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Indoor/outdoor measurements of volatile organic compounds in the Kanawha Valley of West Virginia.

The Kanawha Valley region of West Virginia which is comprised of Charleston and surrounding communities is the center of a heavily industrialized area known for its chemical manufacturing. As part of a larger study designed to investigate the impact of the chemical industry on human exposures to volatile organic compounds (VOC), a study of the relationship between indoor and outdoor concentrations was conducted. Thirty-five homes were selected for monitoring from among volunteers; approximately ten in each of three distinct population-industry centers and four outside the Valley to act as controls. Monitoring was performed using passive, badge samplers with a three-week monitoring period. Two separate questionnaires were administered: one for characterization of the residence; and one to characterize source use during monitoring. Participants were also asked to keep a record of their activities with respect to in-home, outdoors and other indoor environments. Analysis of the samplers was performed by solvent extraction followed by gas chromatography using a flame-ionization detector. Results suggest that indoor VOC concentrations are higher than outdoor concentrations. Additionally, certain ventilation-related parameters were identified that afforded some predictive power for indoor concentrations. No statistically significant differences between regions were identified.

Air Pollutants, Occupational↗

Simulating the emission rate of volatile organic compounds from a quiescent water surface: model development and feasibility evaluation.

Organic solvents are commonly used in industrial manufacturing processes, resulting in large quantities of volatile organic compounds (VOCs) emitted from effluent wastewater treatment facilities. This work presents a novel stainless steel simulator designed for developing a model that estimates VOC emission rates from a quiescent water surface in an open/unaerated basin. The target pollutants were aqueous VOCs: alcohols (ethanol and iso-propanol) and methyl ethyl ketone. Two aromatic hydrocarbons, toluene and benzene, were also used and each mixed with ethanol. A formula, based on penetration theory and the concept of mass balance, was devised for simulating emission rates (N), with the following variables: wind velocity (W) above the air-water interface with a power number of beta, the VOC concentration (Cg*) at equilibrium with aqueous concentration (CL), and the emitted concentration (Cg). Restated, N = kWbetaAS(Cg*-Cg), where k and beta denote dimensionless constants, which were solved herein, and As represents the emission surface area. From the proposed formula, three parameters (CL, water temperature, and W) were controlled during each simulation test to derive k and beta values. To assess the feasibility of the simulation procedures for real water with multiple VOC compositions, a large open neutralization basin was used to measure the VOC emission rate. Comparing the calculated results, respectively using the proposed formula and emission model Water 8 developed by the U.S. EPA in 1985, confirmed that the proposed simulation method was a feasible alternative to Water 8.

Air Pollutants↗

Source apportionment modeling of volatile organic compounds in streams.

It often is of interest to understand the relative importance of the different sources contributing to the concentration c(w) of a contaminant in a stream; the portions related to sources 1, 2, 3, etc. are denoted c(w,1), c(w2), c(w3), etc. Like c(w), the fractions alpha1 = c(w,1)/c(w), alpha2 = c(w,2)/c(w), alpha3 = c(w,3)/c(w), etc. depend on location and time. Volatile organic compounds (VOCs) can undergo absorption from the atmosphere into stream water or loss from stream water to the atmosphere, causing complexities affecting the source apportionment (SA) of VOCs in streams. Two SA rules are elaborated. Rule 1: VOC entering a stream across the air/water interface exclusively is assigned to the atmospheric portion of c(w). Rule 2: VOC loss by volatilization, flow loss to groundwater, in-stream degradation, etc. is distributed over c(w,1), c(w,2), c(w3), etc. in proportion to their corresponding alpha values. How the two SA rules are applied, as well as the nature of the SA output for a given case, will depend on whether transport across the air/water interface is handled using the net flux F convention or using the individual fluxes J convention. Four hypothetical stream cases involving acetone, methyl-tert-butyl ether (MTBE), benzene, chloroform, and perchloroethylene (PCE) are considered. Acetone and MTBE are sufficiently water soluble from air for a domestic atmospheric source to be capable of yielding c(w) values approaching the common water quality guideline range of 1 to 10 microg/L. For most other VOCs, such levels cause net outgassing (F > 0). When F > 0 in a given section of stream, in the net flux convention, all of the alpha(j) for the compound remain unchanged over that section while c(w) decreases. A characteristic time tau(d) can be calculated to predict when there will be differences between SA results obtained by the net flux convention versus the individual fluxes convention. Source apportionment modeling provides the framework necessary for comparing different strategies for mitigating contamination at points of interest along a stream.

Acetone↗

Determination of volatile organic compounds pollution sources in malaysian drinking water using multivariate analysis.

A field investigation was conducted at all water treatment plants throughout 11 states and Federal Territory in Peninsular Malaysia. The sampling points in this study include treatment plant operation, service reservoir outlet and auxiliary outlet point at the water pipelines. Analysis was performed by solid phase micro-extraction technique with a 100 microm polydimethylsiloxane fibre using gas chromatography with mass spectrometry detection to analyse 54 volatile organic compounds (VOCs) of different chemical families in drinking water. The concentration of VOCs ranged from undetectable to 230.2 microg/l. Among all of the VOCs species, chloroform has the highest concentration and was detected in all drinking water samples. Average concentrations of total trihalomethanes (THMs) were almost similar among all states which were in the range of 28.4--33.0 microg/l. Apart from THMs, other abundant compounds detected were cis and trans-1,2-dichloroethylene, trichloroethylene, 1,2-dibromoethane, benzene, toluene, ethylbenzene, chlorobenzene, 1,4-dichlorobenzene and 1,2-dichloro - benzene. Principal component analysis (PCA) with the aid of varimax rotation, and parallel factor analysis (PARAFAC) method were used to statistically verify the correlation between VOCs and the source of pollution. The multivariate analysis pointed out that the maintenance of auxiliary pipelines in the distribution systems is vital as it can become significant point source pollution to Malaysian drinking water.

Chloroform↗

Accumulation and effect of volatile organic compounds in closed life support systems.

Bioregenerative life support systems (BLSS) being considered for long duration space missions will operate with limited resupply and utilize biological systems to revitalize the atmosphere, purify water, and produce food. The presence of man-made materials, plant and microbial communities, and human activities will result in the production of volatile organic compounds (VOCs). A database of VOC production from potential BLSS crops is being developed by the Breadboard Project at Kennedy Space Center. Most research to date has focused on the development of air revitalization systems that minimize the concentration of atmospheric contaminants in a closed environment. Similar approaches are being pursued in the design of atmospheric revitalization systems in bioregenerative life support systems. in a BLSS one must consider the effect of VOC concentration on the performance of plants being used for water and atmospheric purification processes. In addition to phytotoxic responses, the impact of removing biogenic compounds from the atmosphere on BLSS function needs to be assessed. This paper provides a synopsis of criteria for setting exposure limits, gives an overview of existing information, and discusses production of biogenic compounds from plants grown in the Biomass Production Chamber at Kennedy Space Center.

Air Conditioning↗

Vertical and horizontal variability of volatile organic compounds in homes in Eastern Germany.

A German study on Indoor Factors and Genetics in Asthma (INGA) will be conducted for 10 years in towns of Eastern and Western Germany. The study will include an indoor and outdoor exposure assessment of BTEX (BTEX=benzene, toluene, ethyl benzene, ortho-xylene, and meta- plus para-xylene) volatile organic compounds (VOCs). In a pilot study, which was conducted in Erfurt, a city in Eastern Germany, during the winter of 1994, vertical and horizontal variabilities of BTEX concentrations within the homes were examined in detail. Passive sampling was conducted in the living room (at 0.7, 1.2, and 2.0 m height), bedroom (2 m), kitchen (2 m), and outside the window of the living room, in 20 homes of randomly chosen adults. The 20 houses consisted often old concrete constructions ('Altneubauten'=OLD, constructed between 1960 and 1970) and ten new concrete constructions ('Neubauten'=NEW, constructed between 1970 and 1980). At each apartment, Organic Vapour Monitor (OVM) 3500 passive sampling devices (3M Company) were exposed for 7 days. After elution with carbon disulfide (CS2), the samples were analyzed with dual column gas chromatography (GC) with flame ionization detector (FID). No significant differences between the median values of the weekly average air concentrations of the BTEX VOCs in the different heights of measurement in the living rooms could be detected. Kitchen and living room median BTEX concentrations were equal and both significantly higher than the bedroom concentrations (except benzene). The indoor BTEX air concentrations were significantly higher than the outdoor concentrations (except benzene). Significant differences in BTEX indoor concentrations between OLD and NEW buildings could not be detected (except toluene).

Adult↗

The use of multiple-strain algal sensor chips for the detection and identification of volatile organic compounds.

Although biosensors detecting a great variety of toxicants have been developed during the last decades, the simultaneous detection and identification of several targets by one biosensor is not possible in the majority of the biosensor systems. In our study we proved the concept of the detection and identification of two different volatile toxic compounds with a non-selective biochip-based algal biosensor. For that purpose we produced array plate biochips to utilise three membrane-immobilised algal strains of genus Klebsormidium and Chlorella in one biosensor system. A novel IMAGING-PAM chlorophyll fluorometer was applied to measure the impact of volatile organic compounds (VOC) on photosynthesis of chip-immobilized algae in terms of quantum efficiency of electron transport (DeltaF/F'm). Formaldehyde (FA) vapour was detectable with statistical significance in concentrations relevant to human health from 10 ppb to 10 ppm. The biosensor response recorded within minutes was concentration-dependent and reversible. Moreover, vapours of formaldehyde (0.05-1 ppm) and methanol (MeOH) (200-1000 ppm) were significantly identified by the compound-specific response rate as a quotient of the biosensor responses of the respective algal strains. Using the IMAGING-PAM chlorophyll fluorometer, data sampling proved to be highly efficient. Based on our results we conclude that the principle of the algal sensor chip (ASC) suggests further research on the detection and identification of VOCs and other toxic substances in gaseous environment with that biochip system.

Biosensing Techniques↗

Rapid detection of meat spoilage by measuring volatile organic compounds by using proton transfer reaction mass spectrometry.

The evolution of the microbial spoilage population for air- and vacuum-packaged meat (beef and pork) stored at 4 degrees C was investigated over 11 days. We monitored the viable counts (mesophilic total aerobic bacteria, Pseudomonas spp., Enterobacteriaceae, lactic acid bacteria, and Enterococcus spp.) by the microbiological standard technique and by measuring the emission of volatile organic compounds (VOCs) with the recently developed proton transfer reaction mass spectrometry system. Storage time, packaging type, and meat type had statistically significant (P < 0.05) effects on the development of the bacterial numbers. The concentrations of many of the measured VOCs, e.g., sulfur compounds, largely increased over the storage time. We also observed a large difference in the emissions between vacuum- and air-packaged meat. We found statistically significant strong correlations (up to 99%) between some of the VOCs and the bacterial contamination. The concentrations of these VOCs increased linearly with the bacterial numbers. This study is a first step toward replacing the time-consuming plate counting by fast headspace air measurements, where the bacterial spoilage can be determined within minutes instead of days.

Bacteria↗

Determination of complex mixtures of volatile organic compounds in ambient air: canister methodology.

Canister methodology is applicable to 150 polar and nonpolar VOCs found in ambient air from parts-per-billion by volume (ppbv) to parts-per-million (ppmv) levels, and has been validated at parts-per-trillion (pptv) levels for a subset of these analytes. This article is a detailed review of techniques related to the collection of volatile organic compounds (VOCs) in evacuated Summa and fused-silica-lined canisters, and their analysis by gas chromatography/mass spectrometry (GC/MS). Emphasis is placed on canister cleaning, VOC stability in canisters, sample dilution, water management, and VOC cryogenic and sorbent preconcentration methods. A wide range of VOC preconcentration and water management methods are identified from the literature, and their relative merits and disadvantages are discussed. Examples of difficulties that commonly arise when processing canister samples are illustrated, and solutions to these problems are provided.

Air Pollutants↗

Survey of volatile organic compounds found in indoor and outdoor air samples from Japan.

Indoor air quality is currently a growing concern, mainly due to the incidence of sick building syndrome and building related illness. To better understand indoor air quality in Japan, both indoor and outdoor air samples were collected from 50 residences in Iwate, Yamanashi, Shiga, Hyogo, Kochi and Fukuoka Prefectures. More than 100 volatile organic compounds (VOCs) were analyzed by thermal desorption-gas chromatography/mass spectrometry method. The most abundant class of compounds present in the indoor air samples were identified (i.e. alkanes, alkylbenzenes and terpenes). For 30% of the indoor air samples, the sum of each VOC exceeded the current provisional guideline value for total VOC (TVOC, 400 microg/m3). The major component of these samples included linear and branched-chain alkanes (possibly derived from fossil fuels), 1,4-dichlorobenzene (a moth repellent), alpha-pinene (emission from woody building materials) and limonene (probably derived from aroma products). As an unexpected result, one residence was polluted with an extremely high concentration of 1,1,1,2-tetrafluoroethane (720 microg/m3), suggesting accidental leakage from a household appliance such as a refrigerator. The results presented in this paper are important in establishing the Japanese target compound list for TVOC analysis, as well as defining the current status of indoor air quality in Japan.

Air↗

Use of new generation poly(styrene-divinylbenzene) resins for gas-phase trapping-thermal desorption. Application to the retention of seven volatile organic compounds.

Two new generation polymeric resins, Bond Elut ENV (styrene-divinylbenzene) from Varian and LiChrolut EN (ethylvinylbenzene-divinylbenzene) from Merck, commonly used in liquid--solid-phase extraction (SPE) were evaluated as sorbents for gas-phase sampling followed by thermal desorption and compared to Tenax TA, a reference sorbent in this kind of applications. The three resins were tested against seven volatile organic compounds (VOCs): 1-octene, ethylbenzene, (p-, m-, o-)xylenes, styrene and 1,4-dichlorobenzene. Elution curves for all compounds were determined at temperatures from 120 to 180 degrees C, and from such curves, different parameters, such as retention factor (k), distribution coefficient (K), height equivalent to a theoretical plate (H), asymmetry factor (Fa) and breakthrough volume (VB) were calculated and extrapolated at room (25 degrees C) and desorption (220 degrees C) temperatures in order to estimate breakthrough and elution volumes. In average, retention in LiChrolut EN is 10 and 200 times stronger than in Bond Elut ENV and Tenax TA, respectively, but its chromatographic behavior is rather poor giving quite asymmetric elution profiles (Fa >1.8 at 120 degrees C). Bond Elut ENV exhibited the best chromatographic behavior, with H values two or five times lower than those of LiChrolut EN or Tenax TA. An additional advantage of the new sorbents is that retention decreases with T much faster than it does in Tenax (8 or 20 times for Bond Elut ENV or LiChrolut EN). Modeling has finally shown that beds with 60-80 (for Bond Elut ENV) or 300-400 (for LiChrolut EN) times less of sorbent have the same retention properties than standard Tenax TA tubes and similar (LiChrolut EN) or five to six times smaller (Bond Elut ENV) elution volumes. These predictions have been experimentally confirmed.

Organic Chemicals↗

Evaluation of ozone-nitrogen oxides-volatile organic compound sensitivity of Cincinnati, Ohio.

Ambient concentrations of ozone (O3), nitrogen oxides (NOx), total reactive nitrogen (NOy), nitric acid (HNO3), and hydrogen peroxide (H2O2) were measured during September 2003 at an urban site of Cincinnati, OH. The aim of this study was two-fold: to investigate whether O3 formation in this population exposure-type site is NOx, sensitive or volatile organic compound (VOC) sensitive and to test the practicality of using two combined observational-based methods to identify the sensitivity of O3 formation in midlevel polluted locations. The evaluation of the indicator species: NOy, O3/NOy, O3/HNO3, H2O2/ HNO3, and O3/(estimated NOx reaction products), as well as the combined hypothesis testing analysis of the weekend/weekday (WE/WD) differences of 1-hr and 8-hr average maximum O3 and of the 6:00 a.m.-9:00 a.m. average nitric oxide and NOx concentrations, show evidence that Cincinnati is likely VOC sensitive. Average WE 1-hr and 8-hr maximum O3, as well as duration of WE O3 accumulation, were not lower than the corresponding WD levels in spite of the observed significant reduction in NO, emissions on WE, a typical situation in VOC-sensitive locations. The possibility that the seasonal transition from summer to autumn could have influenced the results was also investigated through an exploratory analysis of the afternoon O3 maximum/NOx measured and of the WE/WD differences of peak O3 and morning average NO and NO, concentrations observed at this site from June through September 2003. The results suggest that a VOC-sensitive chemistry regime dominated along the summer season. The findings of this study suggest that additional reductions in regional NO, emissions in Cincinnati, a potential nonattainment area under the 8-hr O3 standard, may cause an increase in local O3. Future strategies to reduce O3 in Southwest Ohio should be further evaluated carefully. The combination of observational-based methods might provide a consistent complementary approach in the identification of the NO,-VOC sensitive characteristics of mid-to-moderate polluted urban areas.

Air Pollutants↗

Case-control study of multiple chemical sensitivity, comparing haematology, biochemistry, vitamins and serum volatile organic compound measures.

BACKGROUND: Multiple chemical sensitivity (MCS), although poorly understood, is associated with considerable morbidity. AIM: To investigate potential biological mechanisms underlying MCS in a case-control study. METHODS: Two hundred and twenty-three MCS cases and 194 controls (urban females, aged 30-64 years) fulfilled reproducible eligibility criteria with discriminant validity. Routine laboratory results and serum levels of volatile organic compounds (VOCs) were compared. Dose-response relationships, a criterion for causality, were examined linking exposures to likelihood of case status. RESULTS: Routine laboratory investigations revealed clinically unimportant case-control differences in means. Confounder-adjusted odds ratios (OR) showed MCS was negatively associated with lymphocyte count and total plasma homocysteine, positively associated with mean cell haemoglobin concentration, alanine aminotransferase and serum vitamin B6, and not associated with thyroid stimulating hormone, folate or serum vitamin B12. More cases than controls had detectable serum chloroform (P = 0.001) with the OR for detectability 2.78 (95% confidence interval = 1.73-4.48, P < 0.001). Chloroform levels were higher in cases. However, cases had significantly lower means of detectable serum levels of ethylbenzene, m&p-xylene, 3-methylpentane and hexane, and means of all serum levels of 1,3,5- and 1,2,3-trimethylbenzene, 2- and 3-methylpentane, and m&p-xylene. CONCLUSIONS: Our findings are inconsistent with proposals that MCS is associated with vitamin deficiency or thyroid dysfunction, but the association of lower lymphocyte counts with an increased likelihood of MCS is consistent with theories of immune dysfunction in MCS. Whether avoidance of exposures or different metabolic pathways in cases explain the observed lower VOC levels or the higher chloroform levels should be investigated.

Adult↗

Application of diffusion-based surveys in the district-wide assessment of benzene and select volatile organic compounds in urban environments--a case study from Renfrewshire, Scotland.

Benzene (with toluene, ethyl benzene and xylene isomers) concentrations were measured at nine locations in Renfrewshire district between February 1996 and July 1998. Samples were collected by both active and diffusion-based sampling and the compounds were quantified by gas chromatography-flame ionization detection (GC-FID) and gas chromatography-mass spectrometry (GC-MS). The study highlighted the ability of diffusion sampling to provide an effective district-wide assessment of volatile organic compounds (VOCs) in urban environmental assessment. Vehicle movement was confirmed as the dominant influence on benzene and associated VOCs in the atmosphere, with strong variations in monthly average concentrations across the study area. For benzene, peak monthly averages were observed on the order of 5-6 ppb v/v, with minimum values of < <0.5 ppb v/v. The impact of a major traffic intervention on benzene levels was followed, and was found to influence atmospheric concentrations over a wide geographical area. An evaluation of the relationship between VOCs and meteorological parameters identified the impact of photo-oxidation and air mass mixing on average atmospheric concentrations.

Air Pollutants↗

Characterization of volatile organic compounds in smoke at experimental fires.

Significant associations between firefighting and cancer have been reported; however, studies finding toxic products of combustion at municipal fires have been limited by (1) technical difficulties encountered at the scene of working fires, (2) the lack of a coherent sampling strategy, and (3) the absence of verified sampling methods. The objective of the present study was to characterize the presence of volatile organic compound (VOC) combustion products in fire smoke. Air samples from experimental fires burning various materials commonly found at structural fires were collected into evacuated Summa canisters and analyzed for 144 target VOCs using cryogenic preconcentration and gas chromatography/mass spectroscopy (GC/MSD) methodology. The resulting chromatograms were characterized by a small number of predominant peaks, with 14 substances (propene, benzene, xylenes, 1-butene/2-methylpropene, toluene, propane, 1,2-butadiene, 2-methylbutane, ethylbenzene, naphthalene, styrene, cyclopentene, 1-methylcyclopentene, isopropylbenzene) being found in proportionately higher concentrations in all experimental fires and accounting for 65% (SD = +/-12%) by mass of total measured VOCs. Benzene, toluene, 1,3-butadiene, naphthalene, and styrene were found at higher concentrations than most other VOCs and increased with the time of combustion together with increasing levels of carbon monoxide. Benzene was found in the highest concentrations, with peak levels ranging from 0.6 ppm to 65 ppm, while the levels of 1,3-butadiene, styrene, and naphthalene peaked at 0.1, 0.4, and 3 ppm, respectively. This study revealed that there were no new or novel, toxic nonpolar VOCs resulting from the burning of common building materials. This is important in view of the studies that have found associations between firefighting and various forms of cancer.

Beds↗

Volatile organic compounds with characteristic odor in bamboo vinegar.

Bamboo vinegar solutions had pHs of 2.5 to 2.8, and the amounts of organic constituents were estimated to be 2.3 to 4.6% (w/w). Volatile organic compounds (28 components) were detected by GC-MS, and among of these, 11 compounds were common to three samples of bamboo vinegar. Perhaps acetic acid, 3-methyl-1,2-cyclohexadione, guaiacol, p-cresol, and syringol contributed to the characteristic odors (sour, smoky, and medicinal note) in bamboo vinegar.

Acetic Acid↗

System for the generation of standard gas mixtures of volatile and semi-volatile organic compounds for calibrations of solid-phase microextraction and other sampling devices.

Standard gases are used for quality control and quality assurance, development of analysis methods and novel air sampling devices. The use of solid-phase microextraction (SPME) and other novel technologies for research in the area of air sampling and analysis requires systems/devices for reliable standard gas generation and sampling. In this paper we describe a new gas standard generating system for volatile organic compounds (VOCs) and semi-VOCs that was designed, built, and tested to facilitate fundamental and applications research with SPME. The system provided for the generation of a wide range of VOC/semi-VOC concentrations and mixing various standard gases, estimation of detection limits, testing the effects of sampling time, air temperature and relative humidity, testing the effects of air velocity and ozone on sampling/extractions. The system can be also used for calibrations of analytical instrumentation, quality control and quality assurance checks, and cross-validations of SPME with/and other sampling techniques.

Calibration↗

Identifying bacteria in human urine: current practice and the potential for rapid, near-patient diagnosis by sensing volatile organic compounds.

Urinary tract infection (UTI) represents a significant burden for the National Health Service. Extensive research has been directed towards rapid detection of UTI in the last thirty years. A wide range of microbiological and chemical techniques are now available to identify and quantify bacteria in urine. However, there is a clear and present need for near, rapid, sensitive, reliable analytical methods, preferably with low-running costs, that could allow early detection of UTI and other diseases in urine. Here we review the "state of the art" of current practice for the detection of bacteria in urine and describe the advantages of the recent "e-nose" technology as a potential tool for rapid, near-patient diagnosis of UTI, by sensing volatile organic compounds (VOCs).

Bacteria↗