Mixing ratios of volatile organic compounds (VOCs) in the atmosphere of Karachi,Pakistan

Mixing ratios of carbon monoxide (CO), methane (CH₄), non-methane hydrocarbons, halocarbons and alkyl nitrates (a total of 72 species) were determined for 78 whole air samples collected during the winter of 1998–1999 in Karachi, Pakistan. This is the first time that volatile organic compound (VOC) levels in Karachi have been extensively characterized. The overall air quality of the urban environment was determined using air samples collected at six locations throughout Karachi. Methane (6.3 ppmv) and ethane (93 ppbv) levels in Karachi were found to be much higher than in other cities that have been studied. The very high CH₄ levels highlight the importance of natural gas leakage in Karachi. The leakage of liquefied petroleum gas contributes to elevated propane and butane levels in Karachi, although the propane and butane burdens were lower than in other cities (e.g., Mexico City, Santiago). High levels of benzene (0.3–19 ppbv) also appear to be of concern in the Karachi urban area. Vehicular emissions were characterized using air samples collected along the busiest thoroughfare of the city (M.A. Jinnah Road). Emissions from vehicular exhaust were found to be the main source of many of the hydrocarbons reported here. Significant levels of isoprene (1.2 ppbv) were detected at the roadside, and vehicular exhaust is estimated to account for about 20% of the isoprene observed in Karachi. 1,2-Dichloroethane, a lead scavenger added to leaded fuel, was also emitted by cars. The photochemical production of ozone (O₃) was calculated for CO and the various VOCs using the Maximum Incremental Reactivity (MIR) scale. Based on the MIR scale, the leading contributors to O₃ production in Karachi are ethene, CO, propene, m-xylene and toluene.     

Volatile organic compounds in the atmosphere of forests

The procedure of sampling and gas chromatographic-mass spectrometric analysis of air containing volatile emissions from living plants has been elaborated. The qualitative composition of volatile organic compounds (VOC) produced by 22 species of plants which are characteristic for Northern hemisphere forests has been studied. The emission rate of isoprene and terpenes for some of them has been determined. Terpene concentrations in coniferous forests of different regions of the U.S.S.R. have been also determined. The list of compounds identified includes more than 70 substances of different classes. Total terpene concentrations in the coniferous forests air usually vary from 3.5 to 35 μg⁻³. Strong influence of meteorological conditions on the emission rate and terpene concentrations in the air under the forest canopy has been noted.     

Smoke concentration in the greater Cairo atmosphere

A study of smoke content of the atmosphere over the Greater Cairo area was conducted during the 12 months from June 1977 to May 1978. Smoke samples were taken continuously over two-hour periods at two sites, one in Shubra El-Kheima industrial sector on the northern boundary of the study area and the other in a purely residential district about 15 km south-south-west of the first site.A comparison was made between the averaged concentrations at both sites. It was found that the industrial area was considerably higher in smoke contamination and that industrial activity is the principal source of smoke in the Cairo atmosphere.Daily and yearly cycles of smoke concentration were also studied and discussed in terms of man-made source activities and meteorological conditions. Concentrations were found to be much higher in the cold months. The daily cycle rhythm was the same at the two sites, having two well developed maxima in the morning and late evening and a pronounced minimum in the mid-afternoon. Daily maxima were almost of the same order of magnitude in each site. The morning maximum seemed to be formed by fumigation just after sunrise in the industrial sector and appeared two hours later in the downwind residential district.No significant difference was found between smoke concentrations during weekdays and weekends.     

Assessment of indoor levels of volatile organic compounds and carbon dioxide in schools in Kuwait

Indoor air quality (IAQ) in schools is a matter of concern because children are most vulnerable and sensitive to pollutant exposure. Conservation of energy at the expense of ventilation in heating, ventilation, and air conditioning (HVAC) systems adversely affects IAQ. Extensive use of new materials in building, fitting, and refurbishing emit various pollutants such that the indoor environment creates its own discomfort and health risks. Various schools in Kuwait were selected to assess their IAQ. Comprehensive measurements of volatile organic compounds (VOCs) consisting of 72 organic compounds consisting of aliphatic (C₃–C₆), aromatic (C₆–C₉), halogenated (C₁–C₇), and oxygenated (C₂–C₉) functional groups in indoor air were made for the first time in schools in Kuwait. The concentrations of indoor air pollutants revealed hot spots (science preparation rooms, science laboratories, arts and crafts classes/paint rooms, and woodworking shops/decoration rooms where local sources contributed to the buildup of pollutants in each school. The most abundant VOC pollutant was chlorodifluoromethane (R22; ClF₂CH), which leaked from air conditioning (AC) systems due to improper operation and maintenance. The other copious VOCs were alcohols and acetone at different locations due to improper handling of the chemicals and their excessive uses as solvents. Indoor carbon dioxide (CO₂) levels were measured, and these levels reflected the performance of HVAC systems; a specific rate or lack of ventilation affected the IAQ. Recommendations are proposed to mitigate the buildup of indoor air pollutants at school sites.

Implications: Indoor air quality in elementary schools has been a subject of extreme importance due to susceptibility and sensibility of children to air pollutants. The schools were selected based on their surrounding environment especially downwind direction from the highly industrialized zone in Kuwait. Extensive sampling from different sites in four schools for comprehensive VOCs and CO₂ were completed for an extended period of over a year. Different hot spots were identified where leaked refrigerant and inadequate handling of laboratory solvents contributed to the high VOCs in the respective locations. CO₂ levels reflected HVAC performance and poor ventilation. A list of recommendations has been proposed to eradicate these high levels of air pollution.     

Verification of diffusive and pumped samplers for volatile organic compounds using a controlled atmosphere test facility

There is a requirement to verify the performance of sorbent-based passive or active samplers and to extend their use, where possible, to monitor volatile organic compounds (VOCs) that are known to be photochemical ozone pre-cursors or are relevant to the activities of the petrochemical industry. We report measurements of the 14-day diffusive uptake rates for the VOCs: i-butane (2-methyl propane), n-butane, i-pentane (2-methyl butane), n-pentane, n-hexane, benzene, toluene, and m-xylene (at environmental level concentrations) for industry standard axial samplers (Perkin–Elmer-type samplers) containing the sorbents Carbopack-X, -Z, -B or Tenax-TA. We also present data on back-diffusion, blank levels, and storage for the above sorbents, and describe the simultaneous use of the sorbent Carbopack-X for pumped sampling of certain VOCs. The results were obtained by dosing samplers in a controlled atmosphere test facility (CATFAC) operating under well-defined conditions of concentration, nominal temperature of 20 °C, wind speed of 0.5 m s^?1, and relative humidities of 0% and 80%. Field measurements were also obtained to provide supplementary data to support the laboratory study. Results are compared to existing published data, where these are available.     

Microwave plasma conversion of volatile organic compounds

A microwave-induced, steam/Ar/O2, plasma "torch" was operated at atmospheric pressure to determine the feasibility of destroying volatile organic compounds (VOCs) of concern. The plasma process can be coupled with adsorbent technology by providing steam as the fluid carrier for desorbing the VOCs from an adsorbent. Hence, N2 can be excluded by using a relatively inexpensive carrier gas, and thermal formation of oxides of nitrogen (NOx) is avoided in the plasma. The objectives of the study were to evaluate the technical feasibility of destroying VOCs from gas streams by using a commercially available microwave plasma torch and to examine whether significant byproducts were produced. Trichloroethene (TCE) and toluene (TOL) were added as representative VOCs of interest to a flow that contained Ar as a carrier gas in addition to O2 and steam. The O2 was necessary to ensure that undesirable byproducts were not formed in the process. Microwave power applied at 500-600 W was found to be sufficient to achieve the destruction of the test compounds, down to the detection limits of the gas chromatograph that was used in the analysis. Samples of the postmicrowave gases were collected on sorbent tubes for the analysis of dioxins and other byproducts. No hazardous byproducts were detected when sufficient O2 was added to the flow. The destruction efficiency at a fixed microwave power improved with the addition of steam to the flow that passed through the torch.     

Lysis of cyanobacteria with volatile organic compounds

One of bacteria collected from Lake Sagami, Japan, Brevibacillus sp., was found to have a lytic activity of cyanobacteria, but did not produce active compounds. Instead, the co-culturing of Microcystis with the Brevibacillus sp. enhanced the production of two volatile compounds, beta-cyclocitral and 3-methyl-1-butanol, and the former had a characteristic lytic activity. It was confirmed that these volatile compounds were derived from the cyanobacteria themselves. beta-Ionone, geosmin and 2-methylisoborneol derived from cyanobacteria and similar volatile compounds, terpenoids, produced by plants also had a lytic activity. The minimum inhibitory concentration values of the cyanobacterial metabolites were estimated to be higher than those of compounds from plants except for a few compounds. Among them, beta-cyclocitral only produced a characteristic color change of culture broth from green to blue. This color change is similar to the phenomenon observed when a sudden decline in growth of cyanobacteria begins in a natural environment.     

Simultaneous passive sampling of volatile organic compounds

In this paper, the results obtained in the simultaneous passive sampling of toluene, hexane, methyl ethyl ketone and ethyl acetate on activated charcoal are presented and compared with results obtained when the compounds were tested individually. Any observed deviations in the sampling rate are possibly due to the variations in the adsorption efficiency or in the coefficients of desorption caused by the presence of more than one adsorbate, though in all cases the values obtained are within the accepted margins recommended by NIOSH     

Inhalation exposure to volatile organic compounds in the printing industry

ABSTRACT

This study reports on the occupational inhalation exposure to VOCs of workers in the Kuwaiti printing industry. Using the evacuated canister methodology, we targeted 72 VOCs in three printeries and compared the concentrations to previous reports and relevant occupational exposure levels (OELs). We found that recent efforts in the printing industry to reduce VOC usage had been successful, as concentrations of key hazardous VOCs were substantially lower than anticipated. On the other hand, nearly all target VOCs were found. Non-production areas were sampled along with the offset printing areas, another strength of this study, and revealed exposures to hazardous VOCs among administers and digital printer and CTP operators. Exposure to ototoxic VOCs amounted to 1–3% of the OEL, consisting mostly of ethylbenzene, which was likely in use in two of the study printeries. Exposure to carcinogenic or probably carcinogenic VOCs was 15–20% of the OEL at four locations across the three printeries, consisting mostly of vinyl chloride and benzyl chloride. Vinyl chloride VOC was partially sourced from outdoors, but was also likely used inside the study printeries. Interestingly, concentrations of vinyl chloride were similar in most sampling locations to that of CFC-114, a CFC banned by the Montreal Protocol and not commonly used as a refrigerant. This unexpected finding suggests further study is warranted to identify the use of these VOCs in printeries. Exposure to hazardous VOCs up to nearly 50% of the OEL, consisting largely of bromoform and vinyl chloride. Bromoform was found in all the study printeries, sourced partially from outdoor air. The higher concentrations found inside the study printeries likely resulted from the use of the desalinated water for washing. This finding raises of emissions from sources other than blanket washes, and inks, etc. adding to the total VOC load in printery indoor air.

Implications: Results from this study indicate that efforts to reduce worker exposure to VOCs particularly dangerous to human health in recent years have been successful, but there is still much to be done to protect workers. Exposures to ototoxic and carcinogenic VOCs were identified, among both production and non-production workers. Unexpected findings included the apparent use in printing activities of the carcinogen vinyl chloride and CFC-114, banned under the Montreal Protocol. Observed lapses in safety procedures included failure to utilize ventilation systems and closing doors between work areas, indicating management and worker education should remain a priority.     

Solubility of volatile organic compounds in aqueous ammonia solution

The Ostwald solubility coefficient, L of 17 volatile organic compounds (VOCs) from the gas phase into water and dilute aqueous ammonia solutions was determined by the equilibrium partitioning in closed system-solid phase micro extraction (EPICS-SPME) method at 303 K and at 0-2.5 mol dm(-3) ammonia concentrations. Ammonia increased the solubility of all VOCs nearly linearly, but to a different extent. The difference in the solubility values in aqueous ammonia solutions (Lmix) compared to pure water (L) is explained on the basis of a Linear Solvation Energy Relationship (LSER) equation made applicable for solvent mixtures, logLmix - logL = x((sNH3 - sH2O)pi2H + (aNH3 - aH2O)Sigma2H + (bNH3 - bH2O)Sigmabeta2H + (vNH3 - VH2O)Vx). sNH3 - sH2O, aNH3 - aH2O, bNH3 - bH2O, vNH3 - vH2O are the differences of solvent parameters, x is the mole fraction, pi2H is the solute dipolarity-polarizability, Sigmaalpha2H is the effective hydrogen bond acidity of the solute, Sigmabeta2H is the effective hydrogen bond basicity of the solute and Vx, the McGowan characteristic volume. The most significant term was v, the phase hydrophobicity. The solubility behavior was explained by the change in structure of the aqueous solution: the presence of ammonia reduces the cavity effect. These findings show that the presence of compounds such as ammonia, frequently observed in environmental waters, especially wastewaters, affect the fugacity of VOCs, having consequences for the environmental partitioning of VOCs and having technical consequences towards wastewater treatment technologies.     

Measuring concentrations of volatile organic compounds in vinyl flooring

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.     

Nonvolatile,semivolatile, or volatile: Redefining volatile for volatile organic compounds

Although widely used in air quality regulatory frameworks, the term “volatile organic compound” (VOC) is poorly defined. Numerous standardized tests are currently used in regulations to determine VOC content (and thus volatility), but in many cases the tests do not agree with each other, nor do they always accurately represent actual evaporation rates under ambient conditions. The parameters (time, temperature, reference material, column polarity, etc.) used in the definitions and the associated test methods were created without a significant evaluation of volatilization characteristics in real world settings. Not only do these differences lead to varying VOC content results, but occasionally they conflict with one another. An ambient evaporation study of selected compounds and a few formulated products was conducted and the results were compared to several current VOC test methodologies: SCAQMD Method 313 (M313), ASTM Standard Test Method E 1868-10 (E1868), and U.S. EPA Reference Method 24 (M24). The ambient evaporation study showed a definite distinction between nonvolatile, semivolatile, and volatile compounds. Some low vapor pressure (LVP) solvents, currently considered exempt as VOCs by some methods, volatilize at ambient conditions nearly as rapidly as the traditional high-volatility solvents they are meant to replace. Conversely, bio-based and heavy hydrocarbons did not readily volatilize, though they often are calculated as VOCs in some traditional test methods. The study suggests that regulatory standards should be reevaluated to more accurately reflect real-world emission from the use of VOC containing products.

Implications:The definition of VOC in current test methods may lead to regulations that exclude otherwise viable alternatives or allow substitutions of chemicals that may limit the environmental benefits sought in the regulation. A study was conducted to examine volatility of several compounds and a few formulated products under several current VOC test methodologies and ambient evaporation. This paper provides ample evidence to warrant a reevaluation of regulatory standards and provides a framework for progressive developments based on reasonable and scientifically justifiable definitions of VOCs.     

Speciation of volatile organic compounds from poultry production

Volatile organic compounds (VOCs) emitted from poultry production are leading source of air quality problems. However, little is known about the speciation and levels of VOCs from poultry production. The objective of this study was the speciation of VOCs from a poultry facility using evacuated canisters and sorbent tubes. Samples were taken during active poultry production cycle and between production cycles. Levels of VOCs were highest in areas with birds and the compounds in those areas had a higher percentage of polar compounds (89%) compared to aliphatic hydrocarbons (2.2%). In areas without birds, levels of VOCs were 1/3 those with birds present and compounds had a higher total percentage of aliphatic hydrocarbons (25%). Of the VOCs quantified in this study, no single sampling method was capable of quantifying more than 55% of compounds and in several sections of the building each sampling method quantified less than 50% of the quantifiable VOCs. Key classes of chemicals quantified using evacuated canisters included both alcohols and ketones, while sorbent tube samples included volatile fatty acids and ketones. The top five compounds made up close to 70% of VOCs and included: 1) acetic acid (830.1 μg m^?3); 2) 2,3-butanedione (680.6 μg m^?3); 3) methanol (195.8 μg m^?3); 4) acetone (104.6 μg m^?3); and 5) ethanol (101.9 μg m^?3). Location variations for top five compounds averaged 49.5% in each section of the building and averaged 87% for the entire building.     

Qualitative analysis of volatile organic compounds on biochar

Qualitative identification of sorbed volatile organic compounds (VOCs) on biochar was conducted by headspace thermal desorption coupled to capillary gas chromatographic-mass spectrometry. VOCs may have a mechanistic role influencing plant and microbial responses to biochar amendments, since VOCs can directly inhibit/stimulate microbial and plant processes. Over 70 biochars encompassing a variety of parent feedstocks and manufacturing processes were evaluated and were observed to possess diverse sorbed VOC composition. There were over 140 individual chemical compounds thermally desorbed from some biochars, with hydrothermal carbonization (HTC) and fast pyrolysis biochars typically possessing the greatest number of sorbed volatiles. In contrast, gasification, thermal or chemical processed biochars, soil kiln mound, and open pit biochars possessed low to non-detectable levels of VOCs. Slow pyrolysis biochars were highly variable in terms of their sorbed VOC content. There were no clear feedstock dependencies to the sorbed VOC composition, suggesting a stronger linkage with biochar production conditions coupled to post-production handling and processing. Lower pyrolytic temperatures (?350 °C) produced biochars with sorbed VOCs consisting of short carbon chain aldehydes, furans and ketones; elevated temperature biochars (>350 °C) typically were dominated by sorbed aromatic compounds and longer carbon chain hydrocarbons. The presence of oxygen during pyrolysis also reduced sorbed VOCs. These compositional results suggest that sorbed VOCs are highly variable and that their chemical dissimilarity could play a role in the wide variety of plant and soil microbial responses to biochar soil amendment noted in the literature. This variability in VOC composition may argue for VOC characterization before land application to predict possible agroecosystem effects.     

Effects of airborne volatile organic compounds on plants

Routine measurements of volatile organic compounds (VOCs) in air have shown that average concentrations are very much smaller than those used in laboratory experiments designed to study the effects of VOCs on plants. However, maximum hourly concentrations of some VOCs can be 100 times larger than the average, even in rural air. Experimental studies have rarely extended for longer than a few days, so there is little information on potential long-term effects of exposure to small concentrations. This review considers the available evidence for long-term effects, based on laboratory and field data. Previous reviews of the literature from Germany and the USA are cited, prior to an assessment of the effects of individual VOCs. Although hydrocarbons from vehicle exhausts have been implicated in the observed effects on roadside vegetation, the evidence suggests that it is the nitrogen oxides in the exhaust gases that are mostly responsible. There is evidence that aromatic hydrocarbons can be metabolised in plants, although the fate of the metabolites is not known. There is a large literature on the effects of ethylene, because of its role as a plant hormone. Effects have been reported in the field, in response to industrial emissions, and dose-response experiments over several weeks in laboratory studies have clearly identified the potential for effects at ambient concentrations. The main responses are morphological (e.g. epinasty), which may be reversible, and on the development of flowers and fruit. Effects on seed production may be positive or negative, depending on the exposure concentration. Chlorinated hydrocarbons have been identified as potentially harmful to vegetation, but only one long-term experiment has studied dose-response relationships. As for ethylene, the most sensitive indication of effect was on seed production, although long-term accumulation of trichloroacetic acid in tissue may also be a problem. There is little evidence of the direct effects of oxygenated hydrocarbons on plants. Plants are a significant emission source of short-chain alcohols, aldehydes and ketones. Peroxyacetyl nitrate (PAN) has a well-documented history as damaging to vegetation. There have been few long-term experimental studies despite the field evidence for damaging effects. Early studies in California have been followed by more recent data from east Asia, but there is still a dearth of information on the potential for effects of PAN and related peroxyacyl nitrates on vegetation typical of regions around tropical and sub-tropical cities where PAN pollution is increasingly important. The lack of long-term measurements, coupled with the available evidence that effects are not linearly related to 'dose' measured as the product of exposure concentration and time, means that the possibility of adverse effects of VOCs on vegetation cannot be safely rejected, particularly in urban and industrial areas. Although reproductive processes (flowering, seed production) appear to be most sensitive, there have been no experimental studies on subsequent seed viability and the consequences at the ecosystem level of changes to plant phenology. The potential for VOC metabolites to accumulate in plant tissue has been demonstrated, but any subsequent effects on herbivores and phytophagous insects have yet to be investigated.     

车内空气中挥发性有机物的研究

采用热脱附-气相色谱/质谱联用法对4辆处于静止状态下的车辆内部空气中挥发性有机物（VOCs）进行了研究,共定性检出了48种有机物,其中C6～C9之间的组分较多;并对VOCs的总浓度进行了定量,1#～4#车分别为1846、2289、1104和3146 μg/m^3;其中BTEX占VOCs总量的20%～30%;车内VOCs浓度与温度及车辆使用年限密切相关.     

车内空气中挥发性有机物的研究

采用热脱附-气相色谱/质谱联用法对4辆处于静止状态下的车辆内部空气中挥发性有机物(VOCs)进行了研究,共定性检出了48种有机物,其中C6~C9之间的组分较多;并对VOCs的总浓度进行了定量,1#~4#车分别为1846、2289、1104和3146μg/m3;其中BTEX占VOCs总量的20%~30%;车内VOCs浓度与温度及车辆使用年限密切相关。     

室内空气中挥发性有机物采样方法进展

介绍了近年来室内空气中挥发性有机物的各种采样方法及适用范围，其中重点介绍了美国环保署最新版的TO－17方法和J.Pawliszyn发明的固相微萃取法（SPME），并对一系列的采样方法进行了比较，阐述了这些方法在国内外的应用及研究进展，同时讨论了这些方法的局限性。     

室内空气中挥发性有机物的释放特征分析

房屋装修后1周、1个月、3个月、6个月、12个月采集其室内空气样品进行甲醛、苯系物浓度的测定,分析释放规律;另选某处新居于装修后24 h、1周、1个月且密闭状态下采集室内空气中总挥发性有机化合物(TVOC)样品分析研究.结果表明,房屋装修后12个月内甲醛浓度随时间呈非线性递减,多项式回归方程为:y=0.277 13-0.199 72x+0.079 74x2-0.011 67x3+0.000 525 61x4,其中y为甲醛质量浓度,mg/m3;x为时间,月;各苯系物浓度也随时间呈逐渐下降趋势,且通过SPSS13.0软件进行Spearman相关性分析,发现各苯系物间显著相关;装修后不同时间段室内空气中TVOC组分发生变化,随着房屋封闭时间延长,TVOC浓度超标严重;TVOC组分的增多或减少是由于室内装修材料TVOC释放的增强或减弱,以及门窗缝隙所带来的微弱通风造成,无二次污染物的生成.