Partition Constants and Adsorption/Desorption Hysteresis for Volatile Organic Compounds on Soil from a Louisiana Superfund Site

The adsorption of four volatile organic compounds (1,4-dichloro-benzene, 1,2-dichloroethane, 1,2,2-trichloroethane and 1,1,2,2,-tetrachloroethane) on three soil types from a Superfund site (Petroprocessors Inc) in Baton Rouge, LA was studied with the purpose of obtaining an overall correlation for inclusion in a groundwater transport model being developed for site remediation. The soil-water partition constant, K_d was determined using a standard ASTM procedure (E–1195–87). Using the data for different soil types (fraction organic carbon between 0.11% and 1.13%) and different mineral surface areas (7 to 45 m²/g), the organic carbon contribution (K_oc) and the mineral matter contribution (K_min) to the partition constant were determined. The soils obtained were either from the Pleistocene period or recent shallow deposits at the site. Both log K_oc and log K_min were linearly correlated to log K_ow, the octanol-water partition constant. This data provided the basis for obtaining a general correlation for K_d on different soil types at the site. The predicted values were in agreement with that for a composite soil from the same site. The desorption of compounds from the high clay soil after the 24 hour adsorption period was observed to show a biphasic behavior, namely, an easily desorbed fraction and a desorption resistant fraction. The easily desorbed fraction was found to be satisfactorily predicted using the conventional K_d as obtained from the adsorption experiment. The slowly desorbing fraction had a time constant of several weeks. The concentration in the desorption resistant compartment was found to be dependant on the initial amount of contaminant available for adsorption. The aqueous phase concentration in equilibrium with the desorption resistant fraction was found to be 8 g/L for dichlorobenzene and 12 g/L for dichloroethane.     

Rate-Limited Desorption of Volatile Organic Compounds from Soils and Implications for the Remediation of a Louisiana Superfund Site

The rates of desorption of trichloroethylene (TCE) and 1,3-dichlorobenzene (DCB) from a silty soil at a Superfund site and a silty-clayey soil from an uncontaminated bottomland hardwoodswamp in Baton Rouge, Louisiana were studied in laboratory batchsystems. The effect of the age of soil contamination was studiedusing a laboratory-spiked soil incubated for 3 days, 3 months and5 months. An empirical non-linear model was used to describe thebi-phasic nature of desorption with one fraction (labile) beingreleased in relatively short periods of time (typically 24–100 hr) and a second fraction (non-labile or irreversible) beingresistant to desorption. The non-linear model parameters, viz.,the fraction of the chemical released rapidly (F), and the firstorder desorption rate coefficients, k ₁ and k ₂respectively for the labile and slowly released fractions weredetermined by fitting the experimental data to the model. Thedata fit the model well as indicated by the high r ² values.The estimate of k ₁ was good. However, the values of k ₂are known with less precision due to the limited duration of theexperiment and number of samples taken at long times. In addition, desorption kinetics of 3 and 5-month old contaminatedsoils showed that progressively less amount of contaminant was available for facile desorption (lower F) compared to freshly contaminated soil. The labile fraction had desorption rate constants of the order of 10^-1 h^-1, whereas the slowlyreleased fraction had rate constants of the order of 10^-4 h^-1 in accord with literature reported values for a varietyof other compounds and soils. Possible mechanisms describing these rates and implications for the site clean up are discussed.     

水质中多种挥发性有机物的同时测定

在采用双柱双检测器的基础上,对水中24种挥发性有机物进行了同时测定。当进样体积为5ml时,最低检测限为0．5俐L,线性范围及测定范围为0．5～50倒L,1μg/L和20μg/L浓度水平的加标回收率在80．0％-110％之间,变异系数为0．6％～9．2％,实验结果令人满意。     

Distribution Of Volatile Organic Compounds In Ambient Air Of Kaohsiung, Taiwan

Automobile emissions have created a major hydrocarbon pollution problem in the ambient air of Taiwan. The aim of this study was to determine the volatile organic compounds (VOCs) in the ambient air of Kaohsiung, Taiwan. The spatial distribution, temporal variation, and correlations of VOCs at three study sites, selected based on traffic densities and distances from a freeway, were discussed. Sixty-four hydrocarbons were identified in the ambient air. Among all of the VOC species, acetone, aromatic and aliphatic compounds constituted the major constituents. Higher concentrations of VOCs existed further away from major arteries as compared to those found near the freeway. Therefore, the distance from the freeway may not be a sufficient index for reflecting actual air quality in the study area. Weather conditions, wind speed and direction did not affect the distribution of VOC concentrations in the three study sites. Other factors, such as the height and density of buildings, traffic conditions or commercial activities, might affect the distribution of VOCs.     

预冷浓缩系统与气相色谱——质谱法测定室内空气中挥发性有机物

针对室内空气挥发性有机物测定方法的不足,本文采用预冷浓缩系统和气相色谱,质谱联用。建立了测定室内空气中39种挥发性有机物的分析方法,该方法采用苏码罐采样,经液氮预冷冻浓缩后,用心城由检测。该方法灵敏度高,操作简便、重现性好、准确度高,适用于室内空气中挥发性有机物的测定。     

Soil Gas Volatile Organic Compound Concentration Contours for Locating Vadose Zone Nonaqueous Phase Liquid Contamination

Diffusion of VOC from cylindrical vadose zone domains contaminatedwith distributed nonaqueous phase liquid is examined in the steadystate approximation. The effects of first-order biodegradation and ofan extended underlying pool of LNAPL floating on the water table belowthe cylindrical domain are explored by means of an orthogonal functionsapproach. The distribution of VOC in the vadose zone above a floatingcircular LNAPL pool of finite size is explored by a numerical method.The results provide information useful in estimating the spacing anddepth at which soil gas samples should be taken in order to detect thepresence of such source areas. Comparison of model results with soilgas VOC measurements at various depths also provides insight into theextent to which natural biodegradation of the VOCs is taking place.     

Characterization of Organic Compounds in Compost-Amended Soil

Samples of compost-amended soil from waste dumping sites in Lagos Metropolis were extracted with dichloromethane (3 × 20 cm³) and the extract was evaporated at 35 °>C. The residue was extracted with 2,2,4-trimethylpentane, and portions of the solution were applied to a column containing silica gel from which aliphatic and aromatic hydrocarbons were eluted with n-hexane and toluene respectively. Analysis of the n-hexane fraction using gas chromatography showed the presence of a mixture of aliphatic hydrocarbons, ranging from C₉ to C₂₅, while ultraviolet analysis of the toluene fraction suggested 1,2-benzanthracene; 2,3-benzphenanthrene, chrysene and pyrene as polyaromatic compounds present in samples analyzed. The crude extracts were highly coloured and viscous. Total extractable organic residues in the 2,2,4-trimethylpentane extracts ranged from 36 to 89 mg g^-1 of soil.     

饮用水源中挥发性有机物分析方法的优化和应用

采用吹扫捕集—气相色谱—质谱联用技术分析水中的24种挥发性有机物。通过优化分析条件,改善了各组份的分离效果,节省了分析时间,得到各组份检测限为0.001-0.099μg/L,相对标准偏差为2.3%-5.6%,加标回收率为91.2%-107.6%,方法具有较好的精密度、准确度和低检测限。同时对漳州市饮用水源中的24种挥发性有机物进行监测分析,结果均低于检测限。     

土壤中挥发性有机物的顶空制备方法研究

对土壤中挥发性有机物（VOCs）有效提取的顶空（HS）前处理条件进行了研究。结果表明,在一定的气相色谱条件下,影响顶空装置对挥发性有机物提取水平的主要有顶空平衡时间、平衡温度、基准修正液的加入量等因素,在一定的HS—GC条件下,土壤中挥发性有机物的准确度可达80%。     

Organic Liquids Storage Tanks Volatile Organic Compounds (VOCS) Emissions Dispersion and Risk Assessment in Developing Countries: The Case of Dar-Es-Salaam City, Tanzania

The emission estimation of nine volatile organic compounds (VOCs) from eight organic liquids storage tanks companies in Dar-es-Salaam City Tanzania has been done by using US EPA standard regulatory storage tanks emission model (TANKS 4.9b). Total VOCs atmospheric emission has been established to be 853.20 metric tones/yr. It has been established further that petrol storage tanks contribute about 87% of total VOCs emitted, while tanks for other refined products and crude oil were emitting 10% and 3% of VOCs respectively. Of the eight sources (companies), the highest emission value from a single source was 233,222.94 kg/yr and the lowest single source emission value was 6881.87 kg/yr. The total VOCs emissions estimated for each of the eight sources were found to be higher than the standard level of 40,000 kg/yr per source for minor source according to US EPA except for two sources, which were emitting VOCs below the standard level. The annual emissions per single source for each of the VOCs were found to be below the US EPA emissions standard which is 2,000~kg/yr in all companies except the emission of hexane from company F1 which was slightly higher than the standard. The type of tanks used seems to significantly influence the emission rate. Vertical fixed roof tanks (VFRT) emit a lot more than externally floating roof tanks (EFRT) and internally floating roof tanks (IFRT). The use of IFRT and EFRT should be encouraged especially for storage of petrol which had highest atmospheric emission contribution. Model predicted atmospheric emissions are less than annual losses measured by companies in all the eight sources. It is possible that there are other routes for losses beside atmospheric emissions. It is therefore important that waste reduction efforts in these companies are directed not only to reducing atmospheric emissions, but also prevention of the spillage and leakage of stored liquid and curbing of the frequently reported illegal siphoning of stored products. Emission rates for benzene, toluene, and xylene were used as input to CALPUFF air dispersion model for the calculation of spatial downwind concentrations from area sources. By using global positioning system (GPS) and geographical information system (GIS) the spatial benzene concentration contributed by organic liquid storage tanks has been mapped for Dar-es-Salaam City. Highest concentrations for all the three toxic pollutants were observed at Kigamboni area, possibly because the area is located at the wind prevailing direction from the locations of the storage tanks. The model predicted concentrations downwind from the sources were below tolerable concentrations by WHO and US-OSHA. The highest 24 hrs averaging time benzene concentration was used for risk assessment in order to determine maximum carcinogenic risk amongst the population exposed at downwind. Established risk for adult and children at 2.9×10^-3 and 1.9×10^-3 respectively, are higher than the acceptable US-EPA risk of 1×10^-6. It is very likely that the actual VOCs concentrations in some urban areas in Tanzania including Dar-es-Salaam City are much higher than the levels reported in this study when other sources such as petrol stations and motor vehicles on the roads are considered. Tanzania Government therefore need to put in place: an air quality policy and legislation, establish air quality guidelines and acquire facilities which will enable the implementation of air quality monitoring and management programmes.     

Volatile Organic Compounds: Sampling Methods and Their Worldwide Profile in Ambient Air

The atmosphere is a particularly difficult analytical system because of the very low levels of substances to be analysed, sharp variations in pollutant levels with time and location, differences in wind, temperature and humidity. This makes the selection of an efficient sampling technique for air analysis a key step to reliable results. Generally, methods for volatile organic compounds sampling include collection of the whole air or preconcentration of samples on adsorbents. All the methods vary from each other according to the sampling technique, type of sorbent, method of extraction and identification technique. In this review paper we discuss various important aspects for sampling of volatile organic compounds by the widely used and advanced sampling methods. Characteristics of various adsorbents used for VOCs sampling are also described. Furthermore, this paper makes an effort to comprehensively review the concentration levels of volatile organic compounds along with the methodology used for analysis, in major cities of the world.     

吹扫捕集-GC/MS-SIM法测定海水中挥发性有机污染物

采用吹扫捕集 -GC/MS -SIM法测定水中挥发性有机物 ,具有定量准确、操作简便等特点 ,检测限可达ng/L级 ,适合环境水中低浓度挥发性有机物的测定。测定实际海水样品 ,其浓度范围在 0 4ng/L～ 1 0 0 0ng/L之间。     

Spatial Analysis of Volatile Organic Compounds from a Community-Based Air Toxics Monitoring Network in Deer Park,Texas, USA

In the summer of 2003, ambient air concentrations of volatile organic compounds (VOCs) were measured at 12 sites within a 3-km radius in Deer Park, Texas near Houston. The purpose of the study was to assess local spatial influence of traffic and other urban sources and was part of a larger investigation of VOC spatial and temporal heterogeneity influences in selected areas of Houston. Seventy 2-h samples were collected using passive organic vapor monitors. Most measurements of 13 VOC species were greater than the method detection limits. Samplers were located at 10 residential sites, a regulatory air monitoring station, and a site located at the centroid of the census tract in which the regulatory station was located. For residential sites, sampler placement locations (e. g., covered porch vs. house eaves) had no effect on concentration with the exception of methyl tertiary-butyl ether (MTBE). Relatively high correlations (Pearson r > 0.8) were found between toluene, ethylbenzene, and o,m,p-xylenes suggesting petroleum-related influence. Chloroform was not correlated with these species or benzene (Pearson r < 0.35) suggesting a different source influence, possibly from process-related activities. As shown in other spatial studies, wind direction relative to source location had an effect on VOC concentrations.     

Characterization of Volatile Organic Compounds (VOCs) and Their Sources in the Air of Izmir, Turkey

Air samples were collected in Izmir, Turkey at two (suburban and urban) sites during three sampling programs in 2002 and 2004 to determine the ambient concentrations of several monoaromatic, chlorinated and oxygenated volatile organic compounds (VOCs). Samples were analyzed for 60 VOCs using gas chromatography/mass spectrometry and 28 compounds were detected in most samples. On the average, urban air VOC concentrations were about four times higher than those measured at the suburban site. Toluene (40.6%) was the most abundant compound in suburban site and was followed by benzene (7.4%), o,m-xylene (6.5%), and 1,2-dichloroethane (5.1%). In urban site, toluene (30.5%), p-xylene (14.9%), o,m-xylene (11.4%), and ethyl benzene (7.2%) were the dominating compounds in summer. In winter, toluene (31.1%), benzene (23.9%), 1,2-dichloroethane (9.5%), and o,m-xylene (8.2%) were the most abundant compounds. Receptor modeling (positive matrix factorization) has been performed to estimate the contribution of specific source types to ambient concentrations. Six source factors (gasoline vehicle exhaust, diesel vehicle exhaust+residential heating, paint production/application, degreasing, dry cleaning, and an undefined source) were extracted from the samples collected in the urban site. Three source factors (gasoline vehicle exhaust, diesel vehicle exhaust, and paint production/application) were identified for the suburban site.     

Qualitative Study of Organic Compounds in Wastewaters of a Swine Slaughterhouse

The main purpose of this work was the preliminary qualitative study of organic compounds in wastewaters of swine slaughterhouses. The samples were collected in a local abattoir and submitted to Liquid-Liquid Extraction (LLE) and Solid-phase Extraction (SPE) with XAD-4^TM resin as stationary phase. The instrumental analysis was performed by Gas Chromatography with Mass Spectrometer Detector (GC/MSD). The compounds present in the LLE and SPE extracts were identified by the GC/MSD library (Wiley). The results pointed out that SPE and LLE can extract practically the same classes of compounds at the same amounts. LLE works well for the extraction of polar organic compounds, with acidified samples, while SPE presents a better performance for the extraction of less polar organic compounds. Aldehydes were main class of the compounds extracted by SPE and LLE and decenal was the major aldehyde identified. Fatty alcohols and carboxylic acids were also identified but in minor proportions.     

GC／MS法测定自来水中挥发性有机化合物

应用ＧＣ／ＭＳ联用仪对自来水中挥发性有机化合物进行了测定,实现了了吹扫－捕集装置与联用仪的连接,并由ＤＰＦＣ控制,使整个过程自动化。检测的自来水样中,主要有氯甲烷类,溴氯甲烷类和苯类等挥发性化合物。     

Ambient Air Quality at the Site of a Former Manufactured Gas Plant

Prior to the 1950's, manufactured gas was commerciallyproduced from the pyrolysis of coal, coke, and oil atfacilities that are termed manufactured gas plants (MGPs). The constituents of residual coal tar present on many MGPsites are an environmental health concern because of theirtoxicity and the possibility for their off-site migration viawater and air. Atmospheric concentrations of five volatileorganic compounds (VOCs, e.g., benzene), sixteen polycyclicaromatic hydrocarbons (PAHs, e.g., naphthalene), and particulate matter less than 10 microns in aerodynamicdiameter (PM₁₀) were measured at the site of a former MGP. Air samples were obtained before, during, and after excavationof subterranean coal tar at the site. The results of thisinvestigation indicate that subterranean coal tar was not aprimary source of VOCs and PAHs in the local atmosphere beforeor after remediation of the site. However, excavation,treatment, blending, and transfer of the coal tar duringremediation generated concentrations of selected aromatic andsemi-volatile organic compounds that were substantiallygreater than typical ambient levels. In addition, these datasuggest that blending and mixing of coal tars could lead toexceedance of the U.S. National Ambient Air Quality Standardfor PM₁₀, although additional research is required to fullyevaluate this possibility. Nuisance odors associated with thesite remediation were likely the result of naphthalene andpossibly isomers of xylene. Air pollutant concentrationsmeasured adjacent to the excavation area and at the siteperimeter during remediation activities were less than therelevant occupational and environmental exposure limits.     

吹扫—捕集／气相色谱法测定水中挥发性有机物

为提高样品分析效率,研究并建立了吹扫-捕集／气相色谱／氢火焰检测器联用同时测定水中1,2-二氯乙烷、苯、甲苯、氯苯、乙苯、对-二甲苯、间-二甲苯、苯乙烯、邻-二甲苯、异丙苯、1,4-二氯苯、1,2-二氯苯、硝基苯、1,3,5-三氯苯、1,2,4-三氯苯、1,2,3-三氯苯、六氯丁二烯17种挥发性有机物的分析方法。结果表明,当进样体积为25．0ml时,最低检出限为0．0034-0．1088μg/L,相对标准偏差为1．8％～6．4％,加标平均回收率为97．6％-105．8％。该方法可快速、简便、准确、高灵敏度的测定水中17种挥发性有机物,并适用于饮用水和地表水中挥发性有机物的测定。     

Sampling and Analysis of Volatile Organic Compounds Emitted from Leaded and Unleaded Gasoline Powered Motor Vehicles

Forecasts of air quality provide information to the general public during periods with high levels of air pollution. Criteria for testing the validity and reliability of forecast systems are discussed. As the objectives of a forecast may widely differ (providing information to the public or triggering short-term emission reduction measures) there is not a single evaluation procedure. It is recommended to use a set of performance indicators. The strong year-to-year variability in occurrence of smog episodes makes it necessarily to use several years of data in the evaluation.     

Soil Aquifer Treatment (SAT) as a Natural and Sustainable Wastewater Reclamation/Reuse Technology: Fate of Wastewater Effluent Organic Matter (EfOM) and Trace Organic Compounds

Through the use of innovative analytical tools, the removal/transformation of wastewater effluent organic matter (EfOM) have been tracked through soil aquifer treatment (SAT). While the total amount of EfOM is significantly reduced by SAT, there are trends of shorter term versus longer term removals of specific EfOM fractions. The preferential removal of non-humic components (e.g., proteins, polysaccharides) of EfOM occurs over shorter travel times/distances while humic components (i.e., humic substances) are removed over longer travel times/distances, with the removal of both by sustainable biodegradation. Dissolved organic nitrogen (DON), a surrogate for protein-like EfOM, is also effectively removed over shorter term SAT. There is some background humic-like natural organic matter (NOM), associated with the drinking water source within the watershed, that persists through SAT. While most effluent-derived trace organic compounds are removed to varying degrees as a function of travel time and redox conditions, a few persist even through longer term SAT.