Emission of volatile organic sulfur compounds from a heavily polluted river in Guangzhou, South China

Emissions of five volatile organic sulfur compounds (VOSCs), including methanethiol, carbonyl sulfide, dimethyl sulfide, carbon disulfide, and dimethyl disulfide, from a heavily polluted river, Shijing River in Guangzhou of South China, was studied. The results showed that the amounts of all VOSCs emitted from the river increased from downstream to upstream along the river with increasing magnitude of water pollution. The emission of carbonyl sulfide was the highest among the target analytes, ranging from 23.8 microg m(-2) h(-1) to 42.6 microg m(-2) h(-1) at the water surface of Shijin River. The concentration levels of VOSCs on the riverbank were lower than those at the water surface either in Shijing River or in Liuxi River. However, the contribution of dimethyl disulfide to the total VOSCs on the riverbank was higher than that at the water surface in most sampling sites, indicating that there might be a point source of dimethyl disulfide on the riverbank besides diffusion from water surface. The 24-h semi-continuous monitoring data revealed that the emissions of VOSCs at the water surface peaked at 9:00 and 21:00, which was consistent with the water quality variability in Shijin River caused by daily tidal variation.     

Soil sampling and analysis for volatile organic compounds

Concerns over data quality have raised many questions related to sampling soils for volatile organic compounds (VOCs). This paper was prepared in response to some of these questions and concerns expressed by Remedial Project Managers (RPMs) and On-Scene Coordinators (OSCs). The following questions are frequently asked:

1. Is there a specific device suggested for sampling soils for VOCs?
2. Are there significant losses of VOCs when transferring a soil sample from a sampling device (e.g., split spoon) into the sample container?
3. What is the best method for getting the sample from the split spoon (or other device) into the sample container?
4. Are there smaller devices such as subcore samplers available for collecting aliquots from the larger core and efficiently transferring the sample into the sample container?
5. Are certain containers better than others for shipping and storing soil samples for VOC analysis?
6. Are there any reliable preservation procedures for reducing VOC losses from soil samples and for extending holding times?

Guidance is provided for selecting the most effective sampling device for collecting samples from soil matrices. The techniques for sample collection, sample handling, containerizing, shipment, and storage described in this paper reduce VOC losses and generally provide more representative samples for volatile organic analyses (VOA) than techniques in current use. For a discussion on the proper use of sampling equipment the reader should refer to other sources (Acker, 1974; U.S. EPA, 1983; U.S. EPA, 1986a). Soil, as referred to in this report, encompasses the mass (surface and subsurface) of unconsolidated mantle of weathered rock and loose material lying above solid rock. Further, a distinction must be made as to what fraction of the unconsolidated material is soil and what fraction is not. The soil component here is defined as all mineral and naturally occurring organic material that is 2 mm or less in size. This is the size normally used to differentiate between soils (consisting of sands, silts, and clays) and gravels. Although numerous sampling situations may be encountered, this paper focuses on three broad categories of sites that might be sampled for VOCs:

1. Open test pit or trench.
2. Surface soils (<5 ft in depth).
3. Subsurface soils (>5 ft in depth).

     

Investigation and assessment of volatile organic compounds in water sources in China

456 water samples collected from 152 water sources in 2006 were analyzed for 21 volatile organic compounds (VOCs). Concentrations of 21 VOCs ranged from below method detection limits of the laboratory to 7.65 ??g/L (toluene), but seldom exceeded the concentration limits set in the National Drinking Water Quality Standards (GB5749-2006) or the National Environmental Quality Standards for Surface Water (GB3838-2002) of China. Of the 21 individual VOCs analyzed, 11 VOCs were detected in at least one sample at or above 1.0 ??g/L; 6.6% of the water samples had a detection of at least one VOC at or above 1.0 ??g/L, and 2.6% had a detection of at least two VOCs at or above 1.0 ??g/L. Based on the statistical data of detection frequencies above the method detection limits, 75% of the samples detected at least one VOC, and 65% of the samples detected at least two VOCs. Chloroform, toluene, and 1,2-dichloroethene were the three most frequently detected VOCs, with detection frequencies of 76.97%, 68.42%, and 44.08%, respectively. Volatile halogenated hydrocarbons and gasoline components were the two most frequently detected VOC groups.     

Analysis of volatile organic compounds released during food decaying processes

A number of volatile organic compounds (VOCs) including acetone, methyl ethyl ketone, toluene, ethylbenzene, m,p-xylene, styrene, and o- xylene released during food decaying processes were measured from three types of decaying food samples (Kimchi (KC), fresh fish (FF), and salted fish (SF)). To begin with, all the food samples were contained in a 100-mL throwaway syringe. These samples were then analyzed sequentially for up to a 14-day period. The patterns of VOC release contrasted sharply between two types of fish (FF and SF) and KC samples. A comparison of data in terms of total VOC showed that the mean values for the two fish types were in the similar magnitude with 280 ± 579 (FF) and 504 ± 1,089 ppmC (SF), while that for KC was much lower with 16.4 ± 7.6 ppmC. There were strong variations in VOC emission patterns during the food decaying processes between fishes and KC that are characterized most sensitively by such component as styrene. The overall results of this study indicate that concentration levels of the VOCs differed significantly between the food types and with the extent of decaying levels through time.     

Vertical concentration gradients of volatile organic compounds in two NS-oriented street canyons

Diffusive samplers were used to measure the vertical concentrations of benzene, toluene, n-hexane, cyclohexane, ethylbenzene and o-, m- and p-xylenes on both sides of two NS-oriented street canyons in Murcia (Spain) during a 5-day period. Non-dimensional relationships of concentration and height were calculated in order to study the behaviour of their concentration vertical profiles. The results show that the vertical profiles of benzene, toluene, n-hexane and cyclohexane concentrations were similar in both streets and on both sides of each street. Some differences were found in vertical profiles between streets and sides for ethylbenzene and xylenes, probably due to their higher affinity for adsorption into building materials. The similarities found for the first set of VOCs suggest that the dynamics of the dispersion was the same for both streets and was mainly influenced by microscale thermal effects. Finally, the concentration measurements of benzene, toluene, n-hexane, cyclohexane, and ethylbenzene were adjusted to expressions in the form c?=?c ₀(h/h ₀) ^A , and a regression coefficient R ²?=?0.962 (p?=?0.0000) was obtained. The decreasing concentration of these compounds with height should be taken into account when assessing population exposure to these pollutants.     

Validation of evacuated canisters for sampling volatile organic compounds in healthcare settings

Healthcare settings present a challenging environment for assessing low-level concentrations of specific volatile organic compounds (VOCs) in the presence of high background concentrations of alcohol from the use of hand sanitizers and surface disinfectants. The purposes of this laboratory-based project were to develop and validate a sampling and analysis methodology for quantifying low-level VOC concentrations as well as high-level alcohol concentrations found together in healthcare settings. Sampling was conducted using evacuated canisters lined with fused silica. Gas chromatography/mass spectrometry analysis was performed using preconcentration (for ppb levels) and loop injection (for ppm levels). For a select list of 14 VOCs, bias, precision, and accuracy of both the preconcentration and loop injection methods were evaluated, as was analyte stability in evacuated canisters over 30 days. Using the preconcentration (ppb-level) method, all validation criteria were met for 13 of the 14 target analytes-ethanol, acetone, methylene chloride, hexane, chloroform, benzene, methyl methacrylate, toluene, ethylbenzene, m,p-xylene, o-xylene, alpha-pinene, and limonene. Using the loop injection (ppm-level) method, all validation criteria were met for each analyte. At ppm levels, alpha-pinene and limonene remained stable over 21 days, while the rest of the analytes were stable for 30 days. All analytes remained stable over 30 days at ppb levels. This sampling and analysis approach is a viable (i.e., accurate and stable) methodology that will enable development of VOC profiles for mixed exposures experienced by healthcare workers.     

Comprehensive screening and priority ranking of volatile organic compounds in Daliao River,China

An analytical strategy for comprehensive screening of target and non-target volatile organic compounds (VOCs) in surface water was developed, and it was applied to the analysis of VOCs in water samples from Daliao River. The target VOCs were quantified using purge and trap-gas chromatography-mass spectrometry (P&T-GC/MS). Among 20 water samples, 34 VOCs were detected at least once. For the screening of non-target VOCs, the double distillation apparatus was used for the pre-concentration of VOCs prior to P&T-GC/MS analysis. Subsequently, deconvolution software and NIST mass spectral library were applied for the identification of the non-target compounds. A total of 17 non-target VOCs were identified. The most frequently detected VOCs (detection frequencies >80 %) included toluene, benzene, naphthalene, 1,2-dichloroethane, 1,1,2-trichloroethane, and methyl tert-butyl ether. The distribution of VOCs obviously varied according to the sampling sites. The total concentrations of VOCs in water samples collected from the heavily industrialized cities (Anshan and Liaoyang) and the busy port city (Yingkou) were relatively high. The top ten priority VOCs, including naphthalene, 1,2-dichloroethane, o-xylene, 1,3-dichlorobenzene, tetrachloroethene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, ethylbenzene, m-xylene, and p-xylene, were obtained by the ranking of the detected VOCs according to their occurrence and ecological effects. These compounds should be given more attention in monitoring and drainage control strategies.     

吹扫捕集/气相色谱法测定空气中挥发性有机物

研究并建立了用吹扫捕集气相色谱法测定空气中挥发性有机物的分析方法。以空气中苯系物为目标化合物,以静态法配制标准气体,分别作了高、中、低三种浓度的标准曲线,其相关系数在0 98以上。该法对空气中苯系物的方法检出限为0 14～0 16μg m3,相对标准偏差在2 1%～6 3%之间,回收率在92%～120%。     

Characterizations of volatile organic compounds during high ozone episodes in Beijing,China

Air samples were collected in Beijing from June through August 2008, and concentrations of volatile organic compounds (VOCs) in those samples are here discussed. This sampling was performed to increase understanding of the distributions of their compositions, illustrate the overall characteristics of different classes of VOCs, assess the ages of air masses, and apportion sources of VOCs using principal compound analysis/absolute principal component scores (PCA/APCS). During the sampling periods, the relative abundance of the four classes of VOCs as determined by the concentration-based method was different from that determined by the reactivity approach. Alkanes were found to be most abundant (44.3–50.1%) by the concentration-based method, but aromatic compounds were most abundant (38.2–44.5%) by the reactivity approach. Aromatics and alkenes contributed most (73–84%) to the ozone formation potential. Toluene was the most abundant compound (11.8–12.7%) during every sampling period. When the maximum incremental reactivity approach was used, propene, toluene, m,p-xylene, 1-butene, and 1,2,4-trimethylbenzene were the five most abundant compounds during two sampling periods. X/B, T/B, and E/B ratios in this study were lower than those found in other cities, possibly due to the aging of the air mass at this site. Four components were extracted from application of PCA to the data. It was found that the contribution of vehicle exhaust to total VOCs accounted for 53% of VOCs, while emissions due to the solvent use contributed 33% of the total VOCs. Industrial sources contributed 3% and biogenic sources contributed 11%. The results showed that vehicle exhausts (i.e., unburned vehicle emissions + vehicle internal engine combustion) were dominant in VOC emissions during the experimental period. The solvent use made the second most significant contribution to ambient VOCs.     

人体接触挥发性有机化合物的生物标志物

生物标志物是阐明接触与健康损害之间关系的工具。综述了３７ 篇文献,简单论述了挥发性有机化合物的各种生物标志物,这些生物标志物包括暴露生物标志物,效应生物标志物和易感性生物标志物。还简述了各种生物标志物之间的相互关系,并介绍了各种生物标志物的研究现状和发展前景,以及应用它们来评价ＶＯＣｓ对人体健康的影响。     

Workplace monitoring for volatile organic compounds using thermal desorption-gas chromatography-mass spectrometry

The interest in the identification of volatile organic compounds in the workplace has been a major focus of many National Institute for Occupational Safety and Health (NIOSH) field studies. A primary technique for sampling and analysis of these compounds is summarized by NIOSH Manual of Analytical Methods (NMAM) 2549. This is a screening method that uses a multi-bed sorbent to trap a wide variety of compounds and compound classes. Thermal desorption techniques are used as a first attempt to characterize potential contaminants in a workplace and to determine what future sampling and analyses must be performed. Field examples are provided to show the versatility of thermal desorption methods and techniques. Due to their sensitivity, thermal desorption tube methods are sometimes required in order to measure the workplace concentrations of unusual compounds. In other situations, the exposures are too high or varied to make thermal desorption tubes practical. In these cases, the identification of contaminants with thermal desorption tubes leads to new method developments for the quantification of specific compounds using more conventional solid sorbent-solvent desorption based methods.     

A dual channel gas chromatograph for atmospheric analysis of volatile organic compounds including oxygenated and monoterpene compounds

A dual channel gas chromatograph with flame ionisation detectors has been used extensively for analysis of volatile organic compounds in the atmosphere and forms the basis of two monitoring instruments contributing VOC data to the World Meteorological Organisation - Global Atmosphere Watch network. Recent modifications to the methodology have broadened the scope of the instrument; to incorporate measurements of selected monoterpenes, and achieve improved accuracy in the measurement of oxygenated volatile organic compounds. Analysis of selected monoterpenes has been achieved without any significant loss of resolution of the non-methane hydrocarbons or oxygenated compounds. Quantification of 64 different VOCs of varying functionalities are reported with detection limits in the range 1-5 parts per trillion. Here we present a summary of the instrumental and calibration details for the methodology, which continues to be used on many field projects, along with a discussion of the associated measurement uncertainties.     

利用保留时间锁定软件对水中挥发性有机物进行气相色谱测定

使用保留时间锁定软件 (RTL) ,在气相色谱体系中建立了水质中 5 3种挥发性有机物的保留时间数据库 ,使原始的保留时间成为化合物定性的可靠参数 ,实现了未知样品在色谱仪上的定性 ,提高了分析效率。     

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 μm 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 μg/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 μg/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.     

Compact semi-automatic incident sampler for personal monitoring of volatile organic compounds in occupational air

Suddenly occurring and time limited chemical exposures caused by unintended incidents might pose a threat to many workers at various work sites. Monitoring of exposure during such occasional incidents is challenging. In this study a compact, low-weight and personal semi-automatic pumped unit for sampling of organic vapor phase compounds from occupational air during sporadic and suddenly occurring incidents has been developed, providing simple activation by the worker potentially subjected to the sudden occurring exposures when a trained occupational hygienist is not available. The sampler encompasses a tube (glass or stainless steel) containing an adsorbent material in combination with a small membrane pump, where the adsorbent is capped at both ends by gas tight solenoid valves. The sampler is operated by a conventional 9 V battery which tolerates long storage time (at least one year), and is activated by pulling a pin followed by automatic operation and subsequent closing of valves, prior to shipping to a laboratory. The adjustable sampling air flow rate and the sampling time are pre-programmed with a standard setting of 200 mL min(-1) and 30 min, respectively. The average airflow in the time interval 25-30 min compared to average airflow in the interval 2-7 min was 92-95% (n = 6), while the flow rate between-assay precisions (RSD) for six different samplers on three days each were in the range 0.5-3.7%. Incident sampler recoveries of VOCs from a generated VOC atmosphere relative to a validated standard method were between 95 and 102% (+/-4-5%). The valves that seal the sampler adsorbent during storage have been shown to prevent an external VOC atmosphere (500 mg m(-3)) to enter the adsorbent tube, in addition to that the sampler adsorbent is storable for at least one month due to absence of ingress of contaminants from internal parts. The sampler was also suitable for trapping of semi-volatile organophosphates.     

A novel in vitro exposure technique for toxicity testing of selected volatile organic compounds

Exposure to vapours of volatile chemicals is a major occupational and environmental health concern. Toxicity testing of volatile organic compounds (VOCs) has always faced significant technological problems due to their high volatility and/or low solubility. The aim of this study was to develop a practical and reproducible in vitro exposure technique for toxicity testing of VOCs. Standard test atmospheres of xylene and toluene were generated in glass chambers using a static method. Human cells including: A549-lung derived cell lines, HepG2-liver derived cell lines and skin fibroblasts, were grown in porous membranes and exposed to various airborne concentrations of selected VOCs directly at the air/liquid interface for 1 h at 37 degrees C. Cytotoxicity of test chemicals was investigated using the MTS (3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium) and NRU (neutral red uptake) assays following 24 h incubation. Airborne IC(50) (50% inhibitory concentration) values were determined using dose response curves for xylene (IC(50)=5350+/- 328 ppm, NRU; IC(50)=5750+/- 433 ppm, MTS in skin fibroblast) and toluene (IC(50)=0 500+/- 527 ppm, NRU; IC(50)=11,200 +/- 1,044 ppm, MTS in skin fibroblast). Our findings suggest that static direct exposure at the air/liquid interface is a practical and reproducible technique for toxicity testing of VOCs. Further, this technique can be used for inhalational and dermal toxicity studies of volatile chemicals in vitro as the exposure pattern in vivo is closely simulated by this method.     

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

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

Analysis of volatile organic compounds (VOCs) in sediments using in situ SPME sampling

A new method of determining the composition of sediment/soil gases and their volatile organic compound (VOC) content is described. VOCs were collected in situ from intertidal sediments in the Menai Strait and surrounding areas. The sampling was performed using a portable sampler comprising a funnel coupled to a SPME fibre. Gases were extracted from the sediments using a small vacuum pump pulling 100 mL min(-1) at atmospheric pressure. Sixty one different compounds were detected in the samples, and their fluxes and concentrations were determined. The compounds were classified into groups: halogenated, sulfur containing compounds, aldehydes, BTEXs (benzene, toluene, ethyl benzene and xylene) and aliphatic hydrocarbons. Results of principal component analysis (PCA) showed that the chemical composition of extracted gas was influenced primarily by sediment type. Muddy anoxic sediments were dominated by halogenated and sulfur containing compounds and sandy sediments had more aldehydes and BTEXs.     

Stabilities of 58 volatile organic compounds in fused-silica-lined and SUMMA polished canisters under various humidified conditions

Fused-silica-lined (FSL) canisters and SUMMA polished (SUMMA) canisters were compared for the recoveries and the stabilities of 58 volatile organic compounds (VOCs) at low ppbv (volume/volume) levels under various humidified conditions using a three-stage preconcentration method followed by GC-MS analysis. The target VOCs included non-polar VOCs (e.g. halogenated hydrocarbons and aromatic hydrocarbons) and polar VOCs (e.g. alcohols, ketones, esters, ethers, nitriles and thiols). The three-stage preconcentration method was initially optimized for simultaneous analysis of non-polar and polar VOCs because determination of canister stability is dependent on the accuracy of analytical measurements. The method showed good linearity over the concentration range from 1 to 25 ppbv for all target analytes, and the correlation coefficients were higher than 0.9974. The method detection limits ranged from 0.023 to 0.39 ppbv. The test mixtures loaded in both type of canisters (n = 3) had concentrations of 1.7-2.5 ppbv per compound at ambient pressure under various humidified conditions (%RH = 1.6, 8.0, 27, 39, 53 and >99% with excess water present). All canister samples were initially analyzed on day 0 (after 6-12 h). The effect of competitive adsorption of water vapor and polar VOCs on active sites of interior surface was remarkably observed for SUMMA canisters. Polar VOCs had a greater requirement for water vapor to be present. The RH percentages that ensured good recovery on day 0 were RH > 8% for non-polar VOCs and RH > 27% for polar VOCs (except alcohols under the condition of RH > 99%). All thiols were not recovered from SUMMA canisters under all conditions. FSL canisters showed good recoveries of more than 86% for all VOCs under all conditions on day 0 (except alcohols under the condition of RH > 99%). The recoveries of alcohols in both canisters under the condition of RH > 99% displayed relatively low recoveries in the range 25-76% because of the partitioning effect into condensed water. The canister samples under the conditions of RH 8.0, 27, 53 and > 99% were analyzed for the stability test on days 3, 7, 14 and 28 after loading. All non-polar VOCs were reasonably stable in the FSL canisters under all examined conditions over 28 days. However, several polar VOCs that have relatively lower vapor pressure, e.g. MIBK, butyl acetate and alcohols except ethanol, showed unstable characteristics under relatively dry conditions (RH 8 and 27%) during 28 days. RH > 53% was needed to ensure good stabilities of all analytes except thiols with the recoveries of > 80% over 28 days for both canisters. Although the FSL canister showed good recoveries of more than 86% for thiols on day 0, drastic degradations were observed after day 3 and they were not detected after day 14.     

某乡镇大气中毒害挥发性有机物的研究

对经济较发达的某乡镇大气的毒害挥发性有机化合物研究表明,该镇城区及其较发达的乡村已受到一定程度的有机污染,大气中主要存在苯系物、萘、氯代烃等毒害挥发性有机化合物.个别样品的苯乙烯含量高达14.50μg/m3,此值已超过中国居住区最高容许浓度.