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Headspace membrane introduction mass spectrometry for trace level analysis of VOCs in soil and other solid matrixes

A new MIMS-derived technique, headspace membrane introduction mass spectrometry (HS-MIMS), is described for direct trace level analysis of volatile organic compounds (VOCs) in soil and other dry or wet solid matrixes. A silicone membrane interface is placed about 15 cm from the ion source, and a closed airspace (headspace) is created by connecting a toggle valve to the 1/4 in. tubing that connects the membrane interface to the ion source. For the VOC analysis, the headspace is evacuated and the solid sample vessel is heated to 90 degrees C. The VOCs are rapidly desorbed from the sample, pervaporated through the membrane, and preconcentrated for 4 min in the evacuated headspace. Then, the toggle valve is opened and the trapped VOCs are released into the ion source region of a quadrupole mass spectrometer. By electron ionization and selected-ion monitoring, a relatively sharp and intense peak is obtained and used for quantification. The HS-MIMS analysis shows excellent linearity and reproducibility and detection limits for many VOCs typically of 50-100 ng/kg (ppt).

Journal Article↗

VOCs, pesticides, nitrate, and their mixtures in groundwater used for drinking water in the United States.

Samples of untreated groundwater from 1255 domestic drinking-water wells and 242 public supply wells were analyzed as part of the National Water-Quality Assessment Program of the U.S. Geological Survey between 1992 and 1999. Wells were sampled to define the regional quality of the groundwater resource and, thus, were distributed geographically across large aquifers, primarily in rural areas. For each sample, as many as 60 volatile organic compounds (VOCs), 83 pesticides, and nitrate were analyzed. On the basis of previous studies, nitrate concentrations as nitrogen > or = 3 mg/L were considered to have an anthropogenic origin. VOCs were detected more frequently (44%) than pesticides (38%) or anthropogenic nitrate (28%). Seventy percent of the samples contained at least one VOC, pesticide, or anthropogenic nitrate; 47% contained at least two compounds; and 33% contained at least three compounds. The combined concentrations of VOCs and pesticides ranged from about 0.001 to 100 microg/L, with a median of 0.02 microg/L. Water from about 12% of the wells contained one or more compounds that exceeded U.S. Environmental Protection Agency drinking-water standards or human health criteria, primarily because of nitrate concentrations exceeding the maximum contaminant level in domestic wells. A mixture is defined as a unique combination of two or more particular compounds, regardless of the presence of other compounds that may occur in the same sample. There were 100 mixtures (significantly associated with agricultural land use) that had a detection frequency between 2% and 19%. There were 302 mixtures (significantly associated with urban land use) that had a detection frequency between 1% and <2%. Only 14 compounds (seven VOCs, six pesticides, and nitrate) contributed over 95% of the detections in these 402 mixtures; however, most samples with these mixtures also contain a variety of other compounds.

Data Collection↗

Trends in Europe to reduce the indoor air pollution of VOCs.

A strong research tradition in the European countries about volatile organic compounds (VOCs) and indoor air quality has led to several consensus reports about stategies for VOC measurements including the development of methods to measure VOC emissions from building products. European and Nordic standards have been developed for emission testing including several national and international labeling schemes. Proposals for guidelines for a number of different VOCs have been developed either nationally or by consensus. A compound-by-compound approach for health evaluation of VOCs has become more common and there appears to be a growing recognition to focus on the biologic relevance of organic compounds in indoor air (OCIAs).

Air Pollution, Indoor↗

Surface acoustic wave (SAW) microsensor array for measuring VOCs in drinking water.

Exposure to volatile organic chemicals (VOCs) in drinking water has been linked to a number of adverse health effects including cancer, liver, and kidney damage. However, the large number of potential contaminants and the cost and complexity of existing analytical methods limits the extent to which water quality is routinely characterized. This project focused on the laboratory development and evaluation of an instrument for field analysis of VOCs in drinking water. The instrument is based on an array of six polymer-coated surface-acoustic-wave microsensors. A test-set consisting of dichloromethane, chloroform, 1,1,1-trichloroethane, perchloroethylene, and m-xylene was used in a series of experiments designed to optimize the purge-trap preconcentration system, calibrate the instrument over the concentration range of 0.2-2 times the USEPA maximum contaminant levels (MCLs), and compare results to those of a reference laboratory. The primary goal was to develop a cost-effective alternative for on-site evaluation of VOCs in water. Calibration and evaluation test results for spiked water samples demonstrate adequate sensitivity for 19 of the 21 regulated VOCs considered using a ten minute sampling and analysis cycle. Monte Carlo simulations characterized the performance of trained artificial neural networks (ANNs) which had correct classification rates of 99%, 90%, and 80% for the five individual test-set vapors and their binary and ternary mixtures, respectively. These results demonstrate the excellent potential of this technology for addressing the need for improved VOC field-screening methods for water supplies.

Acoustics↗

[Air pollution by volatile organic compounds (VOC) and health complaints].

BACKGROUND AND OBJECTIVE: Complaints of well-being and health after moving in a new or redeveloped building occur quite frequently. If these complaints persist for several months and are indicated by the majority of occupants, an examination of the air quality is required. However, the interpretation of these data can be difficult since different recommendations but no threshold limit values for the indoor contamination with volatile organic compounds (VOC's) exist. PATIENTS AND METHODS: This report presents a case with serious health complaints (14 males, average age 40.4 years; 44 females, average age 37.9 years) after moving in a completely redeveloped building. Complaints of well-being and health were investigated by a standardised questionnaire and compared with a control group (11 males, average age 41.4 years; 12 females, average age 33.3 years). The VOC-contamination was analysed by various measurements. RESULTS: Two months after moving into the building a total VOC-concentration of 2000-3000 micrograms/m3 was registered, after 10 months the concentration decreased to 900-1300 micrograms/m3 due to intense airing. The following symptoms showed the clearest differences between exposed persons and the control group: soreness of throat (odds ratio: 10.72; 95%-confidence interval: 1.46-465.2), irritations of mucous membranes (OR: 10.45; 95%-CI: 1.43-453.8), headache (OR: 9.9; 95%-CI: 1.35-430.9) and increased weariness (OR: 7.55; 95%-CI: 1.55-71.2). As a consequence extensive redevelopment measures were initiated. CONCLUSION: Contamination of the indoor air with 900 micrograms/m3 VOC's (total value) can induce serious complaints of well-being and health. Rooms with VOC-concentrations > 1200-1500 micrograms/m3 are not suited for regular stay of unprotected people.

Adult↗

Enhanced in vivo IgE production and T cell polarization toward the type 2 phenotype in association with indoor exposure to VOC: results of the LARS study.

The association between indoor exposure to volatile organic compounds (VOC), prevalence of allergic sensitization and cytokine secretion profile of peripheral T cells was studied in 3 year old children of the LARS study (Leipzig Allergy Risk Children Study) to investigate the role of VOC exposure as a risk factor for the development of atopic disease. Indoor VOC exposure was measured over a period of 4 weeks in infants' bedrooms using a passive sampling system. Specific IgE antibodies to food, indoor and outdoor allergens were measured by the Pharmacia CAP system and correlated to VOC exposure (n = 120). In addition, cytokine producing peripheral T cells (interleukin(IL)-4, interferon(IFN)-gamma) were measured in a subgroup of 28 children by means of intracellular cytokine staining. For the first time we were able to show that exposure to alkanes (C6, C9, C10) and aromatic compounds (toluene, o-xylene, m + p-xylene, 2-, 3- and 4-ethyl-toluene, chlorobenzene) may contribute to the risk of allergic sensitization to the food allergens milk and egg white (Odds ratios between 5.7 and 11.2). Moreover, significantly reduced numbers of CD3+/CD8+ peripheral T cells were found in children exposed to alkanes (C9-C13), naphthalene and chlorobenzene. Exposure to benzene, ethylbenzene and chlorobenzene was associated with higher percentages of IL-4 producing CD3+ T cells. Both an increase in IL-4 producing type 2 T cells and a reduction of IFN-gamma producing type 1 T cells may contribute to a type 2 skewed memory in response to allergens. Therefore, we suggest exposure to VOCs in association with allergic sensitization to be mediated by a T cell polarization toward the type 2 phenotype.

Air Pollution, Indoor↗

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

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.

Air Pollutants↗

The risk of MTBE relative to other VOCs in public drinking water in California.

Ongoing publicity about methyl tertiary butyl ether (MTBE) suggests that this chemical is of greater concern than other contaminants commonly found in drinking water. The purpose of this article is to evaluate the available MTBE data in context with other volatile organic compounds (VOCs) that are detected in public drinking water sources in California. We find that of the 28 VOCs with a primary maximum contaminant level (MCL) in California, 21 were found in 50 or more drinking water sources from 1985 to 2002. Over the last 10 years, the most frequently detected VOCs were chloroform, tetrachloroethylene (PCE), and trichloroethylene (TCE), which were found in about 9-15% of all sampled drinking water sources. These same chemicals were found to have the highest mean detected concentrations over the last 5 years, ranging from 13 to 15 microg/L. Many VOCs were also found to routinely exceed state and federal drinking water standards, including benzene and carbon tetrachloride. By comparison, MTBE was found in approximately 1% of sampled drinking water sources for most years, and of those drinking water sources found to contain MTBE from 1998 to 2002, over 90% had detected concentrations below California's primary MCL of 13 microg/L. Relative to the other VOCs evaluated, MTBE has the lowest estimated California cancer potency value, and was found to pose one of the least cancer risks from household exposures to contaminated drinking water. These findings suggest that MTBE poses an insignificant threat to public drinking water supplies and public health in California, particularly when compared to other common drinking water contaminants.

California↗

Variations of formaldehyde and VOC levels during 3 years in new and older homes.

UNLABELLED: Indoor air organic compounds were continuously monitored during 3 years in new and older homes which were voluntarily selected throughout countries. The levels of volatile organic compounds (VOCs) in the new homes decreased markedly after 1 year, and steady emissions of VOCs were obtained in the initial months. Formaldehyde and a-pinene related to wooden materials need a longer flushing period than the other compounds in the new homes. The levels of the indoor air organic compounds in the older homes showed no significant fluctuation during the 3-year period. Decreases of the indoor-produced compounds in the new homes did not depend upon the ventilation systems. The results indicate that the indoor-produced compounds in the new homes will be more influenced by the aging decreases of emission source strengths than ventilation systems. The quantitative information on the trend of the indoor air organic compound levels will be useful for the risk assessment of indoor exposure to those compounds, and also for Japanese IAQ guidelines. PRACTICAL IMPLICATIONS: The initial levels of VOCs in the new homes decreased dramatically and were close to the mean values for the older homes after one year. The results suggest that steady emissions of VOCs are obtained within initial months. However, formaldehyde and a-pinene did not follow the trend for VOCs, particularly in the wooden framed houses. The results tend to suggest that formaldehyde and a-pinene related to wooden materials will need more long a flushing period than other compounds in the new homes. Decreasing tendency of indoor air organic compound levels in the new homes did not appear to show any dependency upon the ventilation systems over the whole period. Absence of data for ventilation rates in the houses dose not permit interpretation of the relation between ventilation rates and indoor air organic compound levels with statistical certainty, but the results suggest that indoor air organic compound levels in the homes will be more influenced by emission source strengths than ventilation systems. The levels of indoor air organic compounds in the new homes are sufficiently decreased according to the ageing decreases of organic compounds when the home is ventilated with adequate quantities.

Air Pollutants↗

Simple analysis of volatile organic compounds (VOCs) in the atmosphere using passive samplers.

A simple analysis of volatile organic compounds (VOCs), such as benzene, toluene, m,p-xylene, and o-xylene, at low levels in the atmosphere was conducted using passive samplers. The methods were applied to analyzing the behavior and origin of VOCs in Kyoto City. The passive samplers were exposed for 7 - 14 days at sampling sites in Kyoto City and for 30 days in the mountains (Mt. Hiei and Mt. Daimonji). Shibata gas-tube samplers packed with activated carbon were used for the determination of VOCs. The absorbed VOCs were extracted into carbon disulfide (CS2) and measured by FID-GC. The determination limits and relative standard deviations for VOCs were 0.3 microg/m3 and 3%, respectively. The samplers were set up at 5 sites in March, 2001 and at 13 stations on Mt. Hiei in November, 2002. The average concentrations of ambient benzene, which were higher than the environmental criterion (3.0 microg/m3), except for those on Mt. Daimonji from March, 2001, to February, 2002, decreased to below 3.0 microg/m3 from March, 2002, to February, 2003. The decrease in ambient benzene may have been due to a decrease in the benzene content in gasoline by the end of 1999, and also by implementation of the Pollutant Release and Transfer Register (PRTR) Act in 2001.

Journal Article↗

Adequate model complexity for scenario analysis of VOC stripping in a trickling filter.

Two models describing the stripping of volatile organic contaminants (VOCs) in an industrial trickling filter system are developed. The aim of the models is to investigate the effect of different operating conditions (VOC loads and air flow rates) on the efficiency of VOC stripping and the resulting concentrations in the gas and liquid phases. The first model uses the same principles as the steady-state non-equilibrium activated sludge model Simple Treat, in combination with an existing biofilm model. The second model is a simple mass balance based model only incorporating air and liquid and thus neglecting biofilm effects. In a first approach, the first model was incorporated in a five-layer hydrodynamic model of the trickling filter, using the carrier material design specifications for porosity, water hold-up and specific surface area. A tracer test with lithium was used to validate this approach, and the gas mixing in the filters was studied using continuous CO2 and O2 measurements. With the tracer test results, the biodegradation model was adapted, and it became clear that biodegradation and adsorption to solids can be neglected. On this basis, a simple dynamic mass balance model was built. Simulations with this model reveal that changing the air flow rate in the trickling filter system has little effect on the VOC stripping efficiency at steady state. However, immediately after an air flow rate change, quite high flux and concentration peaks of VOCs can be expected. These phenomena are of major importance for the design of an off-gas treatment facility.

Biofilms↗

Quantitative determination of volatile organic compounds (VOC) in milk by multiple dynamic headspace extraction and GC-MS.

A method for the accurate determination of volatile organic compounds (VOC) in milk samples has been developed and tested. It combines multiple dynamic headspace extraction with GC-MS. Absolute amounts of VOC in the liquid phase are obtained by determining the first order kinetic dependence of the stepwise extraction of the analytes and internal standards from the liquid matrix. Compounds released from milk were collected on a train of traps filled with different solid sorbents to cover all components having a number of carbon atoms ranging from 4 to 15. They were analysed by GC-MS after thermal desorption of VOC from the collecting traps. Quantification of VOC in milk was performed using deuterated compounds as internal standards. The method was used to follow seasonal variations of monoterpenes in goat milk and to detect the impact of air pollution on the quality of milk.

Animals↗

Adsorption energy distribution model for VOCs onto activated carbons.

An adsorption isotherm model was proposed for two types of volatile organic compounds (VOCs) on a heterogeneous carbon surface. The Langmuir isotherm was used as a local isotherm for describing heterogeneous surfaces to obtain the adsorption energy distribution. The adsorption temperature studied ranged from 30 to 50 degrees C, and the pressure of VOCs varied from 0 to 0.35 atm. The present model differed from previous studies in assuming that the pre-exponential factor was not to be a constant. The pre-exponential factors were determined directly from the experimental data, and the result empirically showed that the pre-exponential factor was correlated with the adsorption energy by a simple exponential function. We found that both adsorption energy distributions of two VOCs were essentially step functions over the restricted pressure range, indicating adsorbates on the carbon surface with its own uniform distribution. By incorporation of the energy distribution and the relationship between the pre-exponential factor and the adsorption energy, the adsorption isotherms for the two VOCs on the carbons can be well predicted.

Journal Article↗

Spatial distribution of respiratory activity in Pseudomonas putida 54G biofilms degrading volatile organic compounds (VOC).

All over the world, Microbial systems are used to clean soils, waters and air streams that have been contaminated with volatile organic compounds (VOC). Information about the structure and function of the microbes that metabolize these contaminants can be gained by studying these microbial systems. Here we describe the spatial patterns of respiratory activity in Pseudomonas putida 54G aerobic biofilms degrading two VOC, toluene and ethanol. Oxygen concentration profiles within the biofilm were measured using microsensors. These profiles are thought to be most accurate reflection of the structure and function of aerobic microbial biofilms. The degrading process certainly imposed a structural and functional patterns on the microbial biofilm community growing at the expense of the VOC substrate. Cryosectioning coupled with the staining of biofilm samples confirmed a high respiratory activity near the substratum, that decreased towards the biofilm/fluid interface. The accumulation of inactive cells in the outer biofilm layer protects the inner biofilm from high concentrations of toxic compounds and also limits the degradation rate. This stratification phenomenon appeared to be a general pattern for P. putida 54G biofilms degrading VOC.

Biofilms↗

Control of VOCs emissions by condenser pre-treatment in a semiconductor fab.

The performance of a modified design of local condensers to pre-treat a variety of volatile organic compounds (VOCs) emitted from the stripping process of a semiconductor fab was tested in this study. The reaction temperature of the condensers was controlled at around 10 degrees C, it is relatively higher than the traditional condenser reaction temperature. Both VOCs and water vapors were condensed and formed liquid films. This resulted in an enhancement of the VOCs removals, especially for VOCs of high boiling points or solubility. This can help to prevent the follow up zeolite concentrator from damage. The performance of the integrated system of condenser/zeolite concentrator could, therefore, remain highly efficient for a longer operation time. Its annualized cost would also be lower than installing the zeolite concentrator only.

Air Pollution↗

Changes in concentration levels of selected VOCs in newly erected and remodelled building in Gdansk.

Volatile organic compounds such as benzene, toluene, butyl acetate, ethylbenzene, m-xylene, styrene and m-dichlorobenzene were measured in three newly erected and remodelled dwellings. The present study also attempted to examine the time dependence of concentrations of selected VOCs in each investigated dwelling. This was accomplished by at least triplicate measurements of the IAQ. To collect a series of air samples the active and passive methods were used. In both cases activated charcoal was applied as a sorption medium. The samples were recovered by solvent extraction, and analysed by capillary column gas chromatography, employing a flame ionisation detector. The experimental results showed that MAC values for analysed VOCs were exceeded (even a few orders of magnitude) for the measurements made before inhabiting of the occupants, in every investigated dwelling. The concentrations of the investigated VOCs decreased significantly with time, which should be expected, although in some cases the levels of selected VOCs remained still high. Our experience indicates that parallel application of two different indoor air sampling techniques to determine analytes of interest, though more laborious and time consuming, can lead to significant conclusions concerning indoor air quality in monitored spaces.

Air Pollution, Indoor↗

Effects of VOCs on herbaceous plants in an open-top chamber experiment.

A selection of herbaceous plants representing the ground flora around a typical chemical installation in the UK was exposed continuously for 7 weeks to a mixture of six VOCs (acetone, acetonitrile, dichloromethane, ethanol, methyl t-butyl ether and toluene) in open-top chambers. Exposure concentrations were based on predictions of atmospheric dispersion from a single source, at a distance of approximately 2 km. The effects of continuous exposure, representing a worst-case, were measured in terms of uncontrolled water loss from leaves, leaf wettability, chlorophyll content and fluorescence, dry matter production and detailed observations of changes in plant growth and phenology. There were significant effects of VOC exposure on seed production, leaf water content and photosynthetic efficiency in some plant species. Such effects may be detectable in vegetation close to major industrial point sources of VOCs, or as a result of an accidental release of material during manufacture or transport. Some of the species tested e.g. birdsfoot trefoil (Lotus corniculatus L.) seem to be promising as potential bioindicators for VOCs, but there may be other even more sensitive species waiting to be discovered. However, the most obvious and conveniently measured response to VOCexposure in the birdsfoot trefoil (premature senescence i.e. advanced timing of seed pod production) could easily be confused in the field with climatic influences. It is also uncertain at this stage whether any of the effects observed would lead to longer term ecological changes in natural plant communities, through biased competition between sensitive and more tolerant species.

Acetone↗

Recent advances in VOCs removal from water by pervaporation.

Pervaporation (PV) is a separation process in which minor components of a liquid mixture are preferentially transported by partial vaporization through a non-porous permselective (selectively permeable) membrane. PV is an emerging technology in environment cleanup operations, especially in the removal of volatile organic compounds (VOCs) from industrial wastewaters or contaminated groundwaters. Current state of PV membrane development in VOC removal and improvement in process engineering, and better understanding of the interactions between VOCs and membrane materials are reviewed. Among PV process parameters documented here are process temperature, permeate pressure, feed concentration, and feed flow rate. The effects of these parameters on PV selectivity and permeation flux have been studied extensively and these studies have borne fruit in a better understanding of many aspects of PV processes. The challenge in implementing PV in practical operations lies in the further enhancement of membrane quality for specific VOCs as well as improved management and control of possible adverse hurdles coming from real systems.

Humans↗