained for acetaldehyde and formaldehyde, respectively. The THC, CO, CO 2, PM 2.5, PM 10, OC and EC emission factors (g kg -1 fuel burned, dry basis) were 260 ± 88, 268 ± 92, 1200 ± 172, 37 ± 12.2, 40 ± 12.6, 21 ± 6.7 and 0.44 ± 0.21, respectively. The chromatographically resolved organics included n-alkanes, n-alkenes, n-alkanoic acids, n-di-acids, unsaturated fatty acids, phenolic compounds, ketones, steroids, di- and triterpenoids, PAHs, with retene as the major compound, oxygenated PAH and anhydrosugars.

  16. In situ Measurements of Gas- and Particle-Phase Organic Compounds: Insights for SOA Formation Mechanisms and Contributions of SOA to Organic Aerosol

    NASA Astrophysics Data System (ADS)

    Zhao, Y.; Kreisberg, N. M.; Worton, D. R.; Isaacman, G. A.; Weber, R.; Liu, S.; Day, D. A.; Markovic, M. Z.; VandenBoer, T. C.; Russell, L. M.; Murphy, J. G.; Hering, S. V.; Goldstein, A. H.

    2011-12-01

    To investigate formation of secondary organic aerosol (SOA) and the contribution of SOA to organic aerosols, semi-volatile and intermediate-volatile organic compounds (SVOCs/IVOCs) in both gas and particle phases were measured using a modified Thermal Desorption Gas Chromatograph (TAG) instrument in Bakersfield, CA during the CALifornia at the NEXus between air quality and climate (CALNEX) campaign from 31 May through 27 June, 2010. More than 150 organic compounds were identified, spanning a wide range of volatility and functionality. Quantified compounds included organic tracers for primary and secondary organic sources, such as alkanes, PAHs, acids, hopanes and ketones. Hourly gas/particle partitioning was determined by a denuder difference method where the sample flow alternated every other sample through an active charcoal multi-channel denuder that efficiently removed gas-phase components. Gas/particle partitioning of three SOA tracers (phthalic acid, pinonaldehyde and 6, 10, 14-trimethyl-2-pentadecanone) was investigated to understand the formation mechanisms of SOA for different functional group classes in the ambient atmosphere. Comparison with Pankow gas/particle partitioning theory, observed particle-phase phthalic acid and pinonaldehyde, suggests formation by other mechanisms than gas-to-particle condensation. Source attribution is performed using Positive Matrix Factorization (PMF) analysis of speciated particle-phase TAG data along with total submicron organic aerosol (OA) measured by an Aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS). SOA accounts for a major component of OA and the contribution of biogenic SOA to total SOA is comparable to anthropogenic SOA during nights.

  17. Volatile organic compound sensor system

    DOEpatents

    Schabron, John F.; Rovani, Jr., Joseph F.; Bomstad, Theresa M.; Sorini-Wong, Susan S.; Wong, Gregory K.

    2011-03-01

    Generally, this invention relates to the development of field monitoring methodology for new substances and sensing chemical warfare agents (CWAs) and terrorist substances. It also relates to a portable test kit which may be utilized to measure concentrations of halogenated volatile organic compounds (VOCs) in the field. Specifically it relates to systems for reliably field sensing the potential presence of such items while also distinguishing them from other elements potentially present. It also relates to overall systems and processes for sensing, reacting, and responding to an indicated presence of such substance, including modifications of existing halogenated sensors and arrayed sensing systems and methods.

  18. Volatile organic compound sensor system

    DOEpatents

    Schabron, John F.; Rovani, Jr., Joseph F.; Bomstad, Theresa M.; Sorini-Wong, Susan S.

    2009-02-10

    Generally, this invention relates to the development of field monitoring methodology for new substances and sensing chemical warfare agents (CWAs) and terrorist substances. It also relates to a portable test kit which may be utilized to measure concentrations of halogenated volatile organic compounds (VOCs) in the field. Specifically it relates to systems for reliably field sensing the potential presence of such items while also distinguishing them from other elements potentially present. It also relates to overall systems and processes for sensing, reacting, and responding to an indicated presence of such substance, including modifications of existing halogenated sensors and arrayed sensing systems and methods.

  19. Assessing in situ mineralization of recalcitrant organic compounds in vadose zone sediments using delta13C and 14C measurements.

    PubMed

    Kirtland, Brian C; Aelion, C Marjorie; Stone, Peter A

    2005-01-01

    Few techniques exist to measure the biodegradation of recalcitrant organic compounds such as chlorinated hydrocarbons (CHC) in situ, yet predictions of biodegradation rates are needed for assessing monitored natural attenuation. Traditional techniques measuring O2, CO2, or chemical concentrations (in situ respiration, metabolite and soil air monitoring) may not be sufficiently sensitive to estimate biodegradation rates for these compounds. This study combined isotopic measurements (14C and delta13C of CO2 and delta13C of CHCs) in conjunction with traditional methods to assess in situ biodegradation of perchloroethylene (PCE) and its metabolites in PCE-contaminated vadose zone sediments. CHC, ethene, ethane, methane, O2, and CO2 concentrations were measured over 56 days using gas chromatography (GC). delta13C of PCE, trichloroethylene (TCE) and cis-1,2-dichloroethylene (DCE), delta13C and 14C of vadose zone CO2 and sediment organic matter, and delta13C, 14C, and deltaD of methane were measured using a GC-isotope ratio mass spectrometer or accelerator mass spectrometer. PCE metabolites accounted for 0.2% to 18% of CHC concentration suggesting limited reductive dechlorination. Metabolites TCE and DCE were significantly enriched in (13)C with respect to PCE indicating metabolite biodegradation. Average delta13C-CO2 in source area wells (-23.5 per thousand) was significantly lower compared to background wells (-18.4 per thousand) indicating CHC mineralization. Calculated CHC mineralization rates were 0.003 to 0.01 mg DCE/kg soil/day based on lower 14C values of CO2 in the contaminated wells (63% to 107% modern carbon (pMC)) relative to the control well (117 pMC). Approximately 74% of the methane was calculated to be derived from in situ CHC biodegradation based on the 14C measurement of methane (29 pMC). 14C-CO2 analyses was a sensitive measurement for quantifying in situ recalcitrant organic compound mineralization in vadose zone sediments for which limited

  20. ESTIMATES OF REGIONAL NATURAL VOLATILE ORGANIC COMPOUND FLUXES FROM ENCLOSURE AND AMBIENT MEASUREMENTS

    EPA Science Inventory

    The paper discusses results of an investigation at two forested sites in the Southeastern United States. A variety of VOC compounds including methanol, 2-methyl-3-buten-2-ol, 6-methyl-5-hepten-
    2-one, isoprene, and 15 monoterpenes were emitted from vegetation at these sites. D...

  1. Measurement of volatile organic compounds in suburban Bangkok, Thailand: characteristics and influence from combustion related activities

    NASA Astrophysics Data System (ADS)

    Suthawaree, J.; Tajima, Y.; Kato, S.; Khunchornyakong, A.; Sharp, A.; Kajii, Y.

    2009-12-01

    Elucidation of air quality in the suburban area of Bangkok, Thailand is essential in order to achieve effective regulations and mitigation strategies. VOCs plays important role in formation of tropospheric urban ozone. Without overkill NO concentration, transport of O3 precursors into suburban area which add surplus to local O3 formation as well as direct transport of O3 itself results in relatively higher total O3 observed in suburban area rather than urban. Whole air canister sampling was carried out in the suburban Bangkok during 2008, July 2-7. 4 samples per day were collected at 30 min passes 6, 12, 17, 21 hours with sampling time of 1 min. Analysis was achieved by using GC-FID and GC-MS. High concentrations of VOCs detected during the peak periods in the morning and evening are most likely due to vehicular emission. Averaged VOCs concentrations, reveal distinct different between data measured for weekday and weekend which the latter were found with lower concentrations. No difference was found for CFCs which the levels are also comparable to global background level reported by World Meteorological Organization. The most abundance species have found to be propane and toluene with averaged concentration of 3100 and 2891 pptv, respectively. Ratios of benzene over toluene suggest additional concentration owing to industrial emission, of which particularly larger during the weekday. Comparison with C2Cl4 and CH3Cl concentrations obtained for suburban Tokyo reveal relatively higher influence of biomass burning at suburban Bangkok. In order to estimate the role of the different VOCs towards tropospheric ozone formation, ozone formation potential was calculated using maximum incremental reactivity. Toluene was found to contribute the most to O3 production followed by ethylene, m,p-xylene, and propylene.

  2. Organic Compounds in Carbonaceous Meteorites

    NASA Technical Reports Server (NTRS)

    Cooper, Grorge

    2001-01-01

    Carbonaceous meteorites are relatively enriched in soluble organic compounds. To date, these compounds provide the only record available to study a range of organic chemical processes in the early Solar System chemistry. The Murchison meteorite is the best-characterized carbonaceous meteorite with respect to organic chemistry. The study of its organic compounds has related principally to aqueous meteorite parent body chemistry and compounds of potential importance for the origin of life. Among the classes of organic compounds found in Murchison are amino acids, amides, carboxylic acids, hydroxy acids, sulfonic acids, phosphonic acids, purines and pyrimidines (Table 1). Compounds such as these were quite likely delivered to the early Earth in asteroids and comets. Until now, polyhydroxylated compounds (polyols), including sugars (polyhydroxy aldehydes or ketones), sugar alcohols, sugar acids, etc., had not been identified in Murchison. Ribose and deoxyribose, five-carbon sugars, are central to the role of contemporary nucleic acids, DNA and RNA. Glycerol, a three-carbon sugar alcohol, is a constituent of all known biological membranes. Due to the relative lability of sugars, some researchers have questioned the lifetime of sugars under the presumed conditions on the early Earth and postulated other (more stable) compounds as constituents of the first replicating molecules. The identification of potential sources and/or formation mechanisms of pre-biotic polyols would add to the understanding of what organic compounds were available, and for what length of time, on the ancient Earth.

  3. PERSISTENT PERFLUORINATED ORGANIC COMPOUNDS

    EPA Science Inventory

    Perfluorinated compounds (PFCs) have gained notoriety in the recent past. Global distribution of PFCs in wildlife, environmental samples and humans has sparked a recent increase in new investigations concerning PFCs. Historically PFCs have been used in a wide variety of consume...

  4. Biogenic volatile organic compound emissions during BEARPEX 2009 measured by eddy covariance and flux-gradient similarity methods

    NASA Astrophysics Data System (ADS)

    Park, J.-H.; Fares, S.; Weber, R.; Goldstein, A. H.

    2012-09-01

    The Biosphere Effects on AeRosols and Photochemistry EXperiment (BEARPEX) took place in Blodgett Forest, a Ponderosa pine forest in the Sierra Nevada Mountains of California, during summer 2009. We deployed a Proton Transfer Reaction - Mass Spectrometer (PTR-MS) to measure fluxes and concentrations of biogenic volatile organic compounds (BVOCs). Eighteen ion species including the major BVOC expected at the site were measured sequentially at 5 heights to observe their vertical gradient from the forest floor to above the canopy. Fluxes of the 3 dominant BVOCs methanol, 2-Methyl-3-butene-2-ol (MBO), and monoterpenes, were measured above the canopy by the eddy covariance method. Canopy scale fluxes were also determined by the flux-gradient similarity method (K-theory). A universal K (Kuniv) was determined as the mean of individual K's calculated from the measured fluxes divided by vertical gradients for methanol, MBO, and monoterpenes. This Kuniv was then multiplied by the gradients of each observed ion species to compute their fluxes. The flux-gradient similarity method showed very good agreement with the Eddy Covariance method. Fluxes are presented for all measured species and compared to historical measurements from the same site, and used to test emission algorithms used to model fluxes at the regional scale. MBO was the dominant emission observed followed by methanol, monoterpenes, acetone, and acetaldehyde. The flux-gradient similarity method is shown to be a useful, and we recommend its use especially in experimental conditions when fast measurement of BVOC species is not available.

  5. Online measurements of the emissions of intermediate-volatility and semi-volatile organic compounds from aircraft

    NASA Astrophysics Data System (ADS)

    Cross, E. S.; Hunter, J. F.; Carrasquillo, A. J.; Franklin, J. P.; Herndon, S. C.; Jayne, J. T.; Worsnop, D. R.; Miake-Lye, R. C.; Kroll, J. H.

    2013-08-01

    A detailed understanding of the climate and air quality impacts of aviation requires measurements of the emissions of intermediate-volatility and semi-volatile organic compounds (I/SVOCs) from aircraft. Currently both the amount and chemical composition of aircraft I/SVOC emissions remain poorly characterized. Here we characterize I/SVOC emissions from aircraft, using a novel instrument for the online, quantitative measurement of the mass loading and composition of low-volatility organic vapors. Emissions from the NASA DC8 aircraft were sampled on the ground 143 m downwind of the engines and characterized as a function of engine power from idle (4% maximum rated thrust) through 85% power. Results show that I/SVOC emissions are highest during engine idle operating conditions, with decreasing but non-zero I/SVOC emissions at higher engine powers. Comparison of I/SVOC emissions with total hydrocarbon (THC) measurements, VOC measurements, and an established emissions profile indicates that I/SVOCs comprise 10-20% of the total organic gas-phase emissions at idle, and an increasing fraction of the total gas-phase organic emissions at higher powers. Positive matrix factorization of online mass spectra is used to identify three distinct types of I/SVOC emissions: aliphatic, aromatic and oxygenated. The volatility and chemical composition of the emissions suggest that unburned fuel is the dominant source of I/SVOCs at idle, while pyrolysis products make up an increasing fraction of the I/SVOCs at higher powers. Oxygenated I/SVOC emissions were detected at lower engine powers (≤30%) and may be linked to cracked, partially oxidized or unburned fuel components.

  6. Online measurements of the emissions of intermediate-volatility and semi-volatile organic compounds from aircraft

    NASA Astrophysics Data System (ADS)

    Cross, E. S.; Hunter, J. F.; Carrasquillo, A. J.; Franklin, J. P.; Herndon, S. C.; Jayne, J. T.; Worsnop, D. R.; Miake-Lye, R. C.; Kroll, J. H.

    2013-03-01

    A detailed understanding of the climate and air quality impacts of aviation requires detailed measurements of the emissions of intermediate-volatility and semi-volatile organic compounds (I/SVOCs) from aircraft. Currently both the amount and chemical composition of aircraft I/SVOC emissions remain poorly characterized. Here we characterize I/SVOC emissions from aircraft, using a novel instrument for the online, quantitative measurement of the mass loading and composition of low-volatility organic vapors. Emissions from the NASA DC8 aircraft were sampled on the ground, 143 m downwind of the engines and characterized as a function of engine power from ground idle (~4% maximum rated thrust) through 85% power. Results show that I/SVOC emissions are highest during engine-idle operating conditions, with decreasing but non-zero I/SVOC emissions at higher engine powers. Comparison of I/SVOC emissions with total hydrocarbon (THC) measurements, VOC measurements, and an established emissions profile indicates that I/SVOCs comprise 10-20% of the total organic gas phase emissions at idle, and an increasing fraction of the total gas phase organic emissions at higher powers. Positive matrix factorization of online mass spectra is used to identify three distinct types of I/SVOC emissions: aliphatic, aromatic and oxygenated. The volatility and chemical composition of the emissions suggest that unburned fuel is the dominant source of I/SVOCs at idle, while pyrolysis products make up an increasing fraction of the I/SVOCs at higher powers. Oxygenated I/SVOC emissions were detected at lower engine powers (≤30%) and may be linked to cracked, partially oxidized or unburned fuel components.

  7. NEAR-REAL-TIME MEASUREMENT OF TRACE VOLATILE ORGANIC COMPOUNDS FROM COMBUSTION PROCESSES USING AN ON-LINE GAS CHROMATOGRAPH

    EPA Science Inventory

    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...

  8. MEASUREMENT OF VOLATILE ORGANIC COMPOUNDS BY THE US ENVIRONMENTAL PROTECTION AGENCY COMPENDIUM METHOD TO-17 - EVALUATION OF PERFORMANCE CRITERIA

    EPA Science Inventory

    An evaluation of performance criteria for US Environmental Protection Agency Compendium Method TO-17 for monitoring volatile organic compounds (VOCs) in air has been accomplished. The method is a solid adsorbent-based sampling and analytical procedure including performance crit...

  9. Organic Compounds in Stardust

    NASA Technical Reports Server (NTRS)

    McKay, David S.; Clemett. Simon J.; Sandford, Scott A.; Nakamura-Messenger, Keiko; Hoerz, Fredrich

    2011-01-01

    The successful return of the STARDUST spacecraft provides a unique opportunity to investigate the nature and distribution of organic matter in cometary dust particles collected from Comet 81P/Wild-2. Analysis of individual cometary impact tracks in silica aerogel using the technique of two-step laser mass spectrometry (L2MS) demonstrates the presence of complex aromatic organic matter. While concerns remain as to the organic purity of the aerogel collection medium and the thermal effects associated with hypervelocity capture, the majority of the observed organic species appear indigenous to the impacting particles and are hence of cometary origin. While the aromatic fraction of the total organic matter present is believed to be small, it is notable in that it appears to be N-rich. Spectral analysis in combination with instrumental detection sensitivities suggest that N is incorporated predominantly in the form of aromatic nitriles (R-C N). While organic species in the STARDUST samples do share some similarities with those present in the matrices of carbonaceous chondrites, the closest match is found with stratospherically collected interplanetary dust particles. These findings are consistent with the notion that a fraction of interplanetary dust is of cometary origin. The presence of complex organic N-containing species in comets has astrobiological implications since comets are likely to have contributed to the prebiotic chemical inventory of both the Earth and Mars.

  10. Organophosphorus Compounds in Organic Electronics.

    PubMed

    Shameem, Muhammad Anwar; Orthaber, Andreas

    2016-07-25

    This Minireview describes recent advances of organophosphorus compounds as opto-electronic materials in the field of organic electronics. The progress of (hetero-) phospholes, unsaturated phosphanes, and trivalent and pentavalent phosphanes since 2010 is covered. The described applications of organophosphorus materials range from single molecule sensors, field effect transistors, organic light emitting diodes, to polymeric materials for organic photovoltaic applications. PMID:27276233

  11. RADIOCARBON 14C MEASUREMENTS ON ATMOSPHERIC SAMPLES OF PARTICULATE MATTER (& VOLATILE ORGANIC COMPOUNDS)

    EPA Science Inventory

    Following a brief history of radiocarbon work at EPA since the 1980's, the presentation focuses on recent non-winter measurements for PM-2.5 in the Southeastern U.S. (Houston, TX; Nashville, TN; and particularly, Tampa, FL) and what the measurements suggest about the importance o...

  12. Emissions of volatile organic compounds from Quercus ilex L. measured by Proton Transfer Reaction Mass Spectrometry under different environmental conditions

    NASA Astrophysics Data System (ADS)

    Holzinger, R.; Sandoval-Soto, L.; Rottenberger, S.; Crutzen, P. J.; Kesselmeier, J.

    2000-08-01

    Volatile organic compound (VOC) emissions of the Mediterranean holm oak (Quercus ilex L.) were investigated using a fast Proton Transfer Reaction Mass Spectrometry (PTR-MS) instrument for analysis. This technique is able to measure compounds with a proton affinity higher than water with a high time resolution of 1 s per compound. Hence nearly all VOCs can be detected on-line. We could clearly identify the emission of methanol, acetaldehyde, ethanol, acetone, acetic acid, isoprene, monoterpenes, toluene, and C10-benzenes. Some other species could be tentatively denominated. Among these are the masses 67 (cyclo pentadiene), mass 71 (tentatively attributed to methyl vinyl ketone (MVK) and metacrolein (MACR)), 73 (attributed to methyl ethyl ketone (MEK)), 85 (C6H12 or hexanol), and 95 (vinylfuran or phenol). The emissions of all these compounds (identified as well as nonidentified) together represent 99% of all masses detected and account for a carbon loss of 0.7-2.9% of the net photosynthesis. Of special interest was a change in the emission behavior under changing environmental conditions such as flooding or fast light/dark changes. Flooding of the root system caused an increase of several VOCs between 60 and 2000%, dominated by the emission of ethanol and acetaldehyde, which can be explained by the well described production of ethanol under anoxic conditions of the root system and the recently described subsequent transport and partial oxidation to acetaldehyde within the green leaves. However, ethanol emissions were dominant. Additionally, bursts of acetaldehyde with lower ethanol emission were also found under fast light/dark changes. These bursts are not understood.

  13. DEVELOPMENT OF TECHNIQUES FOR EDDY-CORRELATION MEASUREMENTS OF NON-METHANE VOLATILE ORGANIC COMPOUND FLUXED IN THE ATMOSPHERE

    EPA Science Inventory

    An analytical technique for the measurement of the exchange (flux) of trace gases between the earth's surface and the atmosphere will be developed. Measurements will rely on the eddy correlation method (ECM). Target compounds are biogenically and anthropogenically emitted v...

  14. Measurement of emissions from air pollution sources. 5. C1-C32 organic compounds from gasoline-powered motor vehicles.

    PubMed

    Schauer, James J; Kleeman, Michael J; Cass, Glen R; Simoneit, Bernd R T

    2002-03-15

    Gas- and particle-phase organic compounds present in the tailpipe emissions from an in-use fleet of gasoline-powered automobiles and light-duty trucks were quantified using a two-stage dilution source sampling system. The vehicles were driven through the cold-start Federal Test Procedure (FTP) urban driving cycle on a transient dynamometer. Emission rates of 66 volatile hydrocarbons, 96 semi-volatile and particle-phase organic compounds, 27 carbonyls, and fine particle mass and chemical composition were quantified. Six isoprenoids and two tricyclic terpanes, which are quantified using new source sampling techniques for semi-volatile organic compounds, have been identified as potential tracers for gasoline-powered motor vehicle emissions. A composite of the commercially distributed California Phase II Reformulated Gasoline used in these tests was analyzed by several analytical methods to quantify the gasoline composition, including some organic compounds that are found in the atmosphere as semi-volatile and particle-phase organic compounds. These results allow a direct comparison of the semi-volatile and particle-phase organic compound emissions from gasoline-powered motor vehicles to the gasoline burned by these vehicles. The distribution of n-alkanes and isoprenoids emitted from the catalyst-equipped gasoline-powered vehicles is the same as the distribution of these compounds found in the gasoline used, whereas the distribution of these compounds in the emissions from the noncatalyst vehicles is very different from the distribution in the fuel. In contrast, the distribution of the polycyclic aromatic hydrocarbons and their methylated homologues in the gasoline is significantly different from the distribution of the PAH in the tailpipe emissions from both types of vehicles. PMID:11944666

  15. Extraterrestrial Organic Compounds in Meteorites

    NASA Technical Reports Server (NTRS)

    Botta, Oliver; Bada, Jeffrey L.; Meyer, Michael (Technical Monitor)

    2003-01-01

    Many organic compounds or their precursors found in meteorites originated in the interstellar or circumstellar medium and were later incorporated into planetesimals during the formation of the solar system. There they either survived intact or underwent further processing to synthesize secondary products on the meteorite parent body. The most distinct feature of CI and CM carbonaceous chondrites, two types of stony meteorites, is their high carbon content (up to 3% of weight), either in the form of carbonates or of organic compounds. The bulk of the organic carbon consists of an insoluble macromolecular material with a complex structure. Also present is a soluble organic fraction, which has been analyzed by several separation and analytical procedures. Low detection limits can be achieved by derivatization of the organic molecules with reagents that allow for analysis by gas chromatography/mass spectroscopy and high performance liquid chromatography. The CM meteorite Murchison has been found to contain more than 70 extraterrestrial amino acids and several other classes of compounds including carboxylic acids, hydroxy carboxylic acids, sulphonic and phosphonic acids, aliphatic, aromatic and polar hydrocarbons, fullerenes, heterocycles as well as carbonyl compounds, alcohols, amines and amides. The organic matter was found to be enriched in deuterium, and distinct organic compounds show isotopic enrichments of carbon and nitrogen relative to terrestrial matter.

  16. Biomedical Compounds from Marine organisms

    PubMed Central

    Jha, Rajeev Kumar; Zi-rong, Xu

    2004-01-01

    The Ocean, which is called the ‘mother of origin of life’, is also the source of structurally unique natural products that are mainly accumulated in living organisms. Several of these compounds show pharmacological activities and are helpful for the invention and discovery of bioactive compounds, primarily for deadly diseases like cancer, acquired immuno-deficiency syndrome (AIDS), arthritis, etc., while other compounds have been developed as analgesics or to treat inflammation, etc. The life-saving drugs are mainly found abundantly in microorganisms, algae and invertebrates, while they are scarce in vertebrates. Modern technologies have opened vast areas of research for the extraction of biomedical compounds from oceans and seas.

  17. In-situ volatile organic compounds measurements with GC-MSD during the DOMINO campaign in Spain, December 2008

    NASA Astrophysics Data System (ADS)

    Song, W.; Yassaa, N.; Williams, J.

    2009-04-01

    This study presents a new volatile organic compounds (VOC) dataset measured during the DOMINO field campaign in December 2008. The measurements were made from a 10m tower located in a nature reserve on the south west coast of Spain. For the analysis, the VOCs were collected and concentrated on a thermal desorber unit, separated on a gas chromotagraph equipped with an enantiomerically selective column, and detected by mass spectrometry. This experimental set-up allowed the measurement of anthropogenic VOCs such as ethyl benzene, and all xylene isomers, and biogenic species such as isoprene and monoterpenes. Here we examine the VOC mixing ratio variations as a function of air mass origin to characterize the measurement site in terms of biogenic and anthropogenic influences. Mixing ratios of biogenic species were generally low, consistent with the low winter season growth rates. The ratio of (-)-alpha-pinene to (+)-alpha-pinene was variable but showed a clear dominance of the (-)-enantiomer, similar to previous results obtained with the same system in the Tropical rainforest. High mixing ratios of benzene and toluene were related to transport events from Seville (to the northeast) and Huelva (to the west). The ratio of two short lived anthropogenic species ethylbenzene and meta-xylene was found to peak at midday and indicative of the levels of oxidant levels.

  18. Biogenic volatile organic compound emissions during BEARPEX 2009 measured by eddy covariance and flux-gradient similarity methods

    NASA Astrophysics Data System (ADS)

    Park, J.-H.; Fares, S.; Weber, R.; Goldstein, A. H.

    2014-01-01

    The Biosphere Effects on AeRosols and Photochemistry EXperiment (BEARPEX) took place in Blodgett Forest, a Ponderosa pine forest in the Sierra Nevada of California, USA, during summer 2009. We deployed a proton transfer reaction-quadrupole mass spectrometer (PTR-QMS) to measure fluxes and concentrations of biogenic volatile organic compounds (BVOCs). Eighteen ion species, including the major BVOC expected at the site, were measured sequentially at 5 heights to observe their vertical gradient from the forest floor to above the canopy. Fluxes of the 3 dominant BVOCs methanol, 2-Methyl-3-butene-2-ol (MBO), and monoterpenes were measured above the canopy by the disjunct eddy covariance (EC) method. Canopy-scale fluxes were also determined by the flux-gradient similarity method (K-theory). A universal K (Kuniv) was determined as the mean of individual K's calculated from the measured fluxes divided by vertical gradients for methanol, MBO, and monoterpenes. This Kuniv was then multiplied by the gradients of each observed ion species to compute their fluxes. The flux-gradient similarity method showed very good agreement with the disjunct EC method. Fluxes are presented for all measured species and compared to historical measurements from the same site, and used to test emission algorithms used to model fluxes at the regional scale. MBO was the dominant emission observed, followed by methanol, monoterpenes, acetone, and acetaldehyde. The flux-gradient similarity method is shown to be tenable, and we recommend its use, especially in experimental conditions when fast measurement of BVOC species is not available.

  19. MEASUREMENTS OF NON-METHANE VOLATILE ORGANIC COMPOUNDS IN THE LOWER TROPOSPHERE FROM TETHERED BALLOON AND KITE SAMPLING PLATFORMS BY INTERNAL STANDARD CALIBRATION USING AMBIENT CFC REFERENCE COMPOUNDS

    EPA Science Inventory

    A new analytical approach for the sampling and analysis of volatile organic compounds (VOCs) from sampling platforms used in the vertical profiling of the lower troposphere, such as kites, balloons, and remotely piloted vehicles will be developed. These sampling platforms a...

  20. A compact PTR-ToF-MS instrument for airborne measurements of volatile organic compounds at high spatiotemporal resolution

    NASA Astrophysics Data System (ADS)

    Müller, M.; Mikoviny, T.; Feil, S.; Haidacher, S.; Hanel, G.; Hartungen, E.; Jordan, A.; Märk, L.; Mutschlechner, P.; Schottkowsky, R.; Sulzer, P.; Crawford, J. H.; Wisthaler, A.

    2014-11-01

    Herein, we report on the development of a compact proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) for airborne measurements of volatile organic compounds (VOCs). The new instrument resolves isobaric ions with a mass resolving power (m/Δm) of ~1000, provides accurate m/z measurements (Δm < 3 mDa), records full mass spectra at 1 Hz and thus overcomes some of the major analytical deficiencies of quadrupole-MS-based airborne instruments. 1 Hz detection limits for biogenic VOCs (isoprene, α total monoterpenes), aromatic VOCs (benzene, toluene, xylenes) and ketones (acetone, methyl ethyl ketone) range from 0.05 to 0.12 ppbV, making the instrument well-suited for fast measurements of abundant VOCs in the continental boundary layer. The instrument detects and quantifies VOCs in locally confined plumes (< 1 km), which improves our capability of characterizing emission sources and atmospheric processing within plumes. A deployment during the NASA 2013 DISCOVER-AQ mission generated high vertical- and horizontal-resolution in situ data of VOCs and ammonia for the validation of satellite retrievals and chemistry transport models.

  1. Sulfated compounds from marine organisms.

    PubMed

    Kornprobst, J M; Sallenave, C; Barnathan, G

    1998-01-01

    More than 500 sulfated compounds have been isolated from marine organisms so far but most of them originate from two phyla only, Spongia and Echinodermata. The sulfated compounds are presented according to the phyla they have been identified from and to their chemical structures. Biological activities, when available, are also given. Macromolecules have also been included in this review but without structural details. PMID:9530808

  2. Photochemical dimerization of organic compounds

    SciTech Connect

    Crabtree, R.H.; Brown, S.H.; Muedas, C.A.; Ferguson, R.R.

    1992-04-14

    This patent describes improvement in a Group IIb photosensitized vapor phase dimerization of an organic compound in which a gaseous mixture of a Group IIB metal and the organic compound is irradiated in a reaction zone with a photosensitizing amount of radiant energy. The improvement comprises: a continuous stream of the gaseous mixture is passed as a vapor phase in a single pass through the reaction zone at a temperature at which the thus-produced dimer condenses immediately upon the formation thereof; the starting gaseous mixture comprises hydrogen and two ethylenically unsaturated compounds selected from the group consisting of alkenes of at least six carbon atoms, unsaturated nitriles, unsaturated epoxides, unsaturated silanes, unsaturated amines, unsaturated phosphines, and fluorinated alkenes; the gaseous mixture comprises nitrous oxide and the organic compound is a saturated compound with C-H bond strengths greater than 100 kcal/mol or a mixture of the saturated compound and an alkene; or the starting gaseous comprises an activating amount of hydrogen and the dimerization is a dehydrodimerization or cross-dimerization of a saturated hydrocarbon.

  3. Fast sorption measurements of volatile organic compounds on building materials: Part 1 – Methodology developed for field applications

    PubMed Central

    Rizk, M.; Verriele, M.; Dusanter, S.; Schoemaecker, C.; Le Calve, S.; Locoge, N.

    2016-01-01

    A Proton Transfer Reaction-Mass Spectrometer (PTR-MS) has been coupled to the outlet of a Field and Laboratory Emission Cell (FLEC), to measure volatile organic compounds (VOC) concentration during a sorption experiments (Rizk et al., this issue) [1]. The limits of detection of the PTR-MS for three VOCs are presented for different time resolution (2, 10 and 20 s). The mass transfer coefficient was calculated in the FLEC cavity for the different flow rates. The concentration profile obtained from a sorption experiment performed on a gypsum board and a vinyl flooring are also presented in comparison with the profile obtained for a Pyrex glass used as a material that do not present any sorption behavior (no sink). Finally, the correlation between the concentration of VOCs adsorbed on the surface of the gypsum board at equilibrium (Cse) and the concentration of VOCs Ce measured in the gas phase at equilibrium is presented for benzene, C8 aromatics and toluene. PMID:26937475

  4. Fast sorption measurements of volatile organic compounds on building materials: Part 1 - Methodology developed for field applications.

    PubMed

    Rizk, M; Verriele, M; Dusanter, S; Schoemaecker, C; Le Calve, S; Locoge, N

    2016-03-01

    A Proton Transfer Reaction-Mass Spectrometer (PTR-MS) has been coupled to the outlet of a Field and Laboratory Emission Cell (FLEC), to measure volatile organic compounds (VOC) concentration during a sorption experiments (Rizk et al., this issue) [1]. The limits of detection of the PTR-MS for three VOCs are presented for different time resolution (2, 10 and 20 s). The mass transfer coefficient was calculated in the FLEC cavity for the different flow rates. The concentration profile obtained from a sorption experiment performed on a gypsum board and a vinyl flooring are also presented in comparison with the profile obtained for a Pyrex glass used as a material that do not present any sorption behavior (no sink). Finally, the correlation between the concentration of VOCs adsorbed on the surface of the gypsum board at equilibrium (Cse ) and the concentration of VOCs Ce measured in the gas phase at equilibrium is presented for benzene, C8 aromatics and toluene. PMID:26937475

  5. Development of a low-density polyethylene-containing passive sampler for measuring dissolved hydrophobic organic compounds in open waters.

    PubMed

    Bao, Lian-Jun; Xu, Shi-Ping; Liang, Yan; Zeng, Eddy Y

    2012-05-01

    A passive water sampler with low-density polyethylene (LDPE) as the sorbent phase was built and field-tested for sensing freely dissolved concentrations of hydrophobic organic compounds (HOCs) in fresh and coastal water. Based on the measured LDPE-water partition coefficients (K(pew)) of 12 polycyclic aromatic hydrocarbons (PAHs) and dichlorodiphenyltrichloroethane (DDT) and its seven metabolites, the detection limits with the passive sampler containing 10-g LDPE ranged from 0.04 to 56.9 pg/L in the equilibrium sampling mode. Furthermore, the utility of the passive sampler in measuring dissolved HOC concentrations in open waters was examined through a comparison with solid-phase extraction combined with liquid-liquid extraction (SPE-LLE) and poly(dimethyl)siloxane (PDMS) coated fiber samplers. The total concentrations of PAHs (3.8-16 ng/L) obtained by the passive sampler were lower than those (87.7-115.5 ng/L) obtained through SPE-LLE. This large difference was probably attributable to slower water exchange in and out of the passive sampler as time progressed because of blockage by algae in eutrophia reservoirs and high dissolved organic carbon contents resulting in higher-than-expected PAH concentrations by SPE-LLE. Furthermore, the concentrations and compositional profiles of DDXs (sum of p,p'-DDT, p,p'-DDD, p,p'-DDE, o,p'-DDT, o,p'-DDD, o,p'-DDE, and p,p'-DDMU) at site A obtained by the passive sampler agreed with the results obtained with the PDMS-coated fibers, suggesting that the passive sampler was able to reasonably quantify dissolved HOCs in seawater. PMID:22388779

  6. DEVELOPMENT AND TESTING OF A WHOLE-AIR SAMPLER FOR MEASUREMENT OF PERSONAL EXPOSURE TO VOLATILE ORGANIC COMPOUNDS

    EPA Science Inventory

    A small and relatively lightweight (3.35 kg) whole-air (canister) sampler that can be worn to monitor personal exposures to volatile organic compounds was developed and evaluated. The prototype personal whole air sampler (PWAS) consists of a 1-L canister, a mass flow controller, ...

  7. Assessment of Volatile Organic Compound and Hazardous Air Pollutant Emissions from Oil and Natural Gas Well Pads using Mobile Remote and On-site Direct Measurements

    EPA Science Inventory

    Emissions of volatile organic compounds (VOC) and hazardous air pollutants (HAP) from oil and natural gas production were investigated using direct measurements of component-level emissions on well pads in the Denver-Julesburg (DJ) Basin and remote measurements of production pad-...

  8. Volatile organic compounds measured in summer in Beijing and their role in ground-level ozone formation

    NASA Astrophysics Data System (ADS)

    Shao, Min; Lu, Sihua; Liu, Ying; Xie, Xin; Chang, Chichung; Huang, Shan; Chen, Zhongmin

    2009-01-01

    Beijing has long suffered from serious ground-level ozone pollution, and volatile organic compounds (VOCs) play a key role in ozone formation. To understand the chemical speciation of VOCs in Beijing, nonmethane hydrocarbons (NMHCs) and oxygenated VOCs (OVOCs) were measured in summer in Beijing and nearby provinces (VOCs in this work means NMHCs+OVOCs). A variation of VOC mixing ratios and chemical speciation from 2004 to 2006 was observed at an urban site in Beijing. The typical VOC species, e.g., propane, propene, and toluene, had comparable or lower mixing ratios than levels found in other cities that previously hosted the Olympic Games, while the mixing ratios for isoprene were higher. The chemical compositions of VOCs within Beijing were heavily influenced by vehicular emissions and differed from those obtained in Tianjin and Hebei Province. OVOCs were an important component, accounting for 54% and 37% in the VOC mixing ratio in 2005 and 2006, respectively, and about 40% of the OH loss rates. The main reactive VOC compounds were aldehydes and alkenes. By using isoprene chemistry and the ratio of ethylbenzene to mp-xylene, the initial mixing ratios of VOCs were estimated. The VOCs had similar variation patterns to ambient ozone and peroxyacetyl nitrate (PAN) concentrations. The correlation between daily maximum ozone concentrations and initial VOCs revealed that ozone formation was sensitive to VOCs for both urban (Peking University, PKU) and rural (Yufa) sites. A reduction in NOx would lead to a decrease in ozone at Yufa, but would cause increased ozone at the PKU site.

  9. Measurements of Volatile Organic Compounds (VOCs) on Board of the Zeppelin NT during the PEGASOS Campaign in 2012

    NASA Astrophysics Data System (ADS)

    Jäger, Julia; Hofzumahaus, Andreas; Beck, Harry; Rohrer, Franz; Broch, Sebastian; Fuchs, Hendrik; Gomm, Sebastian; Holland, Frank; Lu, Keding; Kiendler-Scharr, Astrid; Mentel, Thomas; Rose, Bernhard; Wegener, Robert; Wahner, Andreas

    2013-04-01

    Volatile Organic Compounds (VOCs) are mostly emitted at the ground and are degraded by the reactions with OH, NO3 or O3 as they rise upwards in the atmosphere. VOCs play an important role as sources and sinks for radicals in the troposphere. Up to date, most of the VOC measurements were performed from ground based platforms; the profile measurements across the whole planetary boundary layer (PBL) are still quite limited which restrained the exploring of the VOCs chemistry of the entire PBL. This although these measurements are particularly interesting, as most of the chemistry of the VOC degradation in the troposphere takes place in the PBL. Moreover, fast VOCs measurements utilizing Gas Chromatography coupled with Mass Spectrometry (GC-MS) are a challenge due to the great chemical variability of VOC species. Therefore accurate in-situ measurements of VOCs together with other species as CO, NOx, O3 and the OH reactivity, encompassing different levels of altitude and fast time resolution, would essentially improve the understanding of the VOC distribution in the lower troposphere. Here we present the setup and the modifications of the fast GC-MS system and the results of the PEGASOS Zeppelin campaigns in summer 2012. First, we present our developments and modifications of an in-flight GC-MS system to detect volatile non methane hydrocarbons (NMHC) with a time resolution of 3 minutes and a detection limit in the order of 2 pptv. The modified setup enabled us to analyze 70 different VOC species, ranging from alkanes (C4 to C11), aromatics and terpenes to oxygenated hydrocarbons (OVOC) such as alcohols and aldehydes. Second, in contrast to previous airplane studies also utilizing a GC-MS system, the Zeppelin NT as a measuring platform during the PEGASOS campaign enabled us to measure vertical profiles up to 1500m at low travelling speeds which means a high spatial resolution. We will present results for selected VOC that offer new insights on height profiles

  10. Volatile organic compounds (VOCs) measured at an urban site of Beijing: intercomparisons, emission ratios and factor analysis

    NASA Astrophysics Data System (ADS)

    Yuan, B.; Shao, M.; De Gouw, J. A.; Bon, D.; Wang, M.; Lu, S.; Zeng, L.; Zhang, Q.; Liu, Y.

    2011-12-01

    A proton transfer reaction mass spectrometer (PTR-MS) were used to measure volatile organic compounds (VOCs) in August - September, 2010 (summer) and December, 2010 - January, 2011 (winter) at an urban site on campus of Peking University. During the summer campaign, other instruments were also deployed at the site, including a custom-built GC-MS/FID, a GC-FID/PID, whole air samples (WAS) collected in canisters, and DNPH cartridges. VOCs concentrations measured by PTR-MS in the summer campaign compared well with the GC methods for most of the measured compounds. VOCs concentrations in winter strongly correlated with the combustion tracer CO for both hydrocarbons and oxygenates VOCs (OVOCs) and emission ratios to CO were calculated from linear fits of ambient concentrations. Emission ratios of aromatics in winter were significantly lower than those in summer, which may be due to: (1) higher CO emissions from coal burning for space heating in winter of Beijing; (2) higher industrial/solvent evaporations of aromatics in summer. The VOCs dataset with 19 species from PTR-MS and 56 species from GC-MS/FID was used for PMF analysis. A solution of five factors with no rotation (fPeak=0) was determined to be the best fit. Uncertainties of PMF analysis were explored by bootstrap method. The five factors included a fresh primary emissions factor (Factor 1, 27%), an aged primary emissions factor (Factor 2, 19%), a secondary & aged factor (Factor 3, 33%), a biogenic factor (Factor 4, 4%) and an industrial-like factor (Factor 5, 17%). The fresh and aged primary factor correlated well with NOx and CO, respectively. And the secondary & aged factor correlated well with PAN and Ox (O3+NO2). The contributions in different factors for various hydrocarbons are dependent on their reactivity. Comparing the obtained factor profiles shows that the aged primary emission factor and the secondary & aged factor are photochemically connected with the fresh primary emission factor. It suggested

  11. Students' Categorizations of Organic Compounds

    ERIC Educational Resources Information Center

    Domin, Daniel S.; Al-Masum, Mohammad; Mensah, John

    2008-01-01

    Categorization is a fundamental psychological ability necessary for problem solving and many other higher-level cognitive tasks. In organic chemistry, students must establish groupings of different chemical compounds in order not only to solve problems, but also to understand course content. Classic models of categorization emphasize similarity as…

  12. Performance of a high flow rate, thermally extractable multicapillary denuder for atmospheric semivolatile organic compound concentration measurement.

    PubMed

    Rowe, Mark D; Perlinger, Judith A

    2010-03-15

    A high flow rate (300 L min(-1)) multicapillary denuder was designed to collect trace atmospheric semivolatile organic compounds (SOCs). The denuder is coated with a reusable, polydimethylsiloxane stationary phase as a nonselective absorbent for SOCs. A solvent-free thermal desorption method was developed, including sample cleanup, that is selective for nonpolar SOCs, and has low consumables cost per sample. The entire sample is transferred into the gas chromatograph to minimize the sampling time required to collect detectable analyte mass. Trace concentrations (0.1-100 pg m(-3)) of polychlorinated biphenyls and hexachlorobenzene were measured in the atmosphere near Lake Superior in sample times of 3.2-6.2 h. Overall method precision was determined using field duplicates and compared to the conventional high-volume sampler method. Method precision (coefficient of variation) of 16% was found for the high-flow denuder compared to 21% for the high-volume method. The relative difference between the two methods was 25%, with the high-flow denuder method giving generally lower concentrations. The high-flow denuder is an alternative to high-volume or passive samplers when it is desirable to separate gaseous from particle-associated SOCs upstream of a filter. The method is advantageous for studies that require high temporal resolution. PMID:20148550

  13. Development of a silicone membrane tube equilibrator for measuring partial pressures of volatile organic compounds in natural water.

    PubMed

    Ooki, Atsushi; Yokouchi, Yoko

    2008-08-01

    Methods for determining volatile organic compounds (VOCs) in water and air are required so that the VOCs' fluxes in water environments can be estimated. We developed a silicone membrane tube equilibrator for collecting gas-phase samples containing VOCs at equilibrium with natural water. The equilibrator consists of six silicone tubes housed in a polyvinyl chloride pipe. Equilibrated air samples collected from the equilibrator were analyzed with an automated preconcentration gas chromatography-mass spectrometry system for hourly measurements of VOC partial pressures. The partial pressures of all the target VOCs reached equilibrium within 1 h in the equilibrator. The system was used to determine VOC partial pressures in Lake Kasumigaura, a shallow eutrophic lake with a high concentration of suspended particulate matter (SPM). Compressed air was used daily to remove SPM deposited on the inner wall of the equilibrator and to maintain the equilibrium conditions for more than a week without the need to shut the system down. CH2Br2, CHCl3, CHBrCl2, CH2BrCl, C2H5I, C2Cl4, CH3I, and CH3Br in the lake were supersaturated with respect to the air, whereas CH3CI was undersaturated. CHCl3 had the highest flux (6.2 nmol m(-2) hr(-1)) during the observation period. PMID:18754497

  14. Predicting personal exposure of Windsor, Ontario residents to volatile organic compounds using indoor measurements and survey data

    NASA Astrophysics Data System (ADS)

    Stocco, Corinne; MacNeill, Morgan; Wang, Daniel; Xu, Xiaohong; Guay, Mireille; Brook, Jeff; Wheeler, Amanda J.

    As part of a multi-year personal exposure monitoring campaign, we collected personal, indoor, and outdoor levels of 188 volatile organic compounds (VOCs). In 2005, data were obtained for 48 non-smoking adults from Windsor, Ontario in order to assess their exposure to VOCs based on their daily routines and characteristics of their homes. During the 8-week winter and summer sampling sessions, five repeated 24-h measurements were obtained for each home. This paper focuses on the analysis of 18 VOCs: 11 have been declared toxic as defined under the Canadian Environmental Protection Act, [1999. Statutes of Canada. Act assented to September 14, 1999. Ottawa: Queen's Printer. Available at Canada Gazette (Part III) 22(3): (Chapter 33). http://canadagazette.gc.ca/partIII/1999/g3-02203.pdf], and seven are commonly found in household and personal care products. Results of mixed effects models indicate that personal exposure to these VOCs can be largely predicted by indoor concentrations, with models including indoor concentrations found to have an r2 value for the fixed effects ranging from 58.4% to 87.2% for the CEPA toxic VOCs and from 41.7% to 90.1% for the commonly found VOCs. Given that people spend the majority of their time inside their home, characteristics of the home such as air exchange rates, type of garage, and type of stove have a greater potential to impact personal exposures.

  15. Potential for Measurement of Trace Volatile Organic Compounds in Closed Environments Using Gas Chromatograph/Differential Mobility Spectrometer

    NASA Technical Reports Server (NTRS)

    Limero, Thomas; Cheng, Patti

    2007-01-01

    For nearly 3.5 years, the Volatile Organic Analyzer (VOA) has routinely analyzed the International Space Station (ISS) atmosphere for a target list of approximately 20 volatile organic compounds (VOCs). Additionally, an early prototype of the VOA collected data aboard submarines in two separate trials. Comparison of the data collected on ISS and submarines showed a surprising similarity in the atmospheres of the two environments. Furthermore, in both cases it was demonstrated that the VOA data can detect hardware issues unrelated to crew health. Finally, it was also clear in both operations that the VOA s size and resource consumption were major disadvantages that would restrict its use in the future. The VOA showed the value of measuring VOCs in closed environments, but it had to be shrunk if it was to be considered for future operations in these environments that are characterized by cramped spaces and limited resources. The Sionex Microanalyzer is a fraction of the VOA s size and this instrument seems capable of maintaining or improving upon the analytical performance of the VOA. The two design improvements that led to a smaller, less complex instrument are the Microanalyzer s use of recirculated air as the gas chromatograph s carrier gas and a micromachined detector. Although the VOA s ion mobility spectrometer and the Microanalyzer s differential mobility spectrometer (DMS) are related detector technologies, the DMS was more amenable to micromachining. This paper will present data from the initial assessment of the Microanalyzer. The instrument was challenged with mixtures that simulated the VOCs typically detected in closed-environment atmospheres.

  16. Potential Organic Aerosol Formation from Biogenic Compounds: Model and Measurement analysis of the BEACHON-RoMBAS 2011 field data

    NASA Astrophysics Data System (ADS)

    Hodzic, A.; Lee-Taylor, J.; Aumont, B.; Madronich, S.; Palm, B. B.; Campuzano Jost, P.; Day, D. A.; Jimenez, J. L.; Karl, T.; Apel, E. C.; Kaser, L.; Hansel, A.

    2012-12-01

    The scientific understanding of the formation of organic aerosols (OA) from biogenic precursors and their ageing, especially in the presence of anthropogenic pollution, is still limited. The Rocky Mountain Biogenic Aerosol field Study (RoMBAS) took place in summer 2011 at the Manitou Forest Observatory in the Colorado Front Range as part of the NCAR Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics & Nitrogen (BEACHON) project with the specific objective of characterizing the formation and growth of biogenic particles in the forest canopy that is dominated by terpene and MBO biogenic emissions. Here we present the results of the box model Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) that was applied at the measurement site to study local production of secondary OA (SOA), as well as the results of the 3D regional Weather Research and Forecasting model with chemistry (WRF/Chem) that was run at 4km horizontal resolution to simulate the regional transport and chemistry. First, we quantify the relative contribution of various biogenic and anthropogenic precursors to SOA levels that were measured by the Aerosol Mass Spectrometer (AMS). The GECKO-A model is initialized from measured VOC concentrations, and uses MEGAN biogenic emissions and WRF/Chem meteorological forcing. The predicted SOA daytime levels at the site of ~0.7-1.0 microg/m3 are consistent with the observations. The SOA production in GECKO from individual VOC precursors is estimated and compared with WRF/Chem predictions which are based on simplified two-product parameterizations as commonly used in regional models. The sensitivity of the SOA formation to the deposition of semi-volatile vapors, and to an increase in NOx and NO3 levels is also discussed for this site that is frequently influenced by advection of the anthropogenic plumes from Denver. Second, we examine how the organic vapors age after several days of atmospheric processing by

  17. Semivolatile Organic Compounds in Homes: Strategies for Efficient and Systematic Exposure Measurement Based on Empirical and Theoretical Factors

    PubMed Central

    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

  18. Airborne flux measurements of methane and volatile organic compounds over the Haynesville and Marcellus shale gas production regions

    NASA Astrophysics Data System (ADS)

    Yuan, Bin; Kaser, Lisa; Karl, Thomas; Graus, Martin; Peischl, Jeff; Campos, Teresa L.; Shertz, Steve; Apel, Eric C.; Hornbrook, Rebecca S.; Hills, Alan; Gilman, Jessica B.; Lerner, Brian M.; Warneke, Carsten; Flocke, Frank M.; Ryerson, Thomas B.; Guenther, Alex B.; Gouw, Joost A.

    2015-06-01

    Emissions of methane (CH4) and volatile organic compounds (VOCs) from oil and gas production may have large impacts on air quality and climate change. Methane and VOCs were measured over the Haynesville and Marcellus shale gas plays on board the National Center for Atmospheric Research C-130 and NOAA WP-3D research aircraft in June-July of 2013. We used an eddy covariance technique to measure in situ fluxes of CH4 and benzene from both C-130 flights with high-resolution data (10 Hz) and WP-3D flights with low-resolution data (1 Hz). Correlation (R = 0.65) between CH4 and benzene fluxes was observed when flying over shale gas operations, and the enhancement ratio of fluxes was consistent with the corresponding concentration observations. Fluxes calculated by the eddy covariance method show agreement with a mass balance approach within their combined uncertainties. In general, CH4 fluxes in the shale gas regions follow a lognormal distribution, with some deviations for relatively large fluxes (>10 µg m-2 s-1). Statistical analysis of the fluxes shows that a small number of facilities (i.e., ~10%) are responsible for up to ~40% of the total CH4 emissions in the two regions. We show that the airborne eddy covariance method can also be applied in some circumstances when meteorological conditions do not favor application of the mass balance method. We suggest that the airborne eddy covariance method is a reliable alternative and complementary analysis method to estimate emissions from oil and gas extraction.

  19. Measured versus Modeled Partitioning of Several Hundred Semi-Volatile Organic Compounds Using SV-TAG with in-situ Derivatization

    NASA Astrophysics Data System (ADS)

    Moss, J.; Isaacman, G. A.; Kreisberg, N. M.; Hu, W.; Campuzano Jost, P.; Day, D. A.; Jimenez, J. L.; Edgerton, E. S.; Baumann, K.; Hering, S. V.; Goldstein, A. H.

    2014-12-01

    Most organic aerosol is secondary, formed by oxidation of primary gas-phase chemicals whose products condense into particles. While gas-particle partitioning is known to depend in part on the volatility of a compound, the process is poorly understood and largely unconstrained by compound-specific measurements. We directly measured gas-to-particle partitioning of over 250 semi-volatile organic compounds during the SOAS campaign in rural Alabama in the summer of 2013, and compare to a partitioning model based on their calculated vapor pressures and chemical properties. All data were collected using an SVTAG (Semi-Volatile Thermal desorption Aerosol Gas chromatograph) which uses two parallel cells to collect gas- and particle-phase organic compounds with volatilities lower than tridecane. By using an activated carbon denuder to remove all gas-phase compounds from one channel, gas-particle partitioning is directly measured on an hourly timescale. Derivatization with MSTFA, a silylating agent, allows analysis of highly oxygenated compounds that have not previously been analyzed by in-situ GC methods. Internal standards are used to correct all compounds for instrument variability in order to remove instrument biases between sampling channels, and compounds lacking temporal variability are not reported so as to exclude any internal contaminant compounds. Chemical characteristics of each compound (i.e. number of derivatized hydroxyl groups) were inferred from their mass spectra using a model we built from data in an available NIST mass spectral database. Based on chromatographic retention time and chemical characteristics we model the vapor pressures of measured compounds to within the error of current structure-activity models (i.e. SIMPOL). Measured partitioning for all observed compounds is compared to partitioning predicted from their estimated vapor pressures. While current models adequately describe the partitioning of some compounds, a large fraction of observed

  20. Volatile Organic Compounds in Uremia

    PubMed Central

    Seifert, Luzia; Slodzinski, Rafael; Jankowski, Joachim; Zidek, Walter; Westhoff, Timm H.

    2012-01-01

    Background Although “uremic fetor” has long been felt to be diagnostic of renal failure, the compounds exhaled in uremia remain largely unknown so far. The present work investigates whether breath analysis by ion mobility spectrometry can be used for the identification of volatile organic compounds retained in uremia. Methods Breath analysis was performed in 28 adults with an eGFR ≥60 ml/min per 1.73 m2, 26 adults with chronic renal failure corresponding to an eGFR of 10–59 ml/min per 1.73 m2, and 28 adults with end-stage renal disease (ESRD) before and after a hemodialysis session. Breath analysis was performed by ion mobility spectrometryafter gas-chromatographic preseparation. Identification of the compounds of interest was performed by thermal desorption gas chromatography/mass spectrometry. Results Breath analyses revealed significant differences in the spectra of patients with and without renal failure. Thirteen compounds were chosen for further evaluation. Some compounds including hydroxyacetone, 3-hydroxy-2-butanone and ammonia accumulated with decreasing renal function and were eliminated by dialysis. The concentrations of these compounds allowed a significant differentiation between healthy, chronic renal failure with an eGFR of 10–59 ml/min, and ESRD (p<0.05 each). Other compounds including 4-heptanal, 4-heptanone, and 2-heptanone preferentially or exclusively occurred in patients undergoing hemodialysis. Conclusion Impairment of renal function induces a characteristic fingerprint of volatile compounds in the breath. The technique of ion mobility spectrometry can be used for the identification of lipophilic uremic retention molecules. PMID:23049998

  1. Comparison of predicted and derived measures of volatile organic compounds inside four relocatable classrooms due to identified interior finish sources

    SciTech Connect

    Hodgson, Alfred T.; Shendell, Derek G.; Fisk, William J.; Apte, Michael G.

    2003-06-01

    Indoor exposures to toxic and odorous volatile organic compounds (VOCs) are of general concern. Recently, VOCs in portable or relocatable classrooms (RCs) have received particular attention. However, very little was known about indoor environmental quality (IEQ) and the sources, composition, and indoor concentrations of VOCs in RCs. This project task focused on developing and demonstrating a process for selecting interior finish materials for RCs that have relatively low impacts with respect to their emissions of toxic and odorous VOCs. This task was part of a larger project to demonstrate the potential for simultaneous improvements in IEQ and energy efficiency in four new RCs equipped both with a continuously ventilating advanced heating, ventilating, and air conditioning system (HVAC) and a standard HVAC system. These HVACs were operated on alternate weeks. One RC per pair was constructed with standard interior finish materials, and the other included alternate interior materials identified in our prior laboratory study to have low VOC emissions. The RCs were sited in side-by-side pairs at two elementary schools in distinct northern California climate zones. Classroom VOC emission rates (mg hr{sup -1}) and concentrations were predicted based on VOC emission factors ({micro}g m{sup -2} hr{sup -1}) measured for individual materials in the laboratory, the quantities of installed materials and design ventilation rates. Predicted emission rates were compared to values derived from classroom measurements of VOC concentrations and ventilation rates made at pre-occupancy, eight weeks, and 27 weeks. Predicted concentrations were compared to measured integrated VOC indoor minus outdoor concentrations during school hours in the fall cooling season with the advanced HVAC operated. These measured concentrations also were compared between standard and material-modified RCs. Our combined laboratory and field process proved effective by correctly predicting that IEQ impacts of

  2. Standardised exhaled breath collection for the measurement of exhaled volatile organic compounds by proton transfer reaction mass spectrometry

    PubMed Central

    2013-01-01

    Background Exhaled breath volatile organic compound (VOC) analysis for airway disease monitoring is promising. However, contrary to nitric oxide the method for exhaled breath collection has not yet been standardized and the effects of expiratory flow and breath-hold have not been sufficiently studied. These manoeuvres may also reveal the origin of exhaled compounds. Methods 15 healthy volunteers (34 ± 7 years) participated in the study. Subjects inhaled through their nose and exhaled immediately at two different flows (5 L/min and 10 L/min) into methylated polyethylene bags. In addition, the effect of a 20 s breath-hold following inhalation to total lung capacity was studied. The samples were analyzed for ethanol and acetone levels immediately using proton-transfer-reaction mass-spectrometer (PTR-MS, Logan Research, UK). Results Ethanol levels were negatively affected by expiratory flow rate (232.70 ± 33.50 ppb vs. 202.30 ± 27.28 ppb at 5 L/min and 10 L/min, respectively, p < 0.05), but remained unchanged following the breath hold (242.50 ± 34.53 vs. 237.90 ± 35.86 ppb, without and with breath hold, respectively, p = 0.11). On the contrary, acetone levels were increased following breath hold (1.50 ± 0.18 ppm) compared to the baseline levels (1.38 ± 0.15 ppm), but were not affected by expiratory flow (1.40 ± 0.14 ppm vs. 1.49 ± 0.14 ppm, 5 L/min vs. 10 L/min, respectively, p = 0.14). The diet had no significant effects on the gasses levels which showed good inter and intra session reproducibility. Conclusions Exhalation parameters such as expiratory flow and breath-hold may affect VOC levels significantly; therefore standardisation of exhaled VOC measurements is mandatory. Our preliminary results suggest a different origin in the respiratory tract for these two gasses. PMID:23837867

  3. COMPARISON OF PRESSURIZED LIQUID EXTRACTION AND MATRIX SOLID PHASE DISPERSION FOR THE MEASUREMENT OF SEMI-VOLATILE ORGANIC COMPOUND ACCUMULATION IN TADPOLES

    EPA Science Inventory

    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 ...

  4. Standardization of flux chamber and wind tunnel flux measurements for quantifying volatile organic compound and ammonia emissions from area sources at animal feeding operations

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A variety of wind tunnels and flux chambers have been used to measure fluxes of volatile organic compounds (VOC) and ammonia (NH3) at animal feeding operations (AFO). However, there has been little regard to the extreme variation and potential inaccuracies caused by inappropriate air velocity or sw...

  5. Phase Transition Enthalpy Measurements of Organic and Organometallic Compounds. Sublimation, Vaporization and Fusion Enthalpies From 1880 to 2015. Part 1. C1 - C10

    NASA Astrophysics Data System (ADS)

    Acree, William; Chickos, James S.

    2016-09-01

    A compendium of phase change enthalpies published in 2010 is updated to include the period 1880-2015. Phase change enthalpies including fusion, vaporization, and sublimation enthalpies are included for organic, organometallic, and a few inorganic compounds. Part 1 of this compendium includes organic compounds from C1 to C10. Part 2 of this compendium, to be published separately, will include organic and organometallic compounds from C11 to C192. Sufficient data are presently available to permit thermodynamic cycles to be constructed as an independent means of evaluating the reliability of the data. Temperature adjustments of phase change enthalpies from the temperature of measurement to the standard reference temperature, T = 298.15 K, and a protocol for doing so are briefly discussed.

  6. Quantifying Marine Emissions of Biogenic Volatile Organic Compounds Using Laboratory Measurements of Plankton Monocultures and Field Samples

    NASA Astrophysics Data System (ADS)

    Sabolis, A. W.; Meskhidze, N.; Kamykowski, D.; Reed, R. E.

    2010-12-01

    Marine biogenic volatile organic compounds (BVOCs) have been suggested to contribute significant portion of the organic carbon present in ocean atmosphere. In this study emission rates of 40 different hydrocarbons are quantified for lab-grown non-axenic phytoplankton monocultures and ambient samples from the Pamlico-Neuse Estuary, NC. The outcome of environmental conditions on production of BVOCs was examined for different light and temperature conditions. These different regimes are considered proxies for physiological stress-induced effects observed in natural ecosystems. The samples were incubated in a climate controlled room; they were then transferred to smaller volumes (200 ml) for analysis. BVOCs accumulated in the water and headspace above the water were measured by bubbling hydrocarbon-free gas mixture through the sample and passing the gas stream through a gas chromatography/mass spectrometry system equipped with a sample pre-concentrator. Inside the pre-concentrator, the compounds were trapped on a sorbent material, heated, and flushed into the GC-MS column. The pre-concentrator/GC-MS system gave at least 1000 times magnification of the sample concentrations, allowing detection of low ppt levels of hydrocarbons. Here we report results for lab-grown diatoms Thalassiosira weissflogii and Thalassiosira pseudonana, prymnesiophyte Pleurochrysis carterae, and dinoflagellates Karina brevis and Procentrum minimum, as well as field samples. To make results widely usable, all the emissions are normalized to Chlorophyll-a (Chl-a) concentration and cell counts. Our results show that diatoms had the highest isoprene production rate of 2.8 μmol (g Chl-a)-1 h-1 with ranges between 1.4 and 3.6 μmol (g Chl-a)-1 h-1 at light levels between 90 and 900 μE m-2 s-1, respectively. The prymnesiophyte and dinoflagellate species had isoprene production rates of 1.3±0.4 μmol (g Chl-a)-1 h-1 with a similar light dependency as diatoms. Field samples had comparable isoprene

  7. Polydimethylsiloxane-air partition ratios for semi-volatile organic compounds by GC-based measurement and COSMO-RS estimation: Rapid measurements and accurate modelling.

    PubMed

    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. PMID:27179237

  8. Field measurements of biogenic volatile organic compounds in the atmosphere by dynamic solid-phase microextraction and portable gas chromatography-mass spectrometry

    NASA Astrophysics Data System (ADS)

    Barreira, Luís Miguel Feijó; Parshintsev, Jevgeni; Kärkkäinen, Niina; Hartonen, Kari; Jussila, Matti; Kajos, Maija; Kulmala, Markku; Riekkola, Marja-Liisa

    2015-08-01

    Biogenic volatile organic compounds (BVOCs) participate in many physicochemical processes in the atmosphere. Studies indicate that some of these volatile compounds can be photo-oxidized to non-volatile species that contribute to atmospheric formation and growth of secondary organic aerosols (SOA). In this study, the applicability of dynamic solid-phase microextraction (SPME) for the sampling of atmospheric BVOCs and their oxidation products was tested. These compounds were then analysed via portable gas chromatography-mass spectrometry (GC-MS). The measurements were performed in mid-summer 2013 at the Station for Measuring Ecosystem-Atmosphere Relations, SMEAR II in Hyytiälä, Finland. Numerous classes of compounds were efficiently sampled on PDMS/DVB coated SPME, thermally desorbed and analysed by GC-MS, including monoterpenes, their oxidation products, and amines. Results were analysed against meteorological conditions observed during the sampling campaign and the total amount of monoterpenes obtained by proton-transfer-reaction mass spectrometry (PTR-MS). The comparison of the referred data with obtained results demonstrated the capability of the dynamic SPME method for fast in-situ sampling and analysis of organic gaseous compounds in the atmosphere with minimal analytical steps.

  9. Biofiltration of volatile organic compounds.

    PubMed

    Malhautier, Luc; Khammar, Nadia; Bayle, Sandrine; Fanlo, Jean-Louis

    2005-07-01

    The removal of volatile organic compounds (VOCs) from contaminated airstreams has become a major air pollution concern. Improvement of the biofiltration process commonly used for the removal of odorous compounds has led to a better control of key parameters, enabling the application of biofiltration to be extended also to the removal of VOCs. Moreover, biofiltration, which is based on the ability of micro-organisms to degrade a large variety of compounds, proves to be economical and environmentally viable. In a biofilter, the waste gas is forced to rise through a layer of packed porous material. Thus, pollutants contained in the gaseous effluent are oxidised or converted into biomass by the action of microorganisms previously fixed on the packing material. The biofiltration process is then based on two principal phenomena: (1) transfer of contaminants from the air to the water phase or support medium, (2) bioconversion of pollutants to biomass, metabolic end-products, or carbon dioxide and water. The diversity of biofiltration mechanisms and their interaction with the microflora mean that the biofilter is defined as a complex and structured ecosystem. As a result, in addition to operating conditions, research into the microbial ecology of biofilters is required in order better to optimise the management of such biological treatment systems. PMID:15803311

  10. Human breath measurements in a clean-air chamber to determine half-lives for volatile organic compounds

    NASA Astrophysics Data System (ADS)

    Gordon, Sydney M.; Wallace, Lance A.; Pelllzzari, Edo D.; O'Neill, Hugh J.

    The expired breath of four non-occupationally exposed subjects was monitored following exposure at near-normal environmental concentrations using a specially developed pulmonary clearance technique. The four were exposed to polluted air on a heavily trafficked freeway or at a local dry-cleaning establishment, then spent the next 10 h in a clean-air environmental chamber. Breath and chamber-air samples were collected at regular intervals throughout the 10-h period and analyzed for the presence of selected target compounds. The breath levels of two of the compounds were elevated and decreased slowly with time once the subjects began to breathe clean air. Nonlinear least-squares fitting of the decay-uptake curves permitted the calculation of biological half-lives. Several of the target compounds occurred, however, at very low levels, and the resultant experimental scatter limited the value of these measurements. Higher initial exposures to most of the target compounds would have improved the reliability of the estimates.

  11. Measurements of volatile organic compounds at a suburban ground site (T1) in Mexico City during the MILAGRO 2006 campaign: Measurement comparison, emission ratios, and source attribution

    SciTech Connect

    Bon, D.M.; Springston, S.; M.Ulbrich, I.; de Gouw, J. A.; Warneke, C.; Kuster, W. C.; Alexander, M. L.; Baker, A.; Beyersdorf, A. J.; Blake, D.; Fall, R.; Jimenez, J. L., Herndon, S. C.; Huey, L. G.; Knighton, W. B.; Ortega, J.; Vargas, O.

    2011-03-16

    Volatile organic compound (VOC) mixing ratios were measured with two different instruments at the T1 ground site in Mexico City during the Megacity Initiative: Local and Global Research Observations (MILAGRO) campaign in March of 2006. A gas chromatograph with flame ionization detector (GC-FID) quantified 18 light alkanes, alkenes and acetylene while a proton-transfer-reaction ion-trap mass spectrometer (PIT-MS) quantified 12 VOC species including oxygenated VOCs (OVOCs) and aromatics. A GC separation system was used in conjunction with the PIT-MS (GC-PIT-MS) to evaluate PIT-MS measurements and to aid in the identification of unknown VOCs. The VOC measurements are also compared to simultaneous canister samples and to two independent proton-transfer-reaction mass spectrometers (PTR-MS) deployed on a mobile and an airborne platform during MILAGRO. VOC diurnal cycles demonstrate the large influence of vehicle traffic and liquid propane gas (LPG) emissions during the night and photochemical processing during the afternoon. Emission ratios for VOCs and OVOCs relative to CO are derived from early-morning measurements. Average emission ratios for non-oxygenated species relative to CO are on average a factor of {approx}2 higher than measured for US cities. Emission ratios for OVOCs are estimated and compared to literature values the northeastern US and to tunnel studies in California. Positive matrix factorization analysis (PMF) is used to provide insight into VOC sources and processing. Three PMF factors were distinguished by the analysis including the emissions from vehicles, the use of liquid propane gas and the production of secondary VOCs + long-lived species. Emission ratios to CO calculated from the results of PMF analysis are compared to emission ratios calculated directly from measurements. The total PIT-MS signal is summed to estimate the fraction of identified versus unidentified VOC species.

  12. Speciated measurements of semivolatile and intermediate volatility organic compounds (S/IVOCs) in a pine forest during BEACHON-RoMBAS 2011

    NASA Astrophysics Data System (ADS)

    Chan, A. W. H.; Kreisberg, N. M.; Hohaus, T.; Campuzano-Jost, P.; Zhao, Y.; Day, D. A.; Kaser, L.; Karl, T.; Hansel, A.; Teng, A. P.; Ruehl, C. R.; Sueper, D. T.; Jayne, J. T.; Worsnop, D. R.; Jimenez, J. L.; Hering, S. V.; Goldstein, A. H.

    2016-02-01

    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, H2O, 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 are complex in composition, but their chemical identities reveal potential sources. Observed compounds of biogenic origin include sesquiterpenes with molecular formula C15H24 (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 C15H22, 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.

  13. Speciated measurements of semivolatile and intermediate volatility organic compounds (S/IVOCs) in a pine forest during BEACHON-RoMBAS 2011

    DOE PAGESBeta

    Chan, A. W. H.; Kreisberg, N. M.; Hohaus, T.; Campuzano-Jost, P.; Zhao, Y.; Day, D. A.; Kaser, L.; Karl, T.; Hansel, A.; Teng, A. P.; et al

    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, H2O, 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 are complexmore » in composition, but their chemical identities reveal potential sources. Observed compounds of biogenic origin include sesquiterpenes with molecular formula C15H24 (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 C15H22, 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

  14. Speciated measurements of semivolatile and intermediate volatility organic compounds (S/IVOCs) in a pine forest during BEACHON-RoMBAS 2011

    NASA Astrophysics Data System (ADS)

    Chan, A. W. H.; Kreisberg, N. M.; Hohaus, T.; Campuzano-Jost, P.; Zhao, Y.; Day, D. A.; Kaser, L.; Karl, T.; Hansel, A.; Teng, A. P.; Ruehl, C. R.; Sueper, D. T.; Jayne, J. T.; Worsnop, D. R.; Jimenez, J. L.; Hering, S. V.; Goldstein, A. H.

    2015-08-01

    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 (SVTAG-AMS) deployed at Manitou Forest, CO during the Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, 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 are complex in composition, but their chemical identities reveal potential sources. Observed compounds of biogenic origin include sesquiterpenes with molecular formula C15H24 (e.g. β-caryophyllene and longifolene), which were most abundant at night. A variety of other biogenic compounds were observed, including sesquiterpernoids with molecular formula C15H22, 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.

  15. SEMI-VOLATILE ORGANIC COMPOUNDS FROM VEHICLES POWERED BY GASOLINE, DIESEL AND ALTERNATIVE FUELS: EMISSIONS AND FIELD MEASUREMENTS

    EPA Science Inventory

    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...

  16. High-precision optical measurements of 13C/12C isotope ratios in organic compounds at natural abundance

    PubMed Central

    Zare, Richard N.; Kuramoto, Douglas S.; Haase, Christa; Tan, Sze M.; Crosson, Eric R.; Saad, Nabil M. R.

    2009-01-01

    A continuous-flow cavity ring-down spectroscopy (CRDS) system integrating a chromatographic separation technique, a catalytic combustor, and an isotopic 13C/12C optical analyzer is described for the isotopic analysis of a mixture of organic compounds. A demonstration of its potential is made for the geochemically important class of short-chain hydrocarbons. The system proved to be linear over a 3-fold injection volume dynamic range with an average precision of 0.95‰ and 0.67‰ for ethane and propane, respectively. The calibrated accuracy for methane, ethane, and propane is within 3‰ of the values determined using isotope ratio mass spectrometry (IRMS), which is the current method of choice for compound-specific isotope analysis. With anticipated improvements, the low-cost, portable, and easy-to-use CRDS-based instrumental setup is poised to evolve into a credible challenge to the high-cost and complex IRMS-based technique. PMID:19564619

  17. Online derivatization for hourly measurements of gas- and particle-phase semi-volatile oxygenated organic compounds by thermal desorption aerosol gas chromatography (SV-TAG)

    NASA Astrophysics Data System (ADS)

    Isaacman, G.; Kreisberg, N. M.; Yee, L. D.; Worton, D. R.; Chan, A. W. H.; Moss, J. A.; Hering, S. V.; Goldstein, A. H.

    2014-12-01

    Laboratory oxidation studies have identified a large number of oxygenated organic compounds that can be used as tracers to understand sources and oxidation chemistry of atmospheric particulate matter. Quantification of these compounds in ambient environments has traditionally relied on low-time-resolution collection of filter samples followed by offline sample treatment with a derivatizing agent to allow analysis by gas chromatography of otherwise non-elutable organic chemicals with hydroxyl groups. We present here an automated in situ instrument for the measurement of highly polar organic semi-volatile and low-volatility compounds in both the gas- and particle-phase with hourly quantification of mass concentrations and gas-particle partitioning. The dual-cell semi-volatile thermal desorption aerosol gas chromatograph (SV-TAG) with derivatization collects particle-only and combined particle-plus-vapor samples on two parallel sampling cells that are analyzed in series by thermal desorption into helium saturated with derivatizing agent. Introduction of MSTFA (N-methyl-N-(trimethylsilyl)trifluoroacetamide), a silylating agent, yields complete derivatization of all tested compounds, including alkanoic acids, polyols, diacids, sugars, and multifunctional compounds. In laboratory tests, derivatization is found to be highly reproducible (< 3% variability). During field deployment, a regularly injected internal standard is used to correct for variability in detector response, consumption of the derivatization agent, desorption efficiency, and transfer losses. Error in quantification from instrument fluctuations is found to be less than 10% for hydrocarbons and less than 15% for all oxygenates for which a functionally similar internal standard is available, with an uncertainty of 20-25% in measurements of particle fraction. After internal standard corrections, calibration curves are found to be linear for all compounds over the span of 1 month, with comparable response on

  18. A full mass spectrum evaluation of semivolatile organic compounds measured during the Southern Oxidant and Aerosol Study in Alabama, USA, 2013

    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.

  19. Toxic organic compounds from energy production

    SciTech Connect

    Hites, R.A.

    1991-09-20

    The US Department of Energy's Office of Health and Environmental Research (OHER) has supported work in our laboratory since 1977. The general theme of this program has been the identification of potentially toxic organic compounds associated with various combustion effluents, following the fates of these compounds in the environment, and improving the analytical methodology for making these measurements. The projects currently investigation include: an improved sampler for semi-volatile compounds in the atmosphere; the wet and dry deposition of dioxins and furans from the atmosphere; the photodegradation and mobile sources of dioxins and furans; and the bioaccumulation of PAH by tree bark. These projects are all responsive to OHER's interest in the pathways and mechanisms by which energy-related agents move through and are modified by the atmosphere''. The projects on gas chromatographic and liquid chromatographic tandem mass spectrometry are both responsive to OHER's interest in new and more sensitive technologies for chemical measurements''. 35 refs., 9 figs.

  20. Measurement of aerosol organic compounds during TexAQS 2006 using a novel collection/thermal-desorption PTR-ITMS instrument

    NASA Astrophysics Data System (ADS)

    Thornberry, T.; Murphy, D. M.; Thomson, D. S.; Welsh-Bon, D.; Warneke, C.; Bates, T. S.; Coffman, D.; Lerner, B.; Williams, E. J.

    2007-12-01

    Knowledge of the organic species present in atmospheric aerosols is needed in order to understand their effect on aerosol microphysical and optical properties, to resolve outstanding questions about important organic aerosol sources and formation mechanisms, and to elucidate the role of aerosols in the chemistry of the atmosphere through their interaction with gas-phase compounds. The measurement of aerosol organic compounds poses a significant experimental challenge due to the complexity and large number of organic species and the low concentration at which individual species are present. A new instrument that utilizes proton- transfer-reaction mass spectrometry (PTR-MS) to probe the organic composition of atmospheric aerosols has been developed to investigate semi-volatile and condensed-phase organic species in the atmosphere. Aerosols are collected by impaction and then thermally desorbed into a carrier gas that transports the organic analyte molecules into a drift tube where they are ionized by reaction with H3O+ ions. Analyte ions are detected using an ion trap mass spectrometer. The instrument was deployed for the first time during summer 2006 in the Texas Air Quality Study (TexAQS 2006) aboard NOAA R.V. Ronald H. Brown. Signals significantly above detection limit were observed at a number of masses during periods of elevated photochemical activity when aerosol loading increased in the 0.5-1 μm size range and aerosol mass spectrometer (AMS) measurements indicated increased organic mass. Different masses exhibited different temporal behaviors, indicating varying composition of the aerosol organic fraction even during periods when the AMS organic mass (OA) loading was relatively constant. Plumes of aerosol-phase pyridine were observed during sampling near the entrance to the Houston Ship Channel, indicating a relatively local source and rapid partitioning to the aerosol phase. These field results and results of laboratory instrument performance experiments

  1. Volatile organic compound sensing devices

    DOEpatents

    Lancaster, G.D.; Moore, G.A.; Stone, M.L.; Reagen, W.K.

    1995-08-29

    Apparatus employing vapochromic materials in the form of inorganic double complex salts which change color reversibly when exposed to volatile organic compound (VOC) vapors is adapted for VOC vapor detection, VOC aqueous matrix detection, and selective VOC vapor detection. The basic VOC vapochromic sensor is incorporated in various devices such as a ground probe sensor, a wristband sensor, a periodic sampling monitor, a soil/water penetrometer, an evaporative purge sensor, and various vacuum-based sensors which are particularly adapted for reversible/reusable detection, remote detection, continuous monitoring, or rapid screening of environmental remediation and waste management sites. The vapochromic sensor is used in combination with various fiber optic arrangements to provide a calibrated qualitative and/or quantitative indication of the presence of VOCs. 15 figs.

  2. Volatile organic compound sensing devices

    DOEpatents

    Lancaster, Gregory D.; Moore, Glenn A.; Stone, Mark L.; Reagen, William K.

    1995-01-01

    Apparatus employing vapochromic materials in the form of inorganic double complex salts which change color reversibly when exposed to volatile organic compound (VOC) vapors is adapted for VOC vapor detection, VOC aqueous matrix detection, and selective VOC vapor detection. The basic VOC vapochromic sensor is incorporated in various devices such as a ground probe sensor, a wristband sensor, a periodic sampling monitor, a soil/water penetrometer, an evaporative purge sensor, and various vacuum-based sensors which are particularly adapted for reversible/reusable detection, remote detection, continuous monitoring, or rapid screening of environmental remediation and waste management sites. The vapochromic sensor is used in combination with various fiber optic arrangements to provide a calibrated qualitative and/or quantitative indication of the presence of VOCs.

  3. On-line derivatization for hourly measurements of gas- and particle-phase Semi-Volatile oxygenated organic compounds by Thermal desorption Aerosol Gas chromatography (SV-TAG)

    NASA Astrophysics Data System (ADS)

    Isaacman, G.; Kreisberg, N. M.; Yee, L. D.; Worton, D. R.; Chan, A. W. H.; Moss, J. A.; Hering, S. V.; Goldstein, A. H.

    2014-07-01

    Laboratory oxidation studies have identified a large number of oxygenated organic compounds that can be used as tracers to understand sources and oxidation chemistry of atmospheric particulate matter. Quantification of these compounds in ambient environments has traditionally relied on low time-resolution collection of filter samples followed by offline sample treatment with a derivatizing agent to allow analysis by gas chromatography of otherwise non-elutable organic chemicals with hydroxyl groups. We present here an automated in situ instrument for the measurement of highly polar organic semi-volatile and low-volatility compounds in both the gas- and particle-phase with hourly time-resolution. The dual-cell Semi-Volatile Thermal desorption Aerosol Gas chromatograph (SV-TAG) with derivatization collects particle-only and combined particle-plus-vapor samples on two parallel sampling cells that are analyzed in series by thermal desorption into helium saturated with derivatizing agent. Introduction of MSTFA, a silylating agent, yields complete derivatization of all tested compounds, including alkanoic acids, polyols, diacids, sugars, and multifunctional compounds. In laboratory tests, derivatization is found to be highly reproducible (< 3% variability). During field deployment, a regularly injected internal standard is used to correct for variability in detector response, derivatization efficiency, desorption efficiency, and transfer efficiency. Error in quantification from instrument fluctuations is found to be less than 10% for hydrocarbons and less than 15% for all oxygenates for which a functionally similar internal standard is available. After internal standard corrections, calibration curves are found to be linear for all compounds over the span of one month with comparable response on both of the parallel sampling cells.

  4. Laboratory and Ambient Measurements of Oxidized Organic Compounds in the Gas Phase Using Nitrate Ion Chemical Ionization Coupled with High Resolution Time-of-Flight Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Massoli, P.; Stark, H.; Canagaratna, M. R.; Krechmer, J.; Lambe, A. T.; Isaacman-VanWertz, G. A.; Nowak, J. B.; Kimmel, J.; Kroll, J. H.; Jayne, J. T.; Worsnop, D. R.

    2015-12-01

    Chemical Ionization Mass Spectrometry (CIMS) is a widely used technique for molecular level characterization of inorganic and organic gas phase species. Here we present laboratory and ambient measurements of gaseous organic compounds by means of a High Resolution Time-of-Flight Chemical Ionization Mass Spectrometry (HR-ToF-CIMS) using nitrate ion (NO3-) chemistry, which recently has proven capable of selectively detecting oxidized organic molecules in the gas-phase via clustering with NO3- and its high order clusters. Such low and extremely low volatility organic compounds (LVOC, ELVOC) have an important role in particulate phase chemistry and formation of secondary organic aerosol (SOA). The HR-ToF-CIMS was deployed during the Southern Oxidant and Aerosol Study (SOAS) at the forest site in Centreville, AL (June 1 - July 15, 2013), where emissions were dominated by biogenic volatile organic compounds (BVOC), occasionally mixing with anthropogenic emissions. During SOAS, the HR-ToF-CIMS detected oxidation products of both isoprene (typically C5 LVOC) and terpenes (typically C10 ELVOC). The isoprene-related LVOC showed a diurnal cycle with a day time peak, while two groups of terpene ELVOC were identified, one peaking at night and one peaking during the day. Positive Matrix Factorization (PMF) analyses are applied to the dataset to further interpret these observations. The effect of anthropogenic pollution on the biogenic-dominated environment was also investigated during periods of elevated nitrous and sulfur dioxide levels. To further aid in interpretation of the SOAS dataset, oxidized organic molecules were produced via OH and O3 initiated oxidation of biogenic gas-phase precursors in targeted laboratory studies and detected using the HR-ToF-CIMS. Spectra were obtained in these studies over a range of simulated atmospheric conditions.

  5. Measurements of Oxidized Organic Compounds during SOAS 2013 using nitrate ion chemical ionization coupled with High Resolution Time-of-Flight Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Massoli, P.; Stark, H.; Cnagaratna, M.; Junninen, H.; Hakala, J. P.; Mauldin, R.; Ehn, M.; Sipila, M.; Krechmer, J.; Kimmel, J.; Jimenez, J. L.; Jayne, J. T.; Worsnop, D. R.

    2013-12-01

    We present ambient measurements of gaseous organic compounds by means of a High Resolution Time-of-Flight Chemical Ionization Mass Spectrometry (HR-ToF-CIMS) using nitrate ion (NO3-) chemistry. This technique allows to selectively detect oxidized gas-phase species, e.g., oxidized organic molecules and sulfuric acid via clustering with NO3- and its high order clusters. The capability of making such measurements is important because both sulfuric acid and organic gas molecules have a recognized key role in new particle formation (NPF) processes and likely have an important role in particulate phase chemistry and formation of secondary organic aerosols (SOA). The HR-ToF-CIMS was deployed during the Southern Oxidant and Aerosol Study (SOAS) at the forest supersite in Centreville, AL, from June 1 to July 15, 2013. The main goal of the SOAS campaign was to investigate the composition and sources of SOA in the Southeast US, where emissions are mainly represented by biogenic volatile organic compounds (BVOC) emissions and in less extent by anthropogenic emissions (AVOC). During SOAS, the HR-ToF-CIMS detected a range of organic ions that based on previous literature could be identified as oxidation products of both isoprene and terpenes. The isoprene products were 5 to 10 times more abundant than the terpene products. The isoprene-related molecules showed a diurnal cycle with a day time peak, typically after 1500 local time, while the terpene products were higher at night (between 2000 and 0600 local time). These results are consistent with the diurnal trends of primary BVOC emissions from other co-located instruments. The ambient data are also compared to laboratory measurements where oxidized organic vapors are produced using a Potential Aerosol Mass (PAM) flow reactor by the OH oxidation of biogenic gas-phase precursors (isoprene, a-pinene) over multiple days of equivalent atmospheric exposure.

  6. Climate impacts of biogenic organic compounds

    NASA Astrophysics Data System (ADS)

    Sengupta, Kamalika; Gordon, Hamish; Almeida, Joao; Rap, Alex; Scott, Catherine; Pringle, Kirsty; Carslaw, Ken

    2016-04-01

    Currently the most uncertain driver of climate change, impact of anthropogenic aerosols on earth's radiative balance depends significantly on estimates of cloud condensation nuclei (CCN), representation of the pre-industrial atmosphere among others. Nearly 90% of aerosols in the tropics are organic in nature of which a major part comes from biogenic sources. About 45% of the CCN in the atmosphere are formed in-situ via nucleation. Understanding the role of biogenic organic compounds in particle formation and their subsequent growth is hence imperative in order to quantify the climate impact of aerosols. The CLOUD experiment at CERN, which measures particle formation and growth rates in a uniquely clean chamber under atmospherically relevant conditions, found evidence of a nucleation mechanism involving only biogenic organic compounds. This mechanism significantly changes our pre-industrial estimates. The experimental results have been parameterized and included in a global aerosol microphysics model, GLOMAP, to quantify the impact of pure biogenic nucleation on CCN formation and their climatic impact. Further the treatment of secondary organic compounds in GLOMAP has been improved and the sensitivity of our estimates of radiative forcing to the same has been evaluated.

  7. ORGANIC COMPOUNDS IN ORGANOPHOSPHORUS PESTICIDE MANUFACTURING WASTEWATERS

    EPA Science Inventory

    Preliminary survey information on the organophosphorus pesticide industry wastewater streams and analytical methods to monitor levels of organic compounds present in these streams are presented. The identification and quantification of organophosphorus compounds was emphasized, b...

  8. Design and laboratory testing of a chamber device to measure total flux of volatile organic compounds from the unsaturated zone under natural conditions

    NASA Astrophysics Data System (ADS)

    Tillman, Fred D.; Smith, James A.

    2004-11-01

    To determine if an aquifer contaminated with volatile organic compounds (VOCs) has potential for natural remediation, all natural processes affecting the fate and transport of VOCs in the subsurface must be identified and quantified. This research addresses the quantification of air-phase volatile organic compounds (VOCs) leaving the unsaturated zone soil gas and entering the atmosphere—including the additional flux provided by advective soil-gas movement induced by barometric pumping. A simple and easy-to-use device for measuring VOC flux under natural conditions is presented. The vertical flux chamber (VFC) was designed using numerical simulations and evaluated in the laboratory. Mass-balance numerical simulations based on continuously stirred tank reactor equations (CSTR) provided information on flux measurement performance of several sampling configurations with the final chamber configuration measuring greater than 96% of model-simulated fluxes. A laboratory device was constructed to evaluate the flux chamber under both diffusion-only and advection-plus-diffusion transport conditions. The flux chamber measured an average of 82% of 15 diffusion-only fluxes and an average of 95% of 15 additional advection-plus-diffusion flux experiments. The vertical flux chamber has the capability of providing reliable measurement of VOC flux from the unsaturated zone under both diffusion and advection transport conditions.

  9. Smart multi-channel two-dimensional micro-gas chromatography for rapid workplace hazardous volatile organic compounds measurement.

    PubMed

    Liu, Jing; Seo, Jung Hwan; Li, Yubo; Chen, Di; Kurabayashi, Katsuo; Fan, Xudong

    2013-03-01

    We developed a novel smart multi-channel two-dimensional (2-D) micro-gas chromatography (μGC) architecture that shows promise to significantly improve 2-D μGC performance. In the smart μGC design, a non-destructive on-column gas detector and a flow routing system are installed between the first dimensional separation column and multiple second dimensional separation columns. The effluent from the first dimensional column is monitored in real-time and decision is then made to route the effluent to one of the second dimensional columns for further separation. As compared to the conventional 2-D μGC, the greatest benefit of the smart multi-channel 2-D μGC architecture is the enhanced separation capability of the second dimensional column and hence the overall 2-D GC performance. All the second dimensional columns are independent of each other, and their coating, length, flow rate and temperature can be customized for best separation results. In particular, there is no more constraint on the upper limit of the second dimensional column length and separation time in our architecture. Such flexibility is critical when long second dimensional separation is needed for optimal gas analysis. In addition, the smart μGC is advantageous in terms of elimination of the power intensive thermal modulator, higher peak amplitude enhancement, simplified 2-D chromatogram re-construction and potential scalability to higher dimensional separation. In this paper, we first constructed a complete smart 1 × 2 channel 2-D μGC system, along with an algorithm for automated control/operation of the system. We then characterized and optimized this μGC system, and finally employed it in two important applications that highlight its uniqueness and advantages, i.e., analysis of 31 workplace hazardous volatile organic compounds, and rapid detection and identification of target gas analytes from interference background. PMID:23303462

  10. Long-term measurement of volatile organic compounds in ambient air by canister-based one-week sampling method.

    PubMed

    Ochiai, Nobuo; Daishima, Shigeki; Cardin, Daniel B

    2003-12-01

    A canister-based 1 week sampling method using a mechanical flow controller and a 6 L fused-silica-lined canister was evaluated for the long-term measurement of 47 VOCs in ambient air at pptv (volume/volume) to ppbv levels by use of a three-stage preconcentation method followed by GC-MS analysis. The GC conditions were initially optimized for complete separations of several pptv-level VOCs (e.g. vinyl chloride, 1,3-butadiene, acrylonitrile, 1,2-dichloroethane and chloroform) in ambient air because the selected ions are easily interfered with by coexisting C4-, C5-hydrocarbons and analytes presented at ppbv levels. Thirty-four VOCs determined by the 1 week and 24 h sampling method in December 16-22 (2002) had concentrations of 6.0-15000 pptv per compound. Concentrations of 28 VOCs (including polar VOCs (e.g. methyl isobutyl ketone and butyl acetate)) obtained by the method were approximately equal to the mean values calculated from 24 h sampling (< +/- 10% deviation). Six VOCs that had low concentrations of 6.0-43 pptv showed more than +/- 10% deviation. Thirteen VOCs were not detected during the entire sampling period. The effect of relative humidity or ozone for the specific VOCs (e.g. MIBK, butyl acetate, vinyl chloride, 1,3-butadiene and styrene) was negligible. PMID:14710945

  11. COMPACT, CONTINUOUS MONITORING FOR VOLATILE ORGANIC COMPOUNDS - PHASE I

    EPA Science Inventory

    Improved methods for onsite measurement of multiple volatile organic compounds are needed for process control, monitoring, and remediation. This Phase I SBIR project sets forth an optical measurement method that meets these needs. The proposed approach provides an instantaneous m...

  12. METHODS FOR THE DETERMINATION OF ORGANIC COMPOUNDS IN DRINKING WATER

    EPA Science Inventory

    Thirteen analytical methods for the identification and measurement of organic compounds in drinking water are described in detail. ix of the methods are for volatile organic compounds (VOC's) and certain disinfection byproducts and these methods were cited in the Federal Register...

  13. Measurement of the stable carbon isotope ratio of atmospheric volatile organic compounds using chromatography, combustion, and isotope ratio mass spectrometry coupled with thermal desorption

    NASA Astrophysics Data System (ADS)

    Kawashima, Hiroto; Murakami, Mai

    2014-06-01

    The isotopic analysis of atmospheric volatile organic compounds (VOCs), and in particular of their stable carbon isotope ratio (δ13C), could potentially be used as an effective tool for identifying the sources of VOCs. However, to date, there have been very few such analyses. In this work, we analyze the δ13C values of VOCs using thermal desorption coupled with chromatography, combustion, and isotope ratio mass spectrometry (TD-GC/C/IRMS). The measured peak shapes were of high quality and 36 compounds in a standard gas containing 58 VOCs (C5-C11) were detected. The measured δ13C varied widely, from -49.7‰ to -22.9‰, while the standard deviation of the δ13C values varied from 0.07‰ to 0.85‰ (n = 5). We then measured samples from two passenger cars in hot and cold modes, three gas stations, roadside air, and ambient air. In comparison with existing studies, the analytical precision for the 36 compounds in this study was reasonable. By comparing the δ13C values obtained from the cars and gas stations, we could identify some degree of the sources of VOCs in the roadside and ambient air samples.

  14. The Atmospheric Fate of Organic Nitrogen Compounds

    NASA Astrophysics Data System (ADS)

    Borduas, Nadine

    Organic nitrogen compounds are present in our atmosphere from biogenic and anthropogenic sources and have impacts on air quality and climate. Due to recent advances in instrumentation, these compounds are being detected in the gas and particle phases, raising questions as to their source, processing and sinks in the environment. With their recently identified role as contributors to aerosol formation and growth, their novel large scale use as solvents in carbon capture and storage (CCS) technology and their emissions from cigarette smoke, it is now important to address the gaps in our understanding of the fate of organic nitrogen. Experimentally and theoretically, I studied the chemical atmospheric fate of specific organic nitrogen compounds in the amine, amide and isocyanate families, yielding information that can be used in chemical transport models to assess the fate of this emerging class of atmospheric molecules. I performed kinetic laboratory studies in a smog chamber to measure the room temperature rate coefficient for reaction with the hydroxyl radical of monoethanolamine, nicotine, and five different amides. I employed online-mass spectrometry techniques to quantify the oxidation products. I found that amines react quickly with OH radicals with lifetimes of a few hours under sunlit conditions, producing amides as oxidation products. My studies on amides revealed that they have much longer lifetimes in the atmosphere, ranging from a few hours to a week. Photo-oxidation of amides produces isocyanates and I investigated these mechanisms in detail using ab initio calculations. Furthermore, I experimentally measured isocyanic acid's Henry's Law constant as well as its hydrolysis rate constants to better understand its sinks in the atmosphere. Finally, I re-examined the structure-activity relationship (SAR) of organic nitrogen molecules for improved model parameterizations.

  15. Comparison of pressurized liquid extraction and matrix solid-phase dispersion for the measurement of semivolatile organic compound accumulation in tadpoles.

    PubMed

    Stanley, Kerri; Simonich, Staci Massey; Bradford, David; Davidson, Carlos; Tallent-Halsell, Nita

    2009-10-01

    Analytical methods capable of trace measurement of semivolatile 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 present study compares the results of two analytical methods, one using pressurized liquid extraction (PLE) and the other using matrix solid-phase dispersion (MSPD), for the trace measurement of more than 70 SOCs in tadpole tissue, including current-use pesticides. The MSPD method resulted in improved SOC recoveries and precision compared to the PLE method. The MSPD method also required less time, consumed less solvent, and resulted in the measurement of a greater number of SOCs than the PLE method. PMID:19432502

  16. Long-Term Measurements of Volatile Organic Compound Fluxes and Concentrations By Proton Transfer Reaction-Mass Spectrometry from an Amazonian Terra Firme Ecosystem (CLAIRE-UK)

    NASA Astrophysics Data System (ADS)

    Valach, A. C.; House, E. R.; Davison, B.; Shaw, M.; Langford, B.; Nemitz, E.; MacKenzie, A. R.; Artaxo, P.; Yanez-Serrano, A. M.; Jardine, K.; Hewitt, C. N.

    2014-12-01

    Tropical broad leaf species are the highest contributors to biogenic volatile organic compounds (BVOCs) globally making the Amazon tropical forest a major global source. BVOCs can affect atmospheric chemistry, air quality and climate by influencing the oxidative capacity and radiative balance of the atmosphere. Isoprene is the main constituent of total BVOC emissions, however, a wide suite of compounds such as methyl vinyl ketone and methacrolein (MVK and MACR), methyl ethyl ketone, acetone, and monoterpenes play an important role. Due to the remoteness of tropical background sites, there are few continuous long-term canopy scale BVOC measurements and more are needed to improve global atmospheric chemistry models. Approximately one year of continuous high temporal resolution BVOC measurements were made during 2013-2014 as part of the CLAIRE-UK project. Measurements were carried out from the top of a tower above a primary terra firme forest canopy situated approximately 60km north of Manaus, Brazil. A high sensitivity proton transfer reaction-(quadrupole) mass spectrometer (PTR-(Q)MS) was deployed alongside a sonic anemometer to quantify BVOC fluxes using disjunct eddy covariance. Mixing ratios of a range of compounds were measured for 45 minutes at a frequency of 0.5 Hz for flux calculation. Here we present the first results of BVOC flux and mixing ratio measurements from September 2013 to July 2014. Diurnal variability, seasonal differences and possible driving factors will be discussed. In example, positive isoprene fluxes were observed during the day, closely following light intensity and temperature. Diurnal maxima, typically in the order of 5-15 mg isoprene m-2 h-1 were observed between 11:00 and 14:00 local time. Higher emissions occurred during the drier and warmer months from September to December. Preliminary analyses suggest deposition of isoprene oxidation products MVK and MACR, though there is evidence of emission at higher temperatures during some

  17. Biodegradation of halogenated organic compounds.

    PubMed Central

    Chaudhry, G R; Chapalamadugu, S

    1991-01-01

    In this review we discuss the degradation of chlorinated hydrocarbons by microorganisms, emphasizing the physiological, biochemical, and genetic basis of the biodegradation of aliphatic, aromatic, and polycyclic compounds. Many environmentally important xenobiotics are halogenated, especially chlorinated. These compounds are manufactured and used as pesticides, plasticizers, paint and printing-ink components, adhesives, flame retardants, hydraulic and heat transfer fluids, refrigerants, solvents, additives for cutting oils, and textile auxiliaries. The hazardous chemicals enter the environment through production, commercial application, and waste. As a result of bioaccumulation in the food chain and groundwater contamination, they pose public health problems because many of them are toxic, mutagenic, or carcinogenic. Although synthetic chemicals are usually recalcitrant to biodegradation, microorganisms have evolved an extensive range of enzymes, pathways, and control mechanisms that are responsible for catabolism of a wide variety of such compounds. Thus, such biological degradation can be exploited to alleviate environmental pollution problems. The pathways by which a given compound is degraded are determined by the physical, chemical, and microbiological aspects of a particular environment. By understanding the genetic basis of catabolism of xenobiotics, it is possible to improve the efficacy of naturally occurring microorganisms or construct new microorganisms capable of degrading pollutants in soil and aquatic environments more efficiently. Recently a number of genes whose enzyme products have a broader substrate specificity for the degradation of aromatic compounds have been cloned and attempts have been made to construct gene cassettes or synthetic operons comprising these degradative genes. Such gene cassettes or operons can be transferred into suitable microbial hosts for extending and custom designing the pathways for rapid degradation of recalcitrant

  18. Biodegradation of halogenated organic compounds.

    PubMed

    Chaudhry, G R; Chapalamadugu, S

    1991-03-01

    In this review we discuss the degradation of chlorinated hydrocarbons by microorganisms, emphasizing the physiological, biochemical, and genetic basis of the biodegradation of aliphatic, aromatic, and polycyclic compounds. Many environmentally important xenobiotics are halogenated, especially chlorinated. These compounds are manufactured and used as pesticides, plasticizers, paint and printing-ink components, adhesives, flame retardants, hydraulic and heat transfer fluids, refrigerants, solvents, additives for cutting oils, and textile auxiliaries. The hazardous chemicals enter the environment through production, commercial application, and waste. As a result of bioaccumulation in the food chain and groundwater contamination, they pose public health problems because many of them are toxic, mutagenic, or carcinogenic. Although synthetic chemicals are usually recalcitrant to biodegradation, microorganisms have evolved an extensive range of enzymes, pathways, and control mechanisms that are responsible for catabolism of a wide variety of such compounds. Thus, such biological degradation can be exploited to alleviate environmental pollution problems. The pathways by which a given compound is degraded are determined by the physical, chemical, and microbiological aspects of a particular environment. By understanding the genetic basis of catabolism of xenobiotics, it is possible to improve the efficacy of naturally occurring microorganisms or construct new microorganisms capable of degrading pollutants in soil and aquatic environments more efficiently. Recently a number of genes whose enzyme products have a broader substrate specificity for the degradation of aromatic compounds have been cloned and attempts have been made to construct gene cassettes or synthetic operons comprising these degradative genes. Such gene cassettes or operons can be transferred into suitable microbial hosts for extending and custom designing the pathways for rapid degradation of recalcitrant

  19. Methods of making organic compounds by metathesis

    DOEpatents

    Abraham, Timothy W.; Kaido, Hiroki; Lee, Choon Woo; Pederson, Richard L.; Schrodi, Yann; Tupy, Michael John

    2015-09-01

    Described are methods of making organic compounds by metathesis chemistry. The methods of the invention are particularly useful for making industrially-important organic compounds beginning with starting compositions derived from renewable feedstocks, such as natural oils. The methods make use of a cross-metathesis step with an olefin compound to produce functionalized alkene intermediates having a pre-determined double bond position. Once isolated, the functionalized alkene intermediate can be self-metathesized or cross-metathesized (e.g., with a second functionalized alkene) to produce the desired organic compound or a precursor thereto. The method may be used to make bifunctional organic compounds, such as diacids, diesters, dicarboxylate salts, acid/esters, acid/amines, acid/alcohols, acid/aldehydes, acid/ketones, acid/halides, acid/nitriles, ester/amines, ester/alcohols, ester/aldehydes, ester/ketones, ester/halides, ester/nitriles, and the like.

  20. PERFORMANCE AUDITS AND LABORATORY COMPARISONS FOR SCOS97-NARSTO MEASUREMENTS OF SPECIATED VOLATILE ORGANIC COMPOUNDS. (R826237)

    EPA Science Inventory

    Performance audits and laboratory comparisons were conducted as part of the quality assurance program for the 1997 Southern California Ozone Study (SCOS97-NARSTO) to document potential measurement biases among laboratories measuring speciated nonmethane hydrocarbons (NMHC), ca...

  1. A comparison of direct measurement and model simulation of total flux of volatile organic compounds from the subsurface to the atmosphere under natural field conditions

    NASA Astrophysics Data System (ADS)

    Tillman, Fred D.; Choi, Jee-Won; Smith, James A.

    2003-10-01

    Accurate quantification of natural attenuation of volatile organic compounds (VOCs) in groundwater requires an accounting of all VOC mass-loss processes, including volatilization into soil gas with ultimate transport to land surface and the atmosphere. This paper compares two methods of estimating VOC flux to the atmosphere. The first method measures VOC flux at land surface using a vertical flux chamber (VFC). The VFC has been shown in a previous laboratory study to reliably measure organic vapor fluxes from soil to the atmosphere that are caused by either gas phase diffusion or a combination of advection plus diffusion [, 2003]. The second method simulates VOC flux using a transient, one-dimensional gas flow and transport model incorporating the effects of gas phase diffusion, equilibrium air-water partitioning of organic vapors, and unsaturated zone airflow caused by atmospheric pressure changes (i.e., barometric pumping). Flux chamber measurements were made concurrently with field data measurements required for the flow and transport model at a trichloroethene (TCE)-contaminated field site. The two methods of VOC flux estimation provided comparable results in nine sets of field comparisons with the flux chamber estimating a lower flux during most of the time periods. Sensitivity analyses of model input parameters produce upper and lower bounds on best estimate flux simulations. Average VFC measurements fall within these upper and lower bounds of combined parameter values for all nine comparison events. The ease of use, lack of a priori site knowledge and accuracy of the VFC compared with the data-intensive flow and transport model suggests that direct measurement of VOC flux from the subsurface to the atmosphere at contaminated sites could become routine practice, providing important information to decision makers about the progress of monitored natural attenuation.

  2. Trace organic compounds in rain—II. Gas scavenging of neutral organic compounds

    NASA Astrophysics Data System (ADS)

    Ligocki, Mary P.; Leuenberger, Christian; Pankow, James F.

    Concurrent rain and air sampling was conducted for seven rain events in Portland, Oregon during February through to April of 1984. Concentration data are presented for a number of neutral organic compounds for both the rain-dissolved phase and the atmospheric gas phase. The ambient temperature averaged 8°C. Measured gas scavenging ratios ranged from 3 for tetrachloroethene to 10 5 for dibutylphthalate, and were generally 3-6 times higher than those calculated from Henry's Law constant ( H) values at 25°C taken from the literature. This discrepancy was due to the inappropriateness of applying 25°C H data at 5-10°C. Indeed, excellent agreement between the measured and predicted gas scavenging ratios was found for several polycyclic aromatic hydrocarbons for which temperature-dependent H data were available. These results demonstrate that equilibrium between rain and the atmospheric gas phase is attained for non-reactive neutral organic compounds.

  3. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, L.A. Jr.; Arganbright, R.P.; Hearn, D.

    1993-09-07

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C[sub 2] to C[sub 10] olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80 C to 500 C, using as the catalyst a molecular sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene to about the mid point of the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms. 1 figures.

  4. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, Jr., Lawrence A.; Arganbright, Robert P.; Hearn, Dennis

    1994-01-01

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C.sub.2 to C.sub.10 olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80.degree. C. to 500.degree. C., using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms.

  5. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, L.A. Jr.; Arganbright, R.P.; Hearn, D.

    1994-06-14

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C[sub 2] to C[sub 10] olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80 C to 500 C, using as the catalyst a molecular sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms. 1 fig.

  6. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, Jr., Lawrence A.

    1989-01-01

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C.sub.2 to C.sub.10 olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80.degree. C. to 500.degree. C., using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms.

  7. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, Jr., Lawrence A.; Arganbright, Robert P.; Hearn, Dennis

    1993-01-01

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C.sub.2 to C.sub.10 olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80.degree. C. to 500.degree. C., using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene to about the mid point of the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms.

  8. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, L.A. Jr.

    1989-07-18

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C[sub 2] to C[sub 10] olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80 C to 500 C, using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms. 1 fig.

  9. Sorbent-coated diffusion denuders for direct measurement of gas/particle partitioning by semi-volatile organic compounds

    SciTech Connect

    Gundel, L.A.; Lane, D.A.

    1998-01-01

    Sorbent-coated annular denuder-based samplers have been developed for direct determination of both gaseous and particulate semi-volatile organic species. The first such sampler, the Integrated Organic Vapor/Particle Sampler, has been validated for sampling semi-volatile PAH in ambient air and environmental tobacco smoke. Multi-channel versions of the IOVPS have been used successfully for investigation of gas/particle partitioning of a variety of semi-volatile organic species in combustion source-enriched environmental chambers. Subsequent improvements have resulted in two new higher-capacity samplers, the IOGAPS and the jumbo-IOGAPS, that use the same sorbent for sampling trace organics in the ambient atmosphere for 24--48 hr periods over a wide temperature range. Construction of these new samplers began by incorporating the IOVPS coating technology onto the gas collection surfaces of the higher capacity GAP sampler. Substantial design effort aims to ensure that vapor phase components as volatile as naphthalene can be trapped efficiently and retained by the sorbent-coated surface while the particles pass through to the filter.

  10. Biogenic volatile organic compounds - small is beautiful

    NASA Astrophysics Data System (ADS)

    Owen, S. M.; Asensio, D.; Li, Q.; Penuelas, J.

    2012-12-01

    While canopy and regional scale flux measurements of biogenic volatile organic compounds (bVOCs) are essential to obtain an integrated picture of total compound reaching the atmosphere, many fascinating and important emission details are waiting to be discovered at smaller scales, in different ecological and functional compartments. We concentrate on bVOCs below ground to <2m above ground level. Emissions at leaf scale are well documented and widely presented, and are not discussed here. Instead we describe some details of recent research on rhizosphere bVOCs, and bVOCs associated with pollination of flowers. Although bVOC emissions from soil surfaces are small, bVOCs are exuded by roots of some plant species, and can be extracted from decaying litter. Naturally occurring monoterpenes in the rhizosphere provide a specialised carbon source for micro-organisms, helping to define the micro-organism community structure, and impacting on nutrient cycles which are partly controlled by microorganisms. Naturally occurring monoterpenes in the soil system could also affect the aboveground structure of ecosystems because of their role in plant defence strategies and as mediating chemicals in allelopathy. A gradient of monoterpene concentration was found in soil around Pinus sylvestris and Pinus halepensis, decreasing with distance from the tree. Some compounds (α-pinene, sabinene, humulene and caryophyllene) in mineral soil were linearly correlated with the total amount of each compound in the overlying litter, indicating that litter might be the dominant source of these compounds. However, α-pinene did not fall within the correlation, indicating a source other than litter, probably root exudates. We also show that rhizosphere bVOCs can be a carbon source for soil microbes. In a horizontal gradient from Populus tremula trees, microbes closest to the tree trunk were better enzymatically equipped to metabolise labeled monoterpene substrate. Monoterpenes can also increase the

  11. Standardization of flux chamber and wind tunnel flux measurements for quantifying volatile organic compound and ammonia emissions from area sources at animal feeding operations

    NASA Astrophysics Data System (ADS)

    Parker, David; Ham, Jay; Woodbury, Bryan; Cai, Lingshuang; Spiehs, Mindy; Rhoades, Marty; Trabue, Steve; Casey, Ken; Todd, Rick; Cole, Andy

    2013-02-01

    A variety of portable wind tunnels and flux chambers have been used to measure fluxes of volatile organic compounds (VOC) and ammonia (NH3) at animal feeding operations (AFO). However, there has been little regard to the extreme variation and potential inaccuracies caused by air velocity or sweep air flow rates that are either too low or too high to simulate field conditions. There is a need for correction factors to standardize flux chamber and wind tunnel measurements. In this manuscript, we present results of water evaporative flux and VOC flux measurements with the EPA flux chamber and a small wind tunnel. In the EPA flux chamber, water evaporative flux was positively correlated with sweep air flow rate (SAFR) between 1 and 20 L min-1 (r2 = 0.981-0.999) and negatively correlated with sweep air relative humidity between 0 and 80% (r2 = 0.982-0.992). Emissions of gas-film controlled compounds like NH3 and VOC at AFOs were positively correlated with evaporation rates between 0.6 and 2.8 mm d-1. We demonstrate a simple methodology for standardizing and comparing different chamber types by measuring water evaporation within the chamber using a gravimetric mass balance approach under controlled laboratory conditions. A water evaporative flux ratio correction factor (EFRCF) was used to improve the accuracy of field-measured VOC and NH3 chamber flux measurements. In a field study, both the EPA flux chamber (SAFR = 5 L min-1) and small wind tunnel (SAFR = 1 L min-1) underestimated the true field emissions of VOC, with EFRCFs of 2.42 and 3.84, respectively. EFRCFs are recommended for all but the driest of soil and manure conditions.

  12. Organic electronic devices using phthalimide compounds

    DOEpatents

    Hassan, Azad M.; Thompson, Mark E.

    2013-03-19

    Organic electronic devices comprising a phthalimide compound. The phthalimide compounds disclosed herein are electron transporters with large HOMO-LUMO gaps, high triplet energies, large reduction potentials, and/or thermal and chemical stability. As such, these phthalimide compounds are suitable for use in any of various organic electronic devices, such as OLEDs and solar cells. In an OLED, the phthalimide compounds may serve various functions, such as a host in the emissive layer, as a hole blocking material, or as an electron transport material. In a solar cell, the phthalimide compounds may serve various functions, such as an exciton blocking material. Various examples of phthalimide compounds which may be suitable for use in the present invention are disclosed.

  13. Organic electronic devices using phthalimide compounds

    DOEpatents

    Hassan, Azad M.; Thompson, Mark E.

    2010-09-07

    Organic electronic devices comprising a phthalimide compound. The phthalimide compounds disclosed herein are electron transporters with large HOMO-LUMO gaps, high triplet energies, large reduction potentials, and/or thermal and chemical stability. As such, these phthalimide compounds are suitable for use in any of various organic electronic devices, such as OLEDs and solar cells. In an OLED, the phthalimide compounds may serve various functions, such as a host in the emissive layer, as a hole blocking material, or as an electron transport material. In a solar cell, the phthalimide compounds may serve various functions, such as an exciton blocking material. Various examples of phthalimide compounds which may be suitable for use in the present invention are disclosed.

  14. Organic electronic devices using phthalimide compounds

    DOEpatents

    Hassan, Azad M.; Thompson, Mark E.

    2012-10-23

    Organic electronic devices comprising a phthalimide compound. The phthalimide compounds disclosed herein are electron transporters with large HOMO-LUMO gaps, high triplet energies, large reduction potentials, and/or thermal and chemical stability. As such, these phthalimide compounds are suitable for use in any of various organic electronic devices, such as OLEDs and solar cells. In an OLED, the phthalimide compounds may serve various functions, such as a host in the emissive layer, as a hole blocking material, or as an electron transport material. In a solar cell, the phthalimide compounds may serve various functions, such as an exciton blocking material. Various examples of phthalimide compounds which may be suitable for use in the present invention are disclosed.

  15. Computational and Experimental Assessment of Benzene Cation Chemistry for the Measurement of Marine Derived Biogenic Volatile Organic Compounds with Chemical Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Zoerb, M.; Kim, M.; Zimmermann, K.; Bertram, T. H.

    2013-12-01

    Chemical ionization mass spectrometry (CIMS) is a highly selective and sensitive technique for the measurement of trace gases in the atmosphere. However, competing side reactions and dependence on relative humidity (RH) can make the transition from the laboratory to the field challenging. Effective implementation of chemical ionization requires a thorough knowledge of the elementary steps leading to ionization of the analyte. We have recently investigated benzene cations for the detection of marine derived biogenic volatile organic compounds (BVOCs), such isoprene and terpene compounds, from algal bloom events. Our experimental results indicate that benzene ion chemistry is an attractive candidate for field measurements, and the RH dependence is weak. To further understand the advantages and limitations of this approach, we have also used electronic structure theory calculations to compliment the experimental work. These theoretical methods can provide valuable insight into the physical chemistry of ion molecule reactions including thermodynamical information, the stability of ions to fragmentation, and potential sources of interference such as dehydration to form isobaric ions. The combined experimental and computational approach also allows validation of the theoretical methods and will provide useful information towards gaining predictive power for the selection of appropriate reagent ions for future experiments.

  16. Microwave spectra of some volatile organic compounds

    NASA Technical Reports Server (NTRS)

    White, W. F.

    1975-01-01

    A computer-controlled microwave (MRR) spectrometer was used to catalog reference spectra for chemical analysis. Tables of absorption frequency, peak absorption intensity, and integrated intensity are included for 26 volatile organic compounds, all but one of which contain oxygen.

  17. VOLATILE ORGANIC COMPOUNDS AS EXPOSURE BIOMARKERS

    EPA Science Inventory

    Alveolar breath sampling and analysis can be extremely useful in exposure assessment studies involving volatile organic compounds (VOCs). Over recent years scientists from the US Environmental Protection Agency's National Exposure Research Laboratory have developed and refined...

  18. (CHINA) PERFLUORINATED ORGANIC COMPOUND EXPOSURE ASSESSMENT RESEARCH

    EPA Science Inventory

    A wide range of perfluorinated organic compounds (PFCs) has been used in a variety of industrial processes and consumer products. The most commonly studied PFCs include perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), but there are many more compounds in this c...

  19. Volatile organic compound emissions from silage systems

    Technology Transfer Automated Retrieval System (TEKTRAN)

    As a precursor to smog, emission of volatile organic compounds (VOCs) to the atmosphere is an environmental concern in some regions. The major source from farms is silage, with emissions coming from the silo face, mixing wagon, and feed bunk. The major compounds emitted are alcohols with other impor...

  20. PERFLUORINATED ORGANIC COMPOUND EXPOSURE ASSESSMENT RESEARCH

    EPA Science Inventory

    A wide range of perfluorinated organic compounds (PFCs) has been used in a variety of industrial processes and consumer products. The most commonly studied PFCs include perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), but there are many more compounds in this c...

  1. VOLATILE ORGANIC COMPOUNDS (VOCS) CHAPTER 31.

    EPA Science Inventory

    The term "volatile organic compounds' (VOCs) was originally coined to refer, as a class, to carbon-containing chemicals that participate in photochemical reactions in the ambient (outdoor) are. The regulatory definition of VOCs used by the U.S. EPA is: Any compound of carbon, ex...

  2. Industrial sector-based volatile organic compound (VOC) source profiles measured in manufacturing facilities in the Pearl River Delta, China.

    PubMed

    Zheng, Junyu; Yu, Yufan; Mo, Ziwei; Zhang, Zhou; Wang, Xinming; Yin, Shasha; Peng, Kang; Yang, Yang; Feng, Xiaoqiong; Cai, Huihua

    2013-07-01

    Industrial sector-based VOC source profiles are reported for the Pearl River Delta (PRD) region, China, based source samples (stack emissions and fugitive emissions) analyzed from sources operating under normal conditions. The industrial sectors considered are printing (letterpress, offset and gravure printing processes), wood furniture coating, shoemaking, paint manufacturing and metal surface coating. More than 250 VOC species were detected following US EPA methods TO-14 and TO-15. The results indicated that benzene and toluene were the major species associated with letterpress printing, while ethyl acetate and isopropyl alcohol were the most abundant compounds of other two printing processes. Acetone and 2-butanone were the major species observed in the shoemaking sector. The source profile patterns were found to be similar for the paint manufacturing, wood furniture coating, and metal surface coating sectors, with aromatics being the most abundant group and oxygenated VOCs (OVOCs) as the second largest contributor in the profiles. While OVOCs were one of the most significant VOC groups detected in these five industrial sectors in the PRD region, they have not been reported in most other source profile studies. Such comparisons with other studies show that there are differences in source profiles for different regions or countries, indicating the importance of developing local source profiles. PMID:23584189

  3. Effect of the presence of chlorates and perchlorates on the pyrolysis of organic compounds: implications for measurements done with the SAM experiment onboard the Curiosity rover

    NASA Astrophysics Data System (ADS)

    Millan, Maeva; Szopa, Cyril; Buch, Arnaud; Belmahdi, Imène; Coll, Patrice; Glavin, Daniel P.; Freissinet, Caroline; Archer, Doug; Sutter, Brad; Summons, Roger E.; Navarro-Gonzalez, Rafael; Cabane, Michel; Mahaffy, Paul

    2016-04-01

    /or quantitative effects. The experiments are performed on a laboratory GC-QMS with a Restek Rxi-5 column (30m x 0.25mm x 0.25μm) and an Intersciences pyrolyser. The mixture is pyrolyzed at different temperatures up to 900°C to cover the SAM temperature range. Different experiments are done to discriminate the pyrolysis products directly coming from the organics, and those produced from the reaction with oxychlorine. These experiments are under progress and should bring key information on the potential to identify Martian organics when pyrolyzing solid samples. Depending on the organic families studied, we may find recurring molecules, which are potentially present in Mars' surface samples. This work could thus highlight some organic precursors of the chlorinated compounds found on Mars, and support the interpretation of SAM measurements. References: [1] Mahaffy, P. et al. (2012) Space Sci Rev, 170, 401-478. [2] Biemann, K. et al (1977) JGR, 82, 4641-4658. [3] Glavin, D. et al. (2013), JGR 118, 1955-1973. [4] Freissinet, C. et al. (2015) JGR. [5] Leshin L. et al. (2013), Science. [6] Hecht, (2009), Science, 325 64-67. [7] Navarro-Gonzalez et al. (2010) JGR 115, EI12010. [8] Steninger, H. et al (2012) Planet. Space Sci. 71, 9-17. Acknowledgments: French Space Agency (CNES) support for SAM-GC development and exploitation.

  4. Tropical Greenhouse Measurements of Volatile Organic Compounds Using Switchable Reagent Ion Proton-Transfer-Reaction Time-of-Flight Mass Spectromety (PTR-TOF-MS)

    NASA Astrophysics Data System (ADS)

    Veres, P.; Auld, J.; Williams, J.

    2012-04-01

    In this presentation, we will summarize the results of measurements made in an approximately 1300 m3 tropical greenhouse at the Johannes Gutenberg University botanical garden in Mainz Germany conducted over a one month period. The greenhouse is home to a large variety of plant species from hot and humid regions of the world. The greenhouse is also host to several crops such as Cocoa and Cola Nut as well as ornamental plants. A particular focus of the species maintained are those which are considered ant plants, or plants which have an intimate relationship with ants in tropical habitats. Volatile organic compounds (VOCs) were measured using a Switchable Reagent Ion Proton-Transfer-Reaction Time-of-Flight Mass Spectrometer (PTR-TOF-MS) using H3O+, NO+, and O2+ ion chemistry. Measurements will be presented both for primary emissions observed in the closed greenhouse atmosphere as well as the oxidation products observed after the introduction of ambient ozone. The high resolving power (5000 m/Δm) of the time-of-flight instrument allows for the separation of isobaric species. In particular, both isoprene (68.1170 amu) and furan (68.0740 amu) were observed and separated as primary emissions during this study. The significance of this will be discussed in terms of both atmospheric implications as well as with respect to previous measurements of isoprene obtained using quadrupole PTR-MS where isobaric separation of these compounds is not possible. Additionally observed species (e.g. Methanol, Acetaldehyde, MVK and MEK) will be discussed in detail with respect to their behavior as a function of light, temperature and relative humidity. The overall instrument performance of the PTR-TOF-MS technique using the H3O+, NO+, and O2+ primary ions for the measurement of VOCs will be evaluated.

  5. Volatile Organic Compound Analysis in Istanbul

    NASA Astrophysics Data System (ADS)

    Ćapraz, Ö.; Deniz, A.; Öztürk, A.; Incecik, S.; Toros, H.; Coşkun, M.

    2012-04-01

    Volatile Organic Compound Analysis in Istanbul Ö. Çapraz1, A. Deniz1,3, A. Ozturk2, S. Incecik1, H. Toros1 and, M. Coskun1 (1) Istanbul Technical University, Faculty of Aeronautics and Astronautics, Department of Meteorology, 34469, Maslak, Istanbul, Turkey. (2) Istanbul Technical University, Faculty of Chemical and Metallurgical, Chemical Engineering, 34469, Maslak, Istanbul, Turkey. (3) Marmara Clean Air Center, Ministry of Environment and Urbanization, Nişantaşı, 34365, İstanbul, Turkey. One of the major problems of megacities is air pollution. Therefore, investigations of air quality are increasing and supported by many institutions in recent years. Air pollution in Istanbul contains many components that originate from a wide range of industrial, heating, motor vehicle, and natural emissions sources. VOC, originating mainly from automobile exhaust, secondhand smoke and building materials, are one of these compounds containing some thousands of chemicals. In spite of the risks to human health, relatively little is known about the levels of VOC in Istanbul. In this study, ambient air quality measurements of 32 VOCs including hydrocarbons, halogenated hydrocarbons and carbonyls were conducted in Kağıthane (Golden Horn) region in Istanbul during the winter season of 2011 in order to develop the necessary scientific framework for the subsequent developments. Kağıthane creek valley is the source part of the Golden Horn and one of the most polluted locations in Istanbul due to its topographical form and pollutant sources in the region. In this valley, horizontal and vertical atmospheric motions are very weak. The target compounds most commonly found were benzene, toluene, xylene and ethyl benzene. Concentrations of total hydrocarbons ranged between 1.0 and 10.0 parts per billion, by volume (ppbv). Ambient air levels of halogenated hydrocarbons appeared to exhibit unique spatial variations and no single factor seemed to explain trends for this group of

  6. Measurements of volatile organic compounds (VOCs) at the puy de Dôme research station (France, 1465m a.s.l.).

    NASA Astrophysics Data System (ADS)

    Colomb, A.; Gaimoz, C.; Fleuret, J.; Jacob, V.; Bouvier, L.; Pichon, J.-M.; Picard, D.; Ribeiro, M.; Freney, E.; Asmi, E.; Hervo, M.; Rose, C.; Jaffrezo, J.-L.; Sellegri, K.

    2012-04-01

    The high altitude puy de Dôme research station is located in central France (45° 46' N, 2° 57' E, 1465 m a.s.l.), 16km away from the city of Clermont-Ferrand. This station has been classified as representative background. At the summit, meteorological parameters including wind speed and direction, temperature, pressure, relative humidity and radiation, atmospheric trace gases (O3, NOx, SO2, CO2, CO), and aerosol physical, optical and chemical properties (particle size, black carbon, mass,... Selected volatile organic compounds (VOCs, including a large set of non-methane hydrocarbons and some terpenes (isoprene, α-pinene, …) and some oxygenated and halogenated compounds) were measured during intensive campaigns in summer 2010, spring 2011, summer 2011 and winter 2012. The analysis of VOCs collected on Tenax/Carbosieve III cartridges was achieved by using thermo-desorption coupled gas-chromatography with mass spectrometry (GC-MS). In order to determine the transport pathways of the air masses prior to arriving at the pdD site, the Hybrid Single Particle Langrangian Trajectory (HYSPLIT) model was used. Trajectories were classified according to their predominant transport direction prior to measurement as either continental (C), marine (M), marine modified (Mod), Mediterranean (Med), or mixed depending on their pathways. The results presented here are discussed in terms of observed levels, diurnal variability and sources influence. Different methods, including examination of ratio between compounds, comparison with other tracers (CO, BC, …) or other variables (temperature, air masses origins, planetary boundary layer height,…), are used to identify main parameters influencing VOCs variability.

  7. [Polar neutral organic compounds (POCN) in city aerosols. 2. Measuring of emissions from domestic fuel and vehicle exhaust and from immission particles in Berlin (West)].

    PubMed

    Moriske, H J; Freise, R; Schneider, C; Rüden, H

    1987-10-01

    During April and May 1985, some emission samples from private coal firing (domestic fuel) were taken and were fired with two different kind of coal (bituminous and brown coal). Also, measurements were done under different combustion conditions (low and high concentrations of oxygenium during the combustion process). In June and November 1985, some emission samples from heavy diesel-engines were taken in a special tunnel equipment, at different engine conditions. During September 1985, also suspended particulates in a highway traffic tunnel were taken. All these samples were taken using high volume cascade impactors which give a fractionation of the suspended particulates into different particle sizes, according to their retention behaviour in the human respiratory system. The results of these emission samples and samples in the highway tunnel were compared with prior immission measurements of urban suspended particulates in Berlin-West, during January 1984. The etherextractable organic matter (= EEOM) of the total suspended particulate matter (= TPM) was determined using ultrasonic extraction method. The EEOM was separated into an acidic (= AF), a basic (= BF) and a neutral fraction (= NF) by dissolution in acidic and basic agents. Of the neutral fraction (NF), further separation was done into aliphatic compounds (= AIP), polycyclic aromatic hydrocarbons (= PAH) and polar neutral organic compounds (POCN) by using thin layer chromatography. From the PAH and POCN, single compounds were identified by gas chromatographic analysis with dual capillary collumns and internal standard method. All organic fractions were tested to their mutagenic activity in the Salmonella typhimurium mammalian microsome bioassay by Ames. The following results were gained: the neutral fraction (NF) made the highest part of the EEOM (greater than or equal to 60%) whereas the part of the AF amounted to 10-25% and of the basic fraction (BF) to approximatively 5-20%. Making further separation of

  8. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, L.A. Jr.; Arganbright, R.P.; Hearn, D.

    1993-01-05

    Aromatic compounds are alkylated in a combination reactor/distillation column comprising a vessel suitable for operating between 70 C and 500 C and from 0.5 to 20 atmospheres pressure; an inert distillation packing in the lower one-third of said vessel; solid acidic catalytic material such as zeolites or an acidic cation exchange resin supported in the middle one-third of said vessel; and inert distillation packing in the upper one-third of said vessel. A benzene inlet is located near the upper end of the vessel; an olefin inlet is juxtaposed with said solid acidic catalytic material; a bottoms outlet is positioned near the bottom of said vessel for removing said cumene and ethyl benzene; and an overhead outlet is placed at the top of said vessel for removing any unreacted benzene and olefin.

  9. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, Jr., Lawrence A.; Arganbright, Robert P.; Hearn, Dennis

    1993-01-01

    Aromatic compounds are alkylated in a combination reactor/distillation column comprising a vessel suitable for operating between 70.degree. C. and 500.degree. C. and from 0.5 to 20 atmospheres pressure; an inert distillation packing in the lower one-third of said vessel; solid acidic catalytic material such as zeolites or an acidic cation exchange resin supported in the middle one-third of said vessel; and inert distillation packing in the upper one-third of said vessel. A benzene inlet is located near the upper end of the vessel; an olefin inlet is juxtaposed with said solid acidic catalytic material; a bottoms outlet is positioned near the bottom of said vessel for removing said cumene and ethyl benzene; and an overhead outlet is placed at the top of said vessel for removing any unreacted benzene and olefin.

  10. Semivolatile organic compounds in indoor environments

    NASA Astrophysics Data System (ADS)

    Weschler, Charles J.; Nazaroff, William W.

    Semivolatile organic compounds (SVOCs) are ubiquitous in indoor environments, redistributing from their original sources to all indoor surfaces. Exposures resulting from their indoor presence contribute to detectable body burdens of diverse SVOCs, including pesticides, plasticizers, and flame retardants. This paper critically examines equilibrium partitioning of SVOCs among indoor compartments. It proceeds to evaluate kinetic constraints on sorptive partitioning to organic matter on fixed surfaces and airborne particles. Analyses indicate that equilibrium partitioning is achieved faster for particles than for typical indoor surfaces; indeed, for a strongly sorbing SVOC and a thick sorptive reservoir, equilibrium partitioning is never achieved. Mass-balance considerations are used to develop physical-science-based models that connect source- and sink-rates to airborne concentrations for commonly encountered situations, such as the application of a pesticide or the emission of a plasticizer or flame retardant from its host material. Calculations suggest that many SVOCs have long indoor persistence, even after the primary source is removed. If the only removal mechanism is ventilation, moderately sorbing compounds ( Koa > 10 10) may persist indoors for hundreds to thousands of hours, while strongly sorbing compounds ( Koa > 10 12) may persist for years. The paper concludes by applying the newly developed framework to explore exposure pathways of building occupants to indoor SVOCs. Accumulation of SVOCs as a consequence of direct air-to-human transport is shown to be potentially large, with a maximum indoor-air processing rate of 10-20 m 3/h for SVOC uptake by human skin, hair and clothing. Levels on human skin calculated with a simple model of direct air-to-skin transfer agree remarkably well with levels measured in dermal hand wipes for SVOCs possessing a wide range of octanol-air partition coefficients.

  11. INDOOR AIR QUALITY DATA BASE FOR ORGANIC COMPOUNDS

    EPA Science Inventory

    The report gives results of the compilation of a data base for concentrations of organic compounds measured indoors. ased on a review of the literature from 1979 through 1990, the data base contains information on over 220 compounds ranging in molecular weight from 30 to 446. he ...

  12. Construction and Operation of a Ventilated Hood System for Measuring Greenhouse Gas and Volatile Organic Compound Emissions from Cattle.

    PubMed

    Place, Sara E; Pan, Yuee; Zhao, Yongjing; Mitloehner, Frank M

    2011-01-01

    Recent interest in greenhouse gas emissions from ruminants, such as cattle, has spawned a need for affordable, precise, and accurate methods for the measurement of gaseous emissions arising from enteric fermentation. A new head hood system for cattle designed to capture and quantify emissions was recently developed at the University of California, Davis. The system consists of two head hoods, two vacuum pumps, and an instrumentation cabinet housing the required data collection equipment. This system has the capability of measuring carbon dioxide, methane, ethanol, methanol, water vapor, nitrous oxide, acetic acid emissions and oxygen consumption in real-time. A unique aspect of the hoods is the front, back, and sides are made of clear polycarbonate sheeting allowing the cattle a full range of vision during gas sampling. Recovery rates for these slightly negative pressure chambers were measured ranging from 97.6 to 99.3 percent. This system can capture high quality data for use in improving emission inventories and evaluating gaseous emission mitigation strategies. PMID:26486626

  13. Canopy-scale flux measurements and bottom-up emission estimates of volatile organic compounds from a mixed oak and hornbeam forest in northern Italy

    NASA Astrophysics Data System (ADS)

    Acton, W. J. F.; Schallhart, S.; Langford, B.; Valach, A.; Rantala, P.; Fares, S.; Carriero, G.; Tillmann, R.; Tomlinson, S. J.; Dragosits, U.; Gianelle, D.; Hewitt, C. N.; Nemitz, E.

    2015-10-01

    This paper reports the fluxes and mixing ratios of biogenically emitted volatile organic compounds (BVOCs) 4 m above a mixed oak and hornbeam forest in northern Italy. Fluxes of methanol, acetaldehyde, isoprene, methyl vinyl ketone + methacrolein, methyl ethyl ketone and monoterpenes were obtained using both a proton transfer reaction-mass spectrometer (PTR-MS) and a proton transfer reaction-time of flight-mass spectrometer (PTR-ToF-MS) together with the methods of virtual disjunct eddy covariance (PTR-MS) and eddy covariance (PTR-ToF-MS). Isoprene was the dominant emitted compound with a mean day-time flux of 1.9 mg m-2 h-1. Mixing ratios, recorded 4 m above the canopy, were dominated by methanol with a mean value of 6.2 ppbv over the 28 day measurement period. Comparison of isoprene fluxes calculated using the PTR-MS and PTR-ToF-MS showed very good agreement while comparison of the monoterpene fluxes suggested a slight over estimation of the flux by the PTR-MS. A basal isoprene emission rate for the forest of 1.7 mg m-2 h-1 was calculated using the MEGAN isoprene emissions algorithms (Guenther et al., 2006). A detailed tree species distribution map for the site enabled the leaf-level emissions of isoprene and monoterpenes recorded using GC-MS to be scaled up to produce a "bottom-up" canopy-scale flux. This was compared with the "top-down" canopy-scale flux obtained by measurements. For monoterpenes, the two estimates were closely correlated and this correlation improved when the plant species composition in the individual flux footprint was taken into account. However, the bottom-up approach significantly underestimated the isoprene flux, compared with the top-down measurements, suggesting that the leaf-level measurements were not representative of actual emission rates.

  14. A system and methodology for measuring volatile organic compounds produced by hydroponic lettuce in a controlled environment

    NASA Technical Reports Server (NTRS)

    Charron, C. S.; Cantliffe, D. J.; Wheeler, R. M.; Manukian, A.; Heath, R. R.

    1996-01-01

    A system and methodology were developed for the nondestructive qualitative and quantitative analysis of volatile emissions from hydroponically grown 'Waldmann's Green' leaf lettuce (Lactuca sativa L.). Photosynthetic photon flux (PPF), photoperiod, and temperature were automatically controlled and monitored in a growth chamber modified for the collection of plant volatiles. The lipoxygenase pathway products (Z)-3-hexenal, (Z)-3-hexenol, and (Z)-3-hexenyl acetate were emitted by lettuce plants after the transition from the light period to the dark period. The volatile collection system developed in this study enabled measurements of volatiles emitted by intact plants, from planting to harvest, under controlled environmental conditions.

  15. Atmospheric Chemistry of Micrometeoritic Organic Compounds

    NASA Technical Reports Server (NTRS)

    Kress, M. E.; Belle, C. L.; Pevyhouse, A. R.; Iraci, L. T.

    2011-01-01

    Micrometeorites approx.100 m in diameter deliver most of the Earth s annual accumulation of extraterrestrial material. These small particles are so strongly heated upon atmospheric entry that most of their volatile content is vaporized. Here we present preliminary results from two sets of experiments to investigate the fate of the organic fraction of micrometeorites. In the first set of experiments, 300 m particles of a CM carbonaceous chondrite were subject to flash pyrolysis, simulating atmospheric entry. In addition to CO and CO2, many organic compounds were released, including functionalized benzenes, hydrocarbons, and small polycyclic aromatic hydrocarbons. In the second set of experiments, we subjected two of these compounds to conditions that simulate the heterogeneous chemistry of Earth s upper atmosphere. We find evidence that meteor-derived compounds can follow reaction pathways leading to the formation of more complex organic compounds.

  16. Sources, Sinks and Chemistry of Volatile Organic Compounds: A Summary of Results from Multiple Airborne, Ship-Based and Surface Measurements

    NASA Astrophysics Data System (ADS)

    de Gouw, J. A.; Gilman, J. B.; Goldan, P. D.; Kuster, W. C.; Roberts, J. M.; Veres, P. R.; Warneke, C.; Welsh-Bon, D.

    2009-12-01

    Volatile Organic compounds (VOCs) are emitted from a wide variety of natural and man-made sources. In the atmosphere, VOCs are oxidized on a time scale ranging from minutes to months by reactions with OH, NO3 and ozone, and by photolysis. While the removal of hydrocarbons is well described by these removal processes, the chemical formation and direct emissions of oxygenated VOCs are poorly characterized and understood. VOC oxidation in the atmosphere contributes to the formation of ozone and secondary organic aerosol (SOA). Both species are important ingredients of polluted air and represent a significant radiative forcing to the climate system. We have measured VOCs during several different field studies using both mass spectrometric and gas chromatographic methods. Airborne measurements from the NOAA WP-3D aircraft were carried out along the U.S. West Coast in 2002, in the northeastern U.S. in 2004, in Texas in 2006 and in Alaska in 2008. Ship-based measurements were conducted in the Gulf of Maine in 2002 and 2004, in the Gulf of Mexico in 2006 and in the northern Atlantic in 2008. Surface measurements were made in Beijing in 2005, in Mexico City in 2006 and at Blodgett Forest in 2007. In this presentation we will first make a comparison of the averaged observations between these different field studies. Average altitude profiles, surface mixing ratios and the diurnal variations therein will be compared, which gives a unique and detailed insight into the atmospheric distribution of VOCs. We will next turn to several case studies describing our observations in urban, forest fire and industrial plumes with a special focus on oxygenated VOCs. Insights into the natural sources of oxygenated VOCs from forests and oceans are described. Finally, we will briefly discuss new instrument developments in our laboratory.

  17. Photocatalytic oxidation of organic compounds on Mars

    NASA Technical Reports Server (NTRS)

    Chun, S. F. S.; Pang, K. D.; Cutts, J. A.; Ajello, J. M.

    1978-01-01

    Ultraviolet-stimulated catalytic oxidation is proposed as a mechanism for the destruction of organic compounds on Mars. The process involves the presence of gaseous oxygen, UV radiation, and a catalyst (titanium dioxide), and all three of these have been found to be present in the Martian environment. Therefore it seems plausible that UV-stimulated oxidation of organics is responsible for degrading organic molecules into inorganic end products.

  18. Reflectance spectroscopy of organic compounds: 1. Alkanes

    USGS Publications Warehouse

    Clark, R.N.; Curchin, J.M.; Hoefen, T.M.; Swayze, G.A.

    2009-01-01

    Reflectance spectra of the organic compounds comprising the alkane series are presented from the ultraviolet to midinfrared, 0.35 to 15.5 /??m. Alkanes are hydrocarbon molecules containing only single carbon-carbon bonds, and are found naturally on the Earth and in the atmospheres of the giant planets and Saturn's moon, Titan. This paper presents the spectral properties of the alkanes as the first in a series of papers to build a spectral database of organic compounds for use in remote sensing studies. Applications range from mapping the environment on the Earth, to the search for organic molecules and life in the solar system and throughout the. universe. We show that the spectral reflectance properties of organic compounds are rich, with major diagnostic spectral features throughout the spectral range studied. Little to no spectral change was observed as a function of temperature and only small shifts and changes in the width of absorption bands were observed between liquids and solids, making remote detection of spectral properties throughout the solar system simpler. Some high molecular weight organic compounds contain single-bonded carbon chains and have spectra similar to alkanes even ' when they fall into other families. Small spectral differences are often present allowing discrimination among some compounds, further illustrating the need to catalog spectral properties for accurate remote sensing identification with spectroscopy.

  19. Enantiomeric and Isotopic Analysis of Organic Compounds in Carbonaceous Meteorites

    NASA Technical Reports Server (NTRS)

    Cooper, George

    2004-01-01

    Carbonaceous meteorites are relatively enriched in soluble organic compounds. The Murchison and Murray meteorites contain numerous compounds of interest in the study of early solar system organic chemistry and organic compounds of potential importance for the origin of life. These include: amino acids, amides, carboxylic acids, and polyols. This talk will focus on the enantiomeric and isotopic analysis of individual meteoritic compounds - primarily polyol acids. The analyses will determine if, in addition to certain amino acids from Murchison, another potentially important class of prebiotic compounds also contains enantiomeric excesses, i.e., excesses that could have contributed to the current homochirality of life. Preliminary enantiomeric and isotopic (C- 13) measurements of Murchison glyceric acid show that it is indeed extraterrestrial. C-13 and D isotope analysis of meteoritic sugar alcohols (glycerol, threitol, ribitol, etc.) has shown that they are also indigenous to the meteorite.

  20. Emissions of volatile organic compounds (VOCs) from oil and natural gas activities: compositional comparison of 13 major shale basins via NOAA airborne measurements

    NASA Astrophysics Data System (ADS)

    Gilman, J.; Lerner, B. M.; Aikin, K. C.; De Gouw, J. A.; Koss, A.; Yuan, B.; Warneke, C.; Peischl, J.; Ryerson, T. B.; Holloway, J. S.; Graus, M.; Tokarek, T. W.; Isaacman-VanWertz, G. A.; Sueper, D.; Worsnop, D. R.

    2015-12-01

    The recent and unprecedented increase in natural gas production from shale formations is associated with a rise in the production of non-methane volatile organic compounds (VOCs) including natural gas plant liquids (e.g., ethane, propane, and butanes) and liquid lease condensate (e.g., pentanes, hexanes, aromatics and cycloalkanes). Since 2010, the production of natural gas liquids and the amount of natural gas vented/flared has increased by factors of ~1.28 and 1.57, respectively (U.S. Energy and Information Administration), indicating an increasingly large potential source of hydrocarbons to the atmosphere. Emission of VOCs may affect local and regional air quality due to the potential to form tropospheric ozone and organic particles as well as from the release of toxic species such as benzene and toluene. The 2015 Shale Oil and Natural Gas Nexus (SONGNex) campaign studied emissions from oil and natural gas activities across the central United States in order to better understand their potential air quality and climate impacts. Here we present VOC measurements from 19 research flights aboard the NOAA WP-3D over 11 shale basins across 8 states. Non-methane hydrocarbons were measured using an improved whole air sampler (iWAS) with post-flight analysis via a custom-built gas chromatograph-mass spectrometer (GC-MS). The whole air samples are complimented by higher-time resolution measurements of methane (Picarro spectrometer), ethane (Aerodyne spectrometer), and VOCs (H3O+ chemical ionization mass spectrometer). Preliminary analysis show that the Permian Basin on the New Mexico/Texas border had the highest observed VOC mixing ratios for all basins studied. We will utilize VOC enhancement ratios to compare the composition of methane and VOC emissions for each basin and the associated reactivities of these gases with the hydroxyl radical, OH, as a proxy for potential ozone formation.

  1. Catalyst for Oxidation of Volatile Organic Compounds

    NASA Technical Reports Server (NTRS)

    Wood, George M. (Inventor); Upchurch, Billy T. (Inventor); Schryer, David R. (Inventor); Davis, Patricia P. (Inventor); Kielin, Erik J. (Inventor); Brown, Kenneth G. (Inventor); Schyryer, Jacqueline L. (Inventor); DAmbrosia, Christine M. (Inventor)

    2000-01-01

    Disclosed is a process for oxidizing volatile organic compounds to carbon dioxide and water with the minimal addition of energy. A mixture of the volatile organic compound and an oxidizing agent (e.g. ambient air containing the volatile organic compound) is exposed to a catalyst which includes a noble metal dispersed on a metal oxide which possesses more than one oxidation state. Especially good results are obtained when the noble metal is platinum, and the metal oxide which possesses more than one oxidation state is tin oxide. A promoter (i.e., a small amount of an oxide of a transition series metal) may be used in association with the tin oxide to provide very beneficial results.

  2. Organic Carbon Delivery to a High Arctic Watershed over the Late Holocene: Insights from Plant Biomarkers and Compound Specific δ13C and Δ14C Measurements

    NASA Astrophysics Data System (ADS)

    Schreiner, K. M.; Bianchi, T. S.; Eglinton, T. I.; Allison, M. A.

    2012-12-01

    The Colville River in Alaska is the largest river in North America which has a drainage basin that is exclusively underlain by permafrost, and as such provides a unique signal of historical changes in one of the world's most vulnerable areas to climate changes. Additionally, the Colville flows into Simpson's Lagoon, an area of the Alaskan Beaufort coast protected by a barrier island chain, lessening the impacts of Arctic storms and ice grounding on sediment mixing. Cores collected from the Colville river delta in August of 2010 were found to be composed of muddy, organic-rich, well-laminated sediments. The 2.5 to 3 meter length of each core spans about one to two thousand years of Holocene history, including the entire Anthropocene and much of the late Holocene. Two cores were sampled for this data set - one from close to the river mouth, and one from farther east in Simpson's Lagoon. Samples were taken every 2 cm for the entire length of both cores. In order to determine how the amount of terrestrial organic matter input changed over the Holocene, bulk analyses including percent organic carbon, percent nitrogen, and stable carbon isotopic analysis were performed, and biomarkers including lignin-phenols and fatty acids were measured. It was shown that lignin-phenol input is positively correlated with Alaskan North Slope temperature reconstructions. To determine whether the source of this increased terrestrial organic matter input was from fresh vegetation (for example, shrub encroachment onto tundra areas) or aged soil organic matter (potentially due to permafrost thawing and breakdown), selected samples were analyzed for compound-specific δ13C and Δ14C of fatty acids and lignin-phenols. These analyses show significant changes in carbon storage and in terrestrial carbon delivery to the Lagoon over time. These results represent the first fine-scale organic biomarker study in a high Arctic North American Lagoon, and have many implications for the future of carbon

  3. From emissions to ambient mixing ratios: online seasonal field measurements of volatile organic compounds over a Norway spruce-dominated forest in central Germany

    NASA Astrophysics Data System (ADS)

    Bourtsoukidis, E.; Williams, J.; Kesselmeier, J.; Jacobi, S.; Bonn, B.

    2014-07-01

    Biogenic volatile organic compounds (BVOCs) are substantial contributors to atmospheric chemistry and physics and demonstrate the close relationship between biosphere and atmosphere. Their emission rates are highly sensitive to meteorological and environmental changes with concomitant impacts on atmospheric chemistry. We have investigated seasonal isoprenoid and oxygenated VOC (oxVOC) fluxes from a Norway spruce (Picea abies) tree in central Germany and explored the emission responses under various atmospheric conditions. Emission rates were quantified by using dynamic branch enclosure and proton-transfer-reaction mass spectrometry (PTR-MS) techniques. Additionally, ambient mixing ratios were derived through application of a new box model treatment on the dynamic chamber measurements. These are compared in terms of abundance and origin with the corresponding emissions. Isoprenoids dominate the BVOC emissions from Norway spruce, with monoterpenes and sesquiterpenes accounting for 50.8 ± 7.2% and 19.8 ± 8.1% respectively of the total emissions. Normalizing the VOC emission rates, we have observed a trend of reduction of carbon-containing emissions from April to November, with an enhancement of oxVOC. Highest emission rates were observed in June for all measured species, with the exception of sesquiterpenes, which were emitted most strongly in April. Finally, we evaluate the temperature-dependent algorithm that seems to describe the temperature-dependent emissions of methanol, acetaldehyde and monoterpenes but only with the use of the monthly derived values for emission potential, Es, and temperature dependency, β factor.

  4. Nonaqueous battery with organic compound cathode

    SciTech Connect

    Yamaji, A.; Yamaki, J.

    1981-02-17

    A battery embodying this invention comprises: an anode including an anode-active material formed of one metal selected from the Group IA metals or preferably lithium metal; a cathode including a cathode-active material formed of metal or metal-free organic compounds having a phthalocyanine function or organic compounds having a porphin function; and an electrolyte prepared from a material which is chemically stable to the cathode and anode materials and permits the migration of the ion of the anode metal to the cathode for electrochemical reaction with the cathode-active material.

  5. Ambient air/near-field measurements of methane and Volatile Organic Compounds (VOCs) from a natural gas facility in Northern Europe

    NASA Astrophysics Data System (ADS)

    Baudic, Alexia; Gros, Valérie; Bonsang, Bernard; Baisnee, Dominique; Vogel, Félix; Yver Kwok, Camille; Ars, Sébastien; Finlayson, Andrew; Innocenti, Fabrizio; Robinson, Rod

    2015-04-01

    Since the 1970's, the natural gas consumption saw a rapid growth in large urban centers, thus becoming an important energy resource to meet continuous needs of factories and inhabitants. Nevertheless, it can be a substantial source of methane (CH4) and pollutants in urban areas. For instance, we have determined that about 20% of Volatile Organic Compounds (VOCs) in downtown Paris are originating from this emission source (Baudic, Gros et al., in preparation). Within the framework of the "Fugitive Methane Emissions" (FuME) project (Climate-KIC, EIT); 2-weeks gas measurements were conducted at a gas compressor station in Northern Europe. Continuous ambient air measurements of methane and VOCs concentrations were performed using a cavity ring-down spectrometer (model G2201, Picarro Inc., Santa Clara, USA) and two portable GC-FID (Chromatotec, Saint-Antoine, France), respectively. On-site near-field samplings were also carried out at the source of two pipelines using stainless steel flasks (later analyzed with a laboratory GC-FID). The objective of this study aims to use VOCs as additional tracers in order to better characterize the fugitive methane emissions in a complex environment, which can be affected by several urban sources (road-traffic, others industries, etc.). Moreover, these measurements have allowed determining the chemical composition of this specific source. Our results revealed that the variability of methane and some VOCs was (rather) well correlated, especially for alkanes (ethane, propane, etc.). An analysis of selected events with strong concentrations enhancement was performed using ambient air measurements; thus allowing the preliminary identification of different emission sources. In addition, some flasks were also sampled in Paris to determine the local natural gas composition. A comparison between both was then performed. Preliminary results from these experiments will be presented here.

  6. Volatile organic compound (VOC) emissions characterization during the flow-back phase of a hydraulically refractured well in the Uintah Basin, Utah using mobile PTR-MS measurements

    NASA Astrophysics Data System (ADS)

    Geiger, F.; Warneke, C.; Brown, S. S.; De Gouw, J. A.; Dube, W. P.; Edwards, P.; Gilman, J.; Graus, M.; Helleis, F.; Kofler, J.; Lerner, B. M.; Orphal, J.; Petron, G.; Roberts, J. M.; Zahn, A.

    2014-12-01

    Ongoing improvements in advanced technologies for crude oil and natural gas extraction from unconventional reserves, such as directional drilling and hydraulic fracturing, have greatly increased the production of fossil fuels within recent years. The latest forecasts even estimate an enhancement of 56% in total natural gas production due to increased development of shale gas, tight gas and offshore natural gas resources from 2012 to 2040 with the largest contribution from shale formations [US EIA: Annual Energy Outlook 2014]. During the field intensive 'Energy and Environment - Uintah Basin Winter Ozone Study (UBWOS)', measurements of volatile organic compounds (VOCs) were made using proton-transfer-reactions mass spectrometry (PTR-MS) at the ground site Horse Pool and using a mobile laboratory in the Uintah Basin, Utah, which is a region well known for intense fossil fuel production. A reworked gas well in the Red Wash fields was sampled regularly within two weeks performing mobile laboratory measurements downwind of the well site. The well had been recently hydraulically refractured at that time and waste water was collected into an open flow-back pond. Very high mixing ratios of aromatic hydrocarbons (C6-C13) up to the ppm range were observed coming from condensate and flow-back reservoirs. The measurements are used to determine sources of specific VOC emissions originating from the different parts of the well site and mass spectra are used to classify the air composition in contrast to samples taken at the Horse Pool field site and crude oil samples from South Louisiana. Enhancement ratios and time series of measured peak values for aromatics showed no clear trend, which indicates changes in emissions with operations at the site.

  7. Canopy-scale flux measurements and bottom-up emission estimates of volatile organic compounds from a mixed oak and hornbeam forest in northern Italy

    NASA Astrophysics Data System (ADS)

    Acton, W. Joe F.; Schallhart, Simon; Langford, Ben; Valach, Amy; Rantala, Pekka; Fares, Silvano; Carriero, Giulia; Tillmann, Ralf; Tomlinson, Sam J.; Dragosits, Ulrike; Gianelle, Damiano; Hewitt, C. Nicholas; Nemitz, Eiko

    2016-06-01

    This paper reports the fluxes and mixing ratios of biogenically emitted volatile organic compounds (BVOCs) 4 m above a mixed oak and hornbeam forest in northern Italy. Fluxes of methanol, acetaldehyde, isoprene, methyl vinyl ketone + methacrolein, methyl ethyl ketone and monoterpenes were obtained using both a proton-transfer-reaction mass spectrometer (PTR-MS) and a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) together with the methods of virtual disjunct eddy covariance (using PTR-MS) and eddy covariance (using PTR-ToF-MS). Isoprene was the dominant emitted compound with a mean daytime flux of 1.9 mg m-2 h-1. Mixing ratios, recorded 4 m above the canopy, were dominated by methanol with a mean value of 6.2 ppbv over the 28-day measurement period. Comparison of isoprene fluxes calculated using the PTR-MS and PTR-ToF-MS showed very good agreement while comparison of the monoterpene fluxes suggested a slight over estimation of the flux by the PTR-MS. A basal isoprene emission rate for the forest of 1.7 mg m-2 h-1 was calculated using the Model of Emissions of Gases and Aerosols from Nature (MEGAN) isoprene emission algorithms (Guenther et al., 2006). A detailed tree-species distribution map for the site enabled the leaf-level emission of isoprene and monoterpenes recorded using gas-chromatography mass spectrometry (GC-MS) to be scaled up to produce a bottom-up canopy-scale flux. This was compared with the top-down canopy-scale flux obtained by measurements. For monoterpenes, the two estimates were closely correlated and this correlation improved when the plant-species composition in the individual flux footprint was taken into account. However, the bottom-up approach significantly underestimated the isoprene flux, compared with the top-down measurements, suggesting that the leaf-level measurements were not representative of actual emission rates.

  8. EMISSION, FATE, AND CONTRIBUTION OF BIOGENIC VOLATILE ORGANIC COMPOUNDS TO ORGANIC AEROSOL FORMATION IN THE PRESENCE OF ANTHROPOGENIC POLLUTION: MEASUREMENTS AND MODELING DURING SOAS

    EPA Science Inventory

    The primary deliverable products will be measurements of VOC emission and deposition on spatial and temporal scales that are optimal for evaluating and improving regional models. Outcomes will include approaches for quantifying VOC emission uncertainties and identifying missing V...

  9. Chlorinated organic compounds in urban river sediments

    SciTech Connect

    Soma, Y.; Shiraishi, H.; Inaba, K.

    1995-12-31

    Among anthropogenic chemicals, many chlorinated organic compounds have been used as insecticides and detected frequently as contaminants in urban river sediments so far. However, the number and total amount of chemicals produced commercially and used are increasing year by year, though each amount of chemicals is not so high. New types of contaminants in the environment may be detected by the use of newly developed chemicals. Chlorinated organic compounds in the urban river sediments around Tokyo and Kyoto, large cities in Japan, were surveyed and recent trends of contaminants were studied. Contaminants of the river sediments in industrial areas had a variety, but PCB (polychlorinated biphenyls) was detected in common in industrial areas. Concentration of PCB related well to the number of factories on both sides of rivers, although the use of PCB was stopped 20 years ago. In domestic areas, Triclosan (5-chloro-2-(2,4-dichlorophenoxy)-phenol) and Triclocarban (3,4,4{prime}-trichlorocarbanilide)(both are contained in soap or shampoo for fungicides), p-dichlorobenzene (insecticides for wears) and TCEP(tris-chloroethyl phosphate) were detected. EOX(extracted organic halogen) in the sediments was 5 to 10 times of chlorinated organic compounds detected by GC/MS. Major part of organic halogen was suggested to be included in chlorinated organics formed by bleaching or sterilization.

  10. Catalytic Destruction Of Toxic Organic Compounds

    NASA Technical Reports Server (NTRS)

    Voecks, Gerald E.

    1990-01-01

    Proposed process disposes of toxic organic compounds in contaminated soil or carbon beds safely and efficiently. Oxidizes toxic materials without producing such other contaminants as nitrogen oxides. Using air, fuel, catalysts, and steam, system consumes less fuel and energy than decontamination processes currently in use. Similar process regenerates carbon beds used in water-treatment plants.

  11. Global Exposure Modelling of Semivolatile Organic Compounds

    NASA Astrophysics Data System (ADS)

    Guglielmo, F.; Lammel, G.; Maier-Reimer, E.

    2008-12-01

    Organic compounds which are persistent and toxic as the agrochemicals γ-hexachlorocyclohexane (γ-HCH, lindane) and dichlorodiphenyltrichloroethane (DDT) pose a hazard for the ecosystems. These compounds are semivolatile, hence multicompartmental substances and subject to long-range transport (LRT) in atmosphere and ocean. Being lipophilic, they accumulate in exposed organism tissues and biomagnify along food chains. The multicompartmental global fate and LRT of DDT and lindane in the atmosphere and ocean have been studied using application data for 1980, on a decadal scale using a model based on the coupling of atmosphere and (for the first time for these compounds) ocean General Circulation Models (ECHAM5 and MPI-OM). The model system encompasses furthermore 2D terrestrial compartments (soil and vegetation) and sea ice, a fully dynamic atmospheric aerosol (HAM) module and an ocean biogeochemistry module (HAMOCC5). Large mass fractions of the compounds are found in soil. Lindane is also found in comparable amount in ocean. DDT has the longest residence time in almost all compartments. The sea ice compartment locally almost inhibits volatilization from the sea. The air/sea exchange is also affected , up to a reduction of 35 % for DDT by partitioning to the organic phases (suspended and dissolved particulate matter) in the global oceans. Partitioning enhances vertical transport in the sea. Ocean dynamics are found to be more significant for vertical transport than sinking associated with particulate matter. LRT in the global environment is determined by the fast atmospheric circulation. Net meridional transport taking place in the ocean is locally effective mostly via western boundary currents, upon applications at mid- latitudes. The pathways of the long-lived semivolatile organic compounds studied include a sequence of several cycles of volatilisation, transport in the atmosphere, deposition and transport in the ocean (multihopping substances). Multihopping is

  12. Comparison of Lichen, Conifer Needles, Passive Air Sampling Devices, and Snowpack as Passive Sampling Media to Measure Semi-Volatile Organic Compounds in Remote Atmospheres

    PubMed Central

    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

  13. The photostabililty of prebiotic organic compounds on cometary dusts.

    NASA Astrophysics Data System (ADS)

    Saiagh, K.; Aleian, A.; Fray, N.; Cloix, M.; Cottin, H.

    2013-09-01

    A new methodology for measuring the photostability of organic compounds in extraterrestrial environments will be presented. It is based on Low Earth Orbit (LEO) and "classical" laboratory photolysis experiments, as well as on quantitative measurements of the VUV/UV ( < 300 nm) absorption cross section spectra. We will discuss the complementarily and limits of each approach, and discuss the astrobiological relevance of such studies in the frame of the importation of organic matter to Earth via micrometeorites.

  14. FIELD SCREENING FOR HALOGENATED VOLATILE ORGANIC COMPOUNDS

    SciTech Connect

    John F. Schabron; Joseph F. Rovani Jr.; Theresa M. Bomstad

    2002-06-01

    Western Research Institute (WRI) initiated exploratory work towards the development of new field screening methodology and a test kit to measure halogenated volatile organic compounds (VOCs) in the field. Heated diode and corona discharge sensors are commonly used to detect leaks of refrigerants from air conditioners, freezers, and refrigerators. They are both selective to the presence of carbon-halogen bonds. Commercially available heated diode and corona discharge leak detectors were procured and evaluated for halogenated VOC response. The units were modified to provide a digital readout of signal related to VOC concentration. Sensor response was evaluated with carbon tetrachloride and tetrachloroethylene (perchloroethylene, PCE), which represent halogenated VOCs with and without double bonds. The response characteristics were determined for the VOCs directly in headspace in Tedlar bag containers. Quantitation limits in air were estimated. Potential interferences from volatile hydrocarbons, such as toluene and heptane, were evaluated. The effect of humidity was studied also. The performance of the new devices was evaluated in the laboratory by spiking soil samples and monitoring headspace for halogenated VOCs. A draft concept of the steps for a new analytical method was outlined. The results of the first year effort show that both devices show potential utility for future analytical method development work towards the goal of developing a portable test kit for screening halogenated VOCs in the field.

  15. Volatile organic compound remedial action project

    SciTech Connect

    1991-12-01

    This Environmental Assessment (EA) reviews a proposed project that is planned to reduce the levels of volatile organic compound (VOC) contaminants present in the Mound domestic water supply. The potable and industrial process water supply for Mound is presently obtained from a shallow aquifer via on-site production wells. The present levels of VOCs in the water supply drawn from the on-site wells are below the maximum contaminant levels (MCLs) permissible for drinking water under Safe Drinking Water Act (SDWA; 40 CFR 141); however, Mound has determined that remedial measures should be taken to further reduce the VOC levels. The proposed project action is the reduction of the VOC levels in the water supply using packed tower aeration (PTA). This document is intended to satisfy the requirements of the National Environmental Policy Act (NEPA) of 1969 and associated Council on Environmental Quality regulations (40 CFR parts 1500 through 1508) as implemented through U.S. Department of Energy (DOE) Order 5440.1D and supporting DOE NEPA Guidelines (52 FR 47662), as amended (54 FR 12474; 55 FR 37174), and as modified by the Secretary of Energy Notice (SEN) 15-90 and associated guidance. As required, this EA provides sufficient information on the probable environmental impacts of the proposed action and alternatives to support a DOE decision either to prepare an Environmental Impact Statement (EIS) or issue a Finding of No Significant Impact (FONSI).

  16. Organic compounds in concrete from demolition works.

    PubMed

    Van Praagh, M; Modin, H; Trygg, J

    2015-11-01

    This study aims to verify the effect of physically removing the outer surface of contaminated concrete on total contents and on potential mobility of pollutants by means of leaching tests. Reclaimed concrete from 3 industrial sites in Sweden were included: A tar impregnated military storage, a military tar track-depot, as well as concrete constructions used for disposing of pesticide production surplus and residues. Solid materials and leachates from batch and column leaching tests were analysed for metals, Cl, F, SO4, DOC and contents of suspected organic compounds (polycyclic aromatic hydrocarbons, PAH, and pesticides/substances for pesticide production such as phenoxy acids, chlorophenols and chlorocresols, respectively). In case of PAH contaminated concrete, results indicate that removing 1 or 5 mm of the surface lead to total concentrations below the Swedish guidelines for recycling of aggregates and soil in groundwork constructions. 3 out of 4 concrete samples contaminated with pesticides fulfilled Swedish guidelines for contaminated soil. Results from batch and column leaching tests indicated, however, that concentrations above environmental quality standards for certain PAH and phenoxy acids, respectively, might occur at site when the crushed concrete is recycled in groundwork constructions. As leaching tests engaged in the study deviated from leaching test standards with a limited number of samples, the potential impact of the leaching tests' equipment on measured PAH and pesticide leachate concentrations has to be evaluated in future work. PMID:26164853

  17. Organic photosensitive devices using subphthalocyanine compounds

    DOEpatents

    Rand, Barry; Forrest, Stephen R.; Mutolo, Kristin L.; Mayo, Elizabeth; Thompson, Mark E.

    2011-07-05

    An organic photosensitive optoelectronic device, having a donor-acceptor heterojunction of a donor-like material and an acceptor-like material and methods of making such devices is provided. At least one of the donor-like material and the acceptor-like material includes a subphthalocyanine, a subporphyrin, and/or a subporphyrazine compound; and/or the device optionally has at least one of a blocking layer or a charge transport layer, where the blocking layer and/or the charge transport layer includes a subphthalocyanine, a subporphyrin, and/or a subporphyrazine compound.

  18. Effect of the Presence of Chlorates and Perchlorates on the Pyrolysis of Organic Compounds: Implications for Measurements Done with the SAM Experiment Onboard the Curiosity Rover

    NASA Technical Reports Server (NTRS)

    Millan, M.; Szopa, C.; Buch, A.; Belmahdi, I.; Coll, P.; Glavin, D. P.; Freissinet, C.; Archer, P. D., Jr.; Sutter, B.; Summons, R. E.; Mahaffy, P.

    2016-01-01

    The Mars Science Laboratory (MSL) Curiosity Rover carries a suite of instruments, one of which is the Sample Analysis at Mars (SAM) experiment. SAM is devoted to the in situ molecular analysis of gases evolving from solid samples collected by Curiosity on Mars surface/sub-surface. Among its three analytical devices, SAM has a gaschromatograph coupled to a quadrupole mass spectrometer (GC-QMS). The GC-QMS is devoted to the separation and identification of organic and inorganic material. Before proceeding to the GC-QMS analysis, the solid sample collected by Curiosity is subjected to a thermal treatment thanks to the pyrolysis oven to release the volatiles into the gas processing system. Depending on the sample, a derivatization method by wet chemistry: MTBSTFA of TMAH can also be applied to analyze the most refractory compounds. The GC is able to separate the organic molecules which are then detected and identified by the QMS (Figure 1). For the second time after the Viking landers in 1976, SAM detected chlorinated organic compounds with the pyrolysis GC-QMS experiment. The detection of perchlorates salts (ClO4-) in soil at the Phoenix Landing site suggests that the chlorohydrocarbons detected could come from the reaction of organics with oxychlorines. Indeed, laboratory pyrolysis experiments have demonstrated that oxychlorines decomposed into molecular oxygen and volatile chlorine (HCl and/or Cl2) when heated which then react with the organic matter in the solid samples by oxidation and/or chlorination processes.

  19. Kinetics of desorption of organic compounds from dissolved organic matter.

    PubMed

    Kopinke, Frank-Dieter; Ramus, Ksenia; Poerschmann, Juergen; Georgi, Anett

    2011-12-01

    This study presents a new experimental technique for measuring rates of desorption of organic compounds from dissolved organic matter (DOM) such as humic substances. The method is based on a fast solid-phase extraction of the freely dissolved fraction of a solute when the solution is flushed through a polymer-coated capillary. The extraction interferes with the solute-DOM sorption equilibrium and drives the desorption process. Solutes which remain sorbed to DOM pass through the extraction capillary and can be analyzed afterward. This technique allows a time resolution for the desorption kinetics from subseconds up to minutes. It is applicable to the study of interaction kinetics between a wide variety of hydrophobic solutes and polyelectrolytes. Due to its simplicity it is accessible for many environmental laboratories. The time-resolved in-tube solid-phase microextraction (TR-IT-SPME) was applied to two humic acids and a surfactant as sorbents together with pyrene, phenanthrene and 1,2-dimethylcyclohexane as solutes. The results give evidence for a two-phase desorption kinetics: a fast desorption step with a half-life of less than 1 s and a slow desorption step with a half-life of more than 1 min. For aliphatic solutes, the fast-desorbing fraction largely dominates, whereas for polycyclic aromatic hydrocarbons such as pyrene, the slowly desorbing, stronger-bound fraction is also important. PMID:22035249

  20. Volatile organic compound sources for Southern Finland

    NASA Astrophysics Data System (ADS)

    Patokoski, Johanna; Ruuskanen, Taina M.; Kajos, Maija K.; Taipale, Risto; Rantala, Pekka; Aalto, Juho; Ryyppö, Timo; Hakola, Hannele; Rinne, Janne

    2014-05-01

    Volatile organic compounds (VOCs) have several sources, both biogenic and anthropogenic. Emissions of biogenic VOCs in a global scale are estimated to be an order of magnitude higher than anthropogenic ones. However, in densely populated areas and during winter time the anthropogenic VOC emissions dominate over the biogenic ones. The aim of this study was to clarify potential local sources and source areas of VOCs in different seasons. Diurnal behaviour in winter and spring were also compared at two different sites in Finland: SMEAR II and III (Station for Measuring Ecosystem - Atmosphere Relations). SMEAR II is a rural site located in Hyytiälä in Southern Finland 220 km North-West from Helsinki whereas SMEAR III is background urban site located 5 km from the downtown of Helsinki. The volume mixing ratios of VOCs were measured with a proton-transfer-reaction mass spectrometer (PTR-MS, Ionicon Analytik GmbH, Austria) during years 2006-2011. Other trace gases such as CO, NOXand SO2 were also measured in both sites and used for source analysis. Source areas for long term VOC measurements were investigated with trajectory analysis and sources for local and regional concentrations were determined by Unmix multivariate receptor model. Forest fires affect air quality and the biggest smoke plumes can be seen in satellite images and even hinder visibility in the plume areas. They provide temporally and spatially well-defined sources that can be used to verify source area estimates. During the measurement periods two different forest fire episodes with several hotspots, happened in Russia. Forest fires which showed up in these measurements were in 2006 near the border of Finland in Vyborg area and 2010 in Moscow area. Forest fire episodes were clearly observed in trajectory analysis for benzene, toluene and methanol and also CO and NOX. In addition to event sources continuous source areas were determined. Anthropogenic local sources seemed to be dominant during winter in

  1. Well-purging criteria for sampling purgeable organic compounds

    USGS Publications Warehouse

    Gibs, J.; Imbrigiotta, T.E.

    1990-01-01

    The results indicate that 1) purgeable organic compound concentrations stabilized when three casing volume were purged in only 55% of the cases evaluated in this study, 2) purgeable organic compounds concentrations did not consistently follow the temporal variation of, nor stabilize at the same time as, the measure field characteristics, and 3) purging to achieve hydraulic equilibrium between casing and aquifer water consistently underestimated the time and casing volumes needed to achieve stable values of water-quality measurements in highly transmissive aquifers. The conclusion from these data is that none of the previously recommended criteria for purging a well can be applied reliably to collecting a "representative' sample of purgeable organic compounds. These results indicate that the criteria for purging a well prior to sampling for purgeable organic compounds must take into account other factors, such as the unique hydrogeologic characteristics of a site, the nature and extent of purgeable organic compounds present, and areal extent of the contamination, the well construction, and the sampling objectives of the investigation. -from Authors

  2. High Arctic Biogenic Volatile Organic Compound emissions

    NASA Astrophysics Data System (ADS)

    Schollert, Michelle; Buchard, Sebrina; Faubert, Patrick; Michelsen, Anders; Rinnan, Riikka

    2013-04-01

    Biogenic volatile organic compounds (BVOCs) emitted from terrestrial vegetation participate in oxidative reactions, affecting the tropospheric ozone concentration and the lifetimes of greenhouse gasses such as methane. Also, they affect the formation of secondary organic aerosols. BVOCs thus provide a strong link between the terrestrial biosphere, the atmosphere and the climate. Global models of BVOC emissions have assumed minimal emissions from the high latitudes due to low temperatures, short growing seasons and sparse vegetation cover. However, measurements from this region of the world are lacking and emissions from the High Arctic have not been published yet. The aim of this study was to obtain the first estimates for BVOC emissions from the High Arctic. Hereby, we wish to add new knowledge to the understanding of global BVOC emissions. Measurements were conducted in NE Greenland (74°30' N, 20°30' W) in four vegetation communities in the study area. These four vegetation communities were dominated by Cassiope tetragona, Salix arctica, Vaccinium uliginosum and Kobresia myosuroides/Dryas octopetela/Salix arctica, respectively. Emissions were measured by enclosure technique and collection of volatiles into adsorbent cartridges in August 2009. The volatiles were analyzed by gas chromatography-mass spectrometry following thermal desorption. Isoprene showed highest emissions in S. arctica-dominated heath, where it was the dominant single BVOC. However, isoprene emission decreased below detection limit in the end of August when the temperature was at or below 10°C. According to a principal component analysis, monoterpene and sesquiterpene emissions were especially associated with C. tetragona-dominated heath. Especially S. arctica and C. tetragona dominated heaths showed distinct patterns of emitted BVOCs. Emissions of BVOC from the studied high arctic heaths were clearly lower than the emissions observed previously in subarctic heaths with more dense vegetation

  3. Late stage trifluoromethylthiolation strategies for organic compounds.

    PubMed

    Barata-Vallejo, Sebastian; Bonesi, Sergio; Postigo, Al

    2016-07-26

    Substitution by the CF3S group allows for an increase in lipophilicity and electron-withdrawing properties along with an improvement in the bioavailability of medicinal targets; consequently, the late stage introduction of CF3S moieties into medicinal scaffolds is a sought-after strategy in synthetic organic chemistry. Different newly-developed electrophilic and nucleophilic reagents are used to effect the trifluoromethylthiolation of (hetero)aromatic compounds, aliphatic compounds (alkyl, alkenyl, alkynyl substrates), the trifluoromethylthiolation at the α- and β-carbonyl positions, and heteroatoms (N- and S-). Such reactions can involve homolytic substitutions, or functional-group substitutions (ipso). Addition reactions of electrophilic reagents to double and triple bonds followed by ring-cyclizations will be shown to yield relevant CF3S-substituted heteroaromatic compounds with relevant pharmacological action. PMID:27354317

  4. Quantifying commuter exposures to volatile organic compounds

    NASA Astrophysics Data System (ADS)

    Kayne, Ashleigh

    Motor-vehicles can be a predominant source of air pollution in cities. Traffic-related air pollution is often unavoidable for people who live in populous areas. Commuters may have high exposures to traffic-related air pollution as they are close to vehicle tailpipes. Volatile organic compounds (VOCs) are one class of air pollutants of concern because exposure to VOCs carries risk for adverse health effects. Specific VOCs of interest for this work include benzene, toluene, ethylbenzene, and xylenes (BTEX), which are often found in gasoline and combustion products. Although methods exist to measure time-integrated personal exposures to BTEX, there are few practical methods to measure a commuter's time-resolved BTEX exposure which could identify peak exposures that could be concealed with a time-integrated measurement. This study evaluated the ability of a photoionization detector (PID) to measure commuters' exposure to BTEX using Tenax TA samples as a reference and quantified the difference in BTEX exposure between cyclists and drivers with windows open and closed. To determine the suitability of two measurement methods (PID and Tenax TA) for use in this study, the precision, linearity, and limits of detection (LODs) for both the PID and Tenax TA measurement methods were determined in the laboratory with standard BTEX calibration gases. Volunteers commuted from their homes to their work places by cycling or driving while wearing a personal exposure backpack containing a collocated PID and Tenax TA sampler. Volunteers completed a survey and indicated if the windows in their vehicle were open or closed. Comparing pairs of exposure data from the Tenax TA and PID sampling methods determined the suitability of the PID to measure the BTEX exposures of commuters. The difference between BTEX exposures of cyclists and drivers with windows open and closed in Fort Collins was determined. Both the PID and Tenax TA measurement methods were precise and linear when evaluated in the

  5. A Laboratory Experiment To Measure Henry's Law Constants of Volatile Organic Compounds with a Bubble Column and a Gas Chromatography Flame Ionization Detector (GC-FID)

    ERIC Educational Resources Information Center

    Lee, Shan-Hu; Mukherjee, Souptik; Brewer, Brittany; Ryan, Raphael; Yu, Huan; Gangoda, Mahinda

    2013-01-01

    An undergraduate laboratory experiment is described to measure Henry's law constants of organic compounds using a bubble column and gas chromatography flame ionization detector (GC-FID). This experiment is designed for upper-division undergraduate laboratory courses and can be implemented in conjunction with physical chemistry, analytical…

  6. Organic compounds in star forming regions.

    PubMed

    Kochina, O; Wiebe, D

    2014-09-01

    The influence of complex dust composition on the general chemical evolution of a prestellar core and the content of complex organic compounds is studied. It is shown that various component groups respond differently to the presence of a small dust population. At early stages the difference is determined primarily by changes in the balance of photo processes due to effective absorption of ultraviolet photons by small dust grains of the second population and collisional reactions with dust particles. At later stages differences are also caused by the growing dominance of additional reaction channels related to surface organic synthesis. PMID:25515345

  7. Metabolic Reactions among Organic Sulfur Compounds

    NASA Technical Reports Server (NTRS)

    Schulte, M.; Rogers, K.

    2005-01-01

    Sulfur is central to the metabolisms of many organisms that inhabit extreme environments. Numerous authors have addressed the energy available from a variety of inorganic sulfur redox pairs. Less attention has been paid, however, to the energy required or gained from metabolic reactions among organic sulfur compounds. Work in this area has focused on the oxidation of alkyl sulfide or disulfide to thiol and formaldehyde, e.g. (CH3)2S + H2O yields CH3SH + HCHO + H2, eventually resulting in the formation of CO2 and SO4(-2). It is also found that reactions among thiols and disulfides may help control redox disequilibria between the cytoplasm and the periplasm. Building on our earlier efforts for thiols, we have compiled and estimated thermodynamic properties for alkyl sulfides. We are investigating metabolic reactions among various sulfur compounds in a variety of extreme environments, ranging from sea floor hydrothermal systems to organic-rich sludge. Using thermodynamic data and the revised HKF equation of state, along with constraints imposed by the geochemical environments sulfur-metabolizing organisms inhabit, we are able to calculate the amount of energy available to these organisms.

  8. Compositional space boundaries for organic compounds.

    PubMed

    Lobodin, Vladislav V; Marshall, Alan G; Hsu, Chang Samuel

    2012-04-01

    An upper elemental compositional boundary for fossil hydrocarbons has previously been established as double-bond equivalents (i.e., DBE = rings plus double bonds) not exceeding 90% of the number of carbons. For heteroatom-containing fossil compounds, the 90% rule still applies if each N atom is counted as a C atom. The 90% rule eliminates more than 10% of the possible elemental compositions at a given mass for fossil database molecules. However, some synthetic compounds can fall outside the upper boundary defined for naturally occurring compounds. Their inclusion defines an "absolute" upper boundary as DBE (rings plus double bonds to carbon) equal to carbon number plus one, and applies to all organic compounds including fullerenes and other molecules containing no hydrogen. Finally, the DBE definition can fail for molecules with particular atomic valences. Therefore, we also present a generalized DBE definition that includes atomic valence to enable calculation of the correct total number of rings, double bonds, and triple bonds for heteroatom-containing compounds. PMID:22376063

  9. Quantifying commuter exposures to volatile organic compounds

    NASA Astrophysics Data System (ADS)

    Kayne, Ashleigh

    Motor-vehicles can be a predominant source of air pollution in cities. Traffic-related air pollution is often unavoidable for people who live in populous areas. Commuters may have high exposures to traffic-related air pollution as they are close to vehicle tailpipes. Volatile organic compounds (VOCs) are one class of air pollutants of concern because exposure to VOCs carries risk for adverse health effects. Specific VOCs of interest for this work include benzene, toluene, ethylbenzene, and xylenes (BTEX), which are often found in gasoline and combustion products. Although methods exist to measure time-integrated personal exposures to BTEX, there are few practical methods to measure a commuter's time-resolved BTEX exposure which could identify peak exposures that could be concealed with a time-integrated measurement. This study evaluated the ability of a photoionization detector (PID) to measure commuters' exposure to BTEX using Tenax TA samples as a reference and quantified the difference in BTEX exposure between cyclists and drivers with windows open and closed. To determine the suitability of two measurement methods (PID and Tenax TA) for use in this study, the precision, linearity, and limits of detection (LODs) for both the PID and Tenax TA measurement methods were determined in the laboratory with standard BTEX calibration gases. Volunteers commuted from their homes to their work places by cycling or driving while wearing a personal exposure backpack containing a collocated PID and Tenax TA sampler. Volunteers completed a survey and indicated if the windows in their vehicle were open or closed. Comparing pairs of exposure data from the Tenax TA and PID sampling methods determined the suitability of the PID to measure the BTEX exposures of commuters. The difference between BTEX exposures of cyclists and drivers with windows open and closed in Fort Collins was determined. Both the PID and Tenax TA measurement methods were precise and linear when evaluated in the

  10. Chemical Composition of Semivolatile Compounds and Organic Aerosol in a Pine Forest: Bulk and Speciated Measurements by In-situ TAG-AMS and Offline GCxGC/HRTOFMS at BEACHON-RoMBAS 2011

    NASA Astrophysics Data System (ADS)

    Chan, A. W.; Kreisberg, N. M.; Zhao, Y.; Hohaus, T.; Campuzano Jost, P.; Teng, A.; Huang, I.; Jayne, J.; Worsnop, D. R.; Jimenez, J. L.; Hering, S. V.; Goldstein, A. H.

    2012-12-01

    Semivolatile organic compounds (SVOCs) represent an important source of organic aerosol (OA) in remote forested regions. Understanding their composition is essential to identifying their sources and processing, but the chemical complexity often limits such analysis. Here we present concurrent bulk and speciated measurements of semivolatile and particle-phase organic compounds using a novel combined instrument (TAG-AMS) at Manitou Forest, CO during the BEACHON-RoMBAS 2011 campaign. The Thermal desorption Aerosol Gas chromatograph (TAG) provides on-line organic speciation of ambient SVOCs with bihourly time resolution, while the AMS provides bulk mass spectral analysis of the concurrent OA sample. This deployment was a unique and experimental version of the TAG-AMS instrument, with a prototype filter cell designed to quantitatively collect and analyze SVOCs. The combined instrument provides quantitative measurements of organic and inorganic mass loadings, and elemental and PMF analysis of the bulk OA, simultaneously with detailed organic speciation of SVOCs. Additionally, filter samples are analyzed by comprehensive GCxGC/HR-TOF-MS to assist in compound identification by TAG. The system provided around-the-clock measurements for a 2-week period. Online and offline measurements reveal > 100 compounds, a subset of which is observed at a bihourly time resolution, and is used to identify the sources of organic aerosol in the region. Bihourly measurements of sesquiterpenes, which represent a major fraction of observed SVOCs, are used to investigate their emission sources and subsequent processing into OA. These observations are also compared to a previous study conducted at a similar pine forest in California.