Measurements of air–surface exchange rates of volatile organic compounds

Vertical gradients of volatile organic compounds (VOCs) were measured over a maize field and a soybean field in 1995 and 1996, respectively, in the Lower Coastal Plains of North Carolina. The measurements over the maize field were conducted in its early growth period, during May 1995, and the measurements over the soybean field were conducted in its middle and later growth periods during July through August 1996 at the same location. These measurements were combined with micrometeorological flux measurements to determine emission flux measurements for various VOCs. This measurement programme was part of project NOVA (Natural emissions of Oxidant precursors: Validation of techniques and Assessment) to estimate the flux of VOCs. Methanol was identified as the major biogenic compound for both years with the average flux of 3450 ± 1456 µg/m²/hr over maize and 3079 ± 2766 µg/m²/hr over soybean. Acetone is another compound that was identified as a biogenic compound for both years with the average flux of 425 ± 223 µg/m²/hr over maize and 2701 ± 1710 µg/m²/hr over soybean. In addition to biogenic compounds, a large number of aromatic compounds, including styrene and 1,2,4-trimethylbenzene, were also identified as emissions from the ground over the soybean field.     

The solvent-extractable organic compounds in the Indonesia biomass burning aerosols – characterization studies

The large-scale air pollution episode due to the out-of-control biomass burning for agricultural purposes in Indonesia started in June 1997, has become a severe environmental problem for itself and the neighboring countries. The fire lasted for almost five months. Its impact on the health and ecology in the affected areas is expected to be substantial, costly and possibly long lasting. Air pollution Index as high as 839 has been reported in Malaysia. API is calculated based on the five pollutants: NO₂, SO₂, O₃, CO, and respirable suspended particulates (PM10). It ranges in value from 0 to 500. An index above 101 is considered to be unhealthy and a value over 201 is very unhealthy (Abidin and Shin, 1996).The solvent-extractable organic compounds from four total suspended particulate (TSP) high-volume samples collected in Kuala Lumpur, Malaysia (Stations Pudu and SIRIM) were subjected to characterization – the abundance was determined and biomarkers were identified. Two of the samples were from early September when the fire was less intense, while the other two were from late September when Kuala Lumpur experienced very heavy smoke coverage which could be easily observed from NOAA/AVHRR satellite images. The samples contained mainly aliphatic hydrocarbons such as n-alkanes and triterpanes, alkanoic acids, alkanols, and polycyclic aromatic hydrocarbons. The difference between the early and late September samples was very significant. The total yield increased from 0.6 to 24.3 μg m^-3 at Pudu and 1.9 to 20.1 μg m^-3 at SIRIM, with increases in concentration in every class. The higher input of vascular plant wax components in the late September samples, when the fire was more intense, was characterized by the distribution patterns of the homologous series n-alkanes, n-alkanoic acids, and n-alkanols, e.g., lower U : R, higher >C₂₂/<C₂₀ for n-alkanoic acids, higher >C₂₀/<C₂₀ for n-alkanols, a shift in C_max from C₁₆ to C₂₆ for n-alkanoic acids and C₁₈ to C₂₈ for n-alkanols, and the presence of abundant moretane (17β(H), 21α(H)-hopanes). The biomarkers dehydroabietic acid and retene were not found in the samples suggesting there is a difference in the long-distance transport samples of an Asian forest fire and the controlled experiments reported in the literature. Similar to the biomass burning in Amazonia (Abas et al., 1995), the present study also showed an absence of conifer tracers in the smoke aerosols indicating tropical wood sources. Abundant friedelin, a specific biomarker for smoke from oak wood fires (Standley and Simoneit, 1990), was present in the late September samples when the fire was more intense. The results were compared to literature values from an earlier study of the haze episode on 29 September 1991 in Kuala Lumpur, Malaysia (Abas and Simoneit, 1996).     

Interaction of volatile organic compounds with indoor materials—a small-scale screening method

Indoor air pollution caused by volatile organic compounds (VOCs) may affect the health and well-being of inhabitants. Uptake and release of these compounds by and from indoor materials alter their concentrations in indoor air: uptake will lower peak concentrations, whereas subsequent (slow) release at lower concentration levels will prolong the presence of VOCs in indoor air. An experimental set-up has been implemented where indoor materials are placed as a “membrane” separating two air compartments. Both compartments – consisting of Field and Laboratory Emission Cells FLECs – are constantly flushed with air, one air stream containing a mixture of 20 VOCs, and concentrations in both compartments are measured after 1 h. Ten materials usually covering extensive surfaces indoors were consecutively exposed to the vapour mixture at concentration levels typically found in indoor environments. Under the chosen experimental conditions, five of these materials exhibited a permeability high enough that VOCs could be detected on the other side. Mass transport of VOCs into and through indoor materials has therefore been confirmed by experiment. The set-up allows for a quick screening of indoor materials with respect to their sorption capacity and permeability.     

Housewives’ exposure to volatile organic compounds relative to proximity to roadside service stations

Residents in neighborhoods near a service station and/or major roadway would be expected to be exposed to elevated ambient volatile organic compound (VOC) levels compared to those further away from such source(s). We confirmed this and examined whether the anticipated high outdoor levels near a service station and/or major roadway outweighed the indoor levels as a factor for the exposure of nearby residents. Unlike the outdoor air concentrations, neither the indoor air nor breath concentrations were different for the two residential zones tested. The outdoor concentrations were higher during the daytime than at night, however, the indoor air and breath concentrations showed no difference between the two periods. The elevated outdoor levels nearby service stations were not identified as a major contributor to the exposure of housewives living in close proximity. Instead, it appeared that the indoor air levels were the major contributor to housewives’ exposure in both residential zones. This was further supported by the finding that the indoor levels were actually higher than the outdoor levels, and that there was a significant correlation between the indoor and breath levels.     

Particulate matter–bound organic compounds: levels,mutagenicity, and health risks

Environmental Science and Pollution Research - Increased industrialization and consumption of fossil fuels in the Metropolitan Region of São Paulo (MRSP), Brazil, have caused a growth of the...     

Use of a gas chromatography–mass spectrometry organic aerosol monitor for in-field detection of fine particulate organic compounds in source apportionment

A study was conducted on the Brigham Young University campus during January and February 2015 to identify winter-time sources of fine particulate material in Utah Valley, Utah. Fine particulate mass and components and related gas-phase species were all measured on an hourly averaged basis. Light scattering was also measured during the study. Included in the sampling was the first-time source apportionment application of a new monitoring instrument for the measurement of fine particulate organic marker compounds on an hourly averaged basis. Organic marker compounds measured included levoglucosan, dehydroabietic acid, stearic acid, pyrene, and anthracene. A total of 248 hourly averaged data sets were available for a positive matrix factorization (PMF) analysis of sources of both primary and secondary fine particulate material. A total of nine factors were identified. The presence of wood smoke emissions was associated with levoglucosan, dehydroabietic acid, and pyrene markers. Fine particulate secondary nitrate, secondary organic material, and wood smoke accounted for 90% of the fine particulate material. Fine particle light scattering was dominated by sources associated with wood smoke and secondary ammonium nitrate with associated modeled fine particulate water.

Implications: The identification of sources and secondary formation pathways leading to observed levels of PM_2.5 (particulate matter with an aerodynmaic diameter <2.5 μm) is important in making regulatory decisions on pollution control. The use of organic marker compounds in this assessment has proven useful; however, data obtained on a daily, or longer, sampling schedule limit the value of the information because diurnal changes associated with emissions and secondary aerosol formation cannot be identified. A new instrument, the gas chromtography–mass spectrometry (GC-MS) organic aerosol monitor, allows for the determination on these compounds on an hourly averaged basis. The demonstrated potential value of hourly averaged data in a source apportionment analysis indicates that significant improvement in the data used for making regulatory decisions is possible.     

Can ornamental potted plants remove volatile organic compounds from indoor air? — a review

Volatile organic compounds (VOCs) are found in indoor air, and many of these can affect human health (e.g. formaldehyde and benzene are carcinogenic). Plants affect the levels of VOCs in indoor environments, thus they represent a potential green solution for improving indoor air quality that at the same time can improve human health. This article reviews scientific studies of plants’ ability to remove VOCs from indoor air. The focus of the review is on pathways of VOC removal by the plants and factors affecting the efficiency and rate of VOC removal by plants. Laboratory based studies indicate that plant induced removal of VOCs is a combination of direct (e.g. absorption) and indirect (e.g. biotransformation by microorganisms) mechanisms. They also demonstrate that plants’ rate of reducing the level of VOCs is influenced by a number of factors such as plant species, light intensity and VOC concentration. For instance, an increase in light intensity has in some studies been shown to lead to an increase in removal of a pollutant. Studies conducted in real-life settings such as offices and homes are few and show mixed results.     

Sample integrity of trace level volatile organic compounds in ambient air stored in SUMMA® polished canisters

Sets of new and used SUMMA® polished stainless steel canisters were tested for storage stability of volatile organic compounds (VOCs). Evacuated canisters were filled at a controlled rate with ambient air containing added concentrations of 15 VOCs (14 chlorinated, one brominated) at < 2 ppbv. Concentrations of VOCs in each canister were then periodically determined during 7-day or 30-day storage periods using simultaneous flame ionization and electron capture detection. No initial decreases in concentrations of target compounds were observed. Statistical analysis of data showed that the relative standard deviation of concentrations of most VOCs in each canister set was 10% or less during the storage periods. For the 7-day tests, the mean change in concentration per day was within ± 3.2 %. These canisters appear suitable as an alternative to other sampling techniques, at least for most of the compounds tested here.     

FT-IR kinetic and product study of the Br-radical initiated oxidation of α, β-unsaturated organic carbonyl compounds

Using the relative kinetic technique the kinetics of the gas-phase reactions of Br radicals with acrolein, methacrolein and methylvinyl ketone have been investigated at (301±3) K in 1013 mbar of (N₂+O₂) bath gas at varying proportions. In 1013 mbar of synthetic air the following rate coefficients have been obtained (in units of cm³ molecule⁻¹ s⁻¹): acrolein (3.21±0.11)×10⁻¹²; methacrolein (2.33±0.08)×10⁻¹¹; methyl vinyl ketone (1.87±0.06)×10⁻¹¹. This study represents the first determination of the rate coefficients for these compounds. As for other unsaturated hydrocarbons the rate coefficient with Br was found to increase with increasing partial pressure of O₂. From the product studies of the reactions it has been established that addition of Br radicals to the terminal C-atom is the major pathway in all three cases. However, for acrolein H atom abstraction from the -CO–H group is also significant. Mechanisms are proposed to explain the observed products, mainly β-brominated carbonyl compounds.     

Emission of non-methane volatile organic compounds (VOCs) from boreal peatland microcosms—effects of ozone exposure

Non-methane volatile organic compounds (VOCs) emitted from boreal peatland microcosms were semiquantitatively determined using gas chromatography–mass spectrometry techniques in a growth chamber experiment. Furthermore, effects of vegetation composition and different ozone concentrations on these emissions were estimated by multivariate data analyses. The study concentrated on the less-studied VOCs, and isoprene was not analyzed. The analyses suggest that a sedge Eriophorum vaginatum is associated with emissions of the four most-emitted VOC groups (cyclic, aromatic, carbonyl and aliphatic hydrocarbon compounds) and also with VOCs emitted in smaller amounts (terpenoids and N-containing compounds). A woody dwarf shrub Andromeda polifolia was strongly associated with emissions of aromatic, carbonyl and terpenoid compounds. Results suggest that exposure to an ozone concentration of 150 ppb leads to an increased emission of most VOC groups. Emission of aromatic compounds seems to increase linearly with increasing ozone concentration. These observations indicate that peatlands may be a source of a vast range of volatile compounds to the atmosphere. For more accurate assessment of the impact of elevated tropospheric ozone on the terpenoid and non-terpenoid VOC emissions from peatlands, well-replicated open-air ozone-exposure experiments should be conducted.     

Survey of volatile organic compounds associated with automotive emissions in the urban airshed of São Paulo,Brazil

The Metropolitan Region of São Paulo (MRSP), Brazil, is one of the largest metropolitan areas in the world (population 17 million, approx.) and relies heavily on alcohol-based fuels for automobiles. It is estimated that about 40% of the total volume of fuel is ethanol with some vehicles using pure ethanol and others a gasoline/ethanol blend. As such, São Paulo is an excellent example of an oxygenates-dominated airshed of mobile sources and is most likely indicative of the future in heavily populated areas in the US such as Los Angeles where “oxy-fuels” are becoming an important replacement for the conventional pure petroleum-based fuels. In this work, we surveyed the ambient air to identify and quantify the organic compounds associated with the evaporative and exhaust emissions of these fuels and to begin to understand the potential for human exposure. Because this was an initial test without detailed prior knowledge of the airshed of the area, we applied two different air sampling methods for various time periods to assess the ambient concentrations of a variety of polar and nonpolar volatile organic compounds (VOCs). For quality assurance (QA), we collected all the samples in duplicate (whole-air samples in Summa canisters and adsorbent-based samples on Perkin-Elmer Air Toxics tubes) at various flow rates to test performance. All samples were collected over identical time frames, typically for 1-, 2-, and 4-h periods per day at six different locations over a period of 1 week. Overall São Paulo results demonstrate that mean concentrations of single-ring aromatics are 2–3 times higher, volatile aldehydes are 5–10 times higher, and simple alcohols 10–100 times higher as compared to results of a recent study performed by EPA in the Los Angeles basin. C₄–C₁₁ n-alkanes were only slightly elevated in São Paulo.     

Air filters from HVAC systems as possible source of volatile organic compounds (VOC) – laboratory and field assays

The emission of volatile organic compounds (VOC) from air filters of HVAC systems was to be evaluated. In a first study carbonyl compounds (14 aldehydes and two ketones) were measured by reacting them with 2,4-dinitrophenylhydrazine (DNPH). Analysis was done by HPLC and UV detection. In laboratory experiments pieces of used and unused HVAC filters were incubated in test chambers. Filters to be investigated were taken from a filter bank of a large HVAC system in the centre of Berlin. First results show that – among those compounds – formaldehyde and acetone were found in higher concentrations in the test chambers filled with used filters in comparison to those with unused filters. Parallel field measurements were carried out at the prefilter and main filter banks of the two HVAC systems. Here measurements were carried out simultaneously before and after the filters to investigate whether those aldehydes or ketones arise from the filter material on site. Formaldehyde and acetone significantly increased in concentration after the filters of one HVAC system. In parallel experiments microorganisms were proved to be able to survive on air filters. Therefore, a possible source of formaldehyde and acetone might be microbes.     

Derivation of soil values for the path ‘Soil-Soil Organisms’ for metals and selected organic compounds using species sensitivity distributions

BACKGROUND, AIMS AND SCOPE: According to the German Federal Soil Protection Act, the natural function of soil as a habitat for human beings, animals, plants and soil organisms is, among other things, to be protected by deriving soil values for important chemicals regarding their amounts in the environment, their persistence and/or their toxicity. This contribution presents the results of the mathematical derivation of such values for nine metals and ten organic substances from soil ecotoxicological effect values available in the literature for microbial processes, plants and soil invertebrates. MATERIAL AND METHODS: Ecotoxicological data were mostly extracted from published papers and reports and had to originate from valid studies that were performed according to internationally standardised guidelines (e.g. ISO) or were otherwise well documented, plausible and performed according to accepted laboratory practice. As test results, both structural (i.e., effects on mortality, growth or reproduction) and functional (i.e., effects on microbial activity or organic matter breakdown) parameters were included. The derivation of soil values was performed using the distribution based extrapolation model (DIBAEX) and EC(50)s (Effective Concentration) as input data. RESULTS: For 19 compounds, soil values could be calculated. In 18 of these 19 cases clear laboratory ecotoxicological effects (i.e., EC50 values) below the calculated soil value have been found in the literature. DISCUSSION: In those few cases where a comparison with field studies is possible, effects have been observed in the same order of magnitude as the calculated soil values. A comparison with other similar approaches confirmed the plausibility of the calculated values. CONCLUSIONS: The DIBAEX-method is a feasible and widely accepted method for deriving soil values from ecotoxicological input data. Data availability was already satisfactory for some substances, but other substances, especially organics, were only poorly covered. The soil values presented here were based on EC50 input data. However, depending on the protection level aimed at by using soil values in legislation, it might be appropriate to use other input data such as NOECs in the derivation process. RECOMMENDATIONS AND PERSPECTIVES: It is recommended to generate an appropriate number of data for further relevant substances by means of a test battery or multi-species approaches such as terrestrial model ecosystems. These tests should also consider the influence of the bioavailability of substances. A final recommendation for legally binding soil values demands a plausibility check of the mathematically derived values. This should include a comparison with natural background concentrations, soil values for other pathways and soil values used in legislation of other countries. Finally, expert judgement always has to be considered.     

Soils impacted by PAHs: Would the stabilized organic matter be a green tool for the immobilization of these noxious compounds?

The objective of this study was to investigate the role of stabilized organic matter (vermicompost) and tropical soils in the sorption of naphthalene, anthracene and benzo[a]pyrene. The results obtained for the three compounds were extrapolated for the priority polycyclic aromatic hydrocarbons (PAHs) pollutants according to Environmental Protection Agency (US EPA). To evaluate the sorption process, high performance liquid chromatography was employed and the data was fitted by Freundlich isotherms. The results suggest that the sorption effect generally increases with the number of benzene rings of the PAHs, and that the persistence of PAHs in the environment is possibly related to the number of benzene rings in the PAH molecule. In addition, the pH of the vermicompost can strongly affect the adsorption process in this matrix.     

Hygroscopic organic aerosols during BRAVO?

The hygroscopic properties of the organic fraction of aerosols are poorly understood. The ability of organic aerosols to absorb water as a function of relative humidity (RH) was examined using data collected during the 1999 Big Bend Regional Aerosol and Visibility Observational Study (BRAVO). (On average, organics accounted for 22% of fine particulate matter with an aerodynamic diameter less than 2.5 microm (PM2.5) mass). Hourly RH exceeded 80% only 3.5% of the time and averaged 44%. BRAVO aerosol chemical composition and dry particle size distributions were used to estimate PM2.5 light scattering (Bsp) at low and high ambient RH. Liquid water growth associated with inorganic species was sufficient to account for measured Bsp for RH between 70 and 95%.     

C5–C12 volatile organic compounds at roadside,residential, and background locations in Ankara,Turkey: Temporal and spatial variations and sources

Abstract

Particle emissions of modern diesel engines are of a particular interest because of their negative health effects. The special interest is in nanosized solid particles. The effect of an open channel filter on particle emissions of a modern heavy-duty diesel engine (MAN D2066 LF31, model year 2006) was studied. Here, the authors show that the open channel filter made from metal screen efficiently reduced the number of the smallest particles and, notably, the number and mass concentration of soot particles. The filter used in this study reached 78% particle mass reduction over the European Steady Cycle. Considering the size-segregated number concentration reduction, the collection efficiency was over 95% for particles smaller than 10 nm. The diffusion is the dominant collection mechanism in small particle sizes, thus the collection efficiency decreased as particle size increased, attaining 50% at 100 nm. The overall particle number reduction was 66–99%, and for accumulation-mode particles the number concentration reduction was 62–69%, both depending on the engine load.     

Use of thermal desorption–gas chromatography–mass spectrometry (TD–GC–MS) on identification of odorant emission focus by volatile organic compounds characterisation

Volatile organic compounds (VOCs) from several different municipal solid wastes’ treatment plants in Mallorca (Spain) have been analysed by thermal desorption–gas chromatography–mass spectrometry (TD–GC–MS). Ambient (immission) air was collected during February and March 2011 by active sampling onto sorbents Tenax™ TA and Carboxen™ 1000. The study presents the chemical characterisation of 93 volatile organic compounds (VOCs) from an overall set of 84 immission air samples. 70 VOCs were positively identified.The linear fit for all 93 external standard calibration, from 10 mg L⁻¹ to 150 mg L⁻¹ (n = 4), was within the range 0.974 < r² < 0.998. Limits of detection of the method (LOD) for all the standards were within the range 1.1–4,213 pg, as the absolute standard amount spiked into sorbent tubes in 1 μL standard mixture (dissolved in methanol).Overall results stated systematic correlation between waste’s nature and VOCs’ air composition. Organic wastes show main contribution of terpenes, waste water sludge residues’ of reduced sulphured compounds (RSCs) and municipal solid wastes show contribution of a wide sort of VOCs. The use of a chemometric approach for variable’s reduction to 12 principal components enables evaluation of similarities and dissimilarities between facilities. PCA clearly related samples to its corresponding facility on the basis of their VOCs composition and the ambient temperature.     

Photocatalytic decomposition on nano-TiO₂: destruction of chloroaromatic compounds

Photocatalysis is applied increasingly in addressing and solving environmental and energy-related problems. Especially the TiO₂-derived catalysts attract attention because of their catalytic efficiency, wide range of applications, ease in use, and low cost (it costs about 150 Yuan a kilogram in China). This review first describes the principles of photocatalytic destruction by semiconductors and then focuses on degradation rates and reaction mechanisms in a variety of photocatalytic uses of modified TiO₂. Finally, these concepts are illustrated by selected examples relating to the photocatalytic degradation of organic persistent pollutants, such as polychlorinated benzenes (PCBz), biphenyls (PCB) and dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). And some approaches towards industrial application are analyzed.