Occurrence of Volatile Organic Compounds in Aquifers of the United States1

Abstract: Samples of ambient ground water were collected during 1985‐2002 from 3,498 wells in 98 aquifer studies throughout the United States. None of the sampled wells were selected because of prior knowledge of nearby contamination. Most of these samples were analyzed for 55 volatile organic compounds (VOCs) to characterize their national occurrence. Volatile organic compounds were found in samples collected from 90 of the 98 aquifer studies. Occurrence frequencies of one or more VOCs for the 98 aquifer studies ranged from 0 to about 77% at an assessment level of 0.2 microgram per liter (μg/l). The aquifer studies with the largest occurrence frequencies were in southern Florida, southern New York, southern California, New Jersey, and Nevada. Trihalomethanes and solvents were the most frequently occurring VOC groups. Of the 55 VOCs included in this assessment, 42 occurred in at least one sample at an assessment level of 0.2 μg/l. Chloroform, perchloroethene, and methyl tert‐butyl ether were the most frequently occurring VOCs. Many factors, such as the hydrogeology of the aquifer, use of VOCs, land use, and the transport and fate properties of VOCs, affect the occurrence of VOCs in ground water.     

VOLATILE ORGANIC COMPOUNDS IN GROUND WATER FROM RURAL PRIVATE WELLS, 1986 TO 19991

ABSTRACT: The U.S. Geological Survey (USGS) collected or compiled data on volatile organic compounds (VOCs) in samples of untreated ground water from 1,926 rural private wells during 1986 to 1999. At least one VOC was detected in 12 percent of samples from rural private wells. Individual VOCs were not commonly detected with the seven most frequently detected compounds found in only 1 to 5 percent of samples at or above a concentration of 0.2 microgram per liter (μg/l). An assessment level of 0.2 μg/l was selected so that comparisons of detection frequencies between VOCs could be made. The seven most frequently detected VOCs were: trichloromethane, methyl tert‐butyl ether, tetrachloroethene, dichlorodifluoromethane, methylbenzene, 1,1,1‐trichloroethane, and 1,2‐dibromo‐3‐chloropropane. Solvents and trihalomethanes were the most frequently detected VOC groups in private wells. The distributions of detections of gasoline oxygenates and fumigants seemed to be related to the use patterns of compounds in these groups. Mixtures were a common mode of occurrence of VOCs with one‐quarter of all samples with detections including two or more VOCs. The concentrations of most detected VOCs were relatively small and only 1.4 percent of samples had one or more VOC concentrations that exceeded a federally established drinking water standard or health criterion.     

Statistical evidence on the effectiveness of sewering to protect groundwater from VOC contamination

Volatile organic compounds (VOCs) are an important source of contamination of groundwater supplies in Massachusetts and many parts of the United States. One local response is to require sewering in wellhead protection areas as an easily enforceable policy designed to reduce the probability of VOC contamination of groundwater. Data were collected for 238 wellhead protection areas in Massachusetts on VOC contamination levels and the sewered and unsewered land uses in those aquifer recharge areas. Logistic regression procedures were used to see whether sewering had any statistical effect on likelihood of contamination of well water. The results provided limited, but not overpowering, support for the idea that requiring commercial and industrial land uses to use sewers would reduce the chance of VOC contamination.     

Combining steam injection with hydraulic fracturing for the in situ remediation of the unsaturated zone of a fractured soil polluted by jet fuel

A steam injection pilot-scale experiment was performed on the unsaturated zone of a strongly heterogeneous fractured soil contaminated by jet fuel. Before the treatment, the soil was stimulated by creating sub-horizontal sand-filled hydraulic fractures at three depths. The steam was injected through one hydraulic fracture and gas/water/non-aqueous phase liquid (NAPL) was extracted from the remaining fractures by applying a vacuum to extraction wells. The injection strategy was designed to maximize the heat delivery over the entire cell (10 m × 10 m × 5 m). The soil temperature profile, the recovered NAPL, the extracted water, and the concentrations of volatile organic compounds (VOCs) in the gas phase were monitored during the field test. GC-MS chemical analyses of pre- and post-treatment soil samples allowed for the quantitative assessment of the remediation efficiency. The growth of the heat front followed the configuration of hydraulic fractures. The average concentration of total hydrocarbons (g/kg of soil) was reduced by ～ 43% in the upper target zone (depth = 1.5-3.9 m) and by ～ 72% over the entire zone (depth = 1.5-5.5 m). The total NAPL mass removal based on gas and liquid stream measurements and the free-NAPL product were almost 30% and 2%, respectively, of those estimated from chemical analyses of pre- and post-treatment soil samples. The dominant mechanisms of soil remediation was the vaporization of jet fuel compounds at temperatures lower than their normal boiling points (steam distillation) enhanced by the ventilation of porous matrix due to the forced convective flow of air. In addition, the significant reduction of the NAPL mass in the less-heated deeper zone may be attributed to the counter-current imbibition of condensed water from natural fractures into the porous matrix and the gravity drainage associated with seasonal fluctuations of the water table.     

ENHANCEMENTS OF NONPOINT SOURCE MONITORING OF VOLATILE ORGANIC COMPOUNDS IN GROUND WATER1

ABSTRACT: The U.S. Geological Survey (USGS) has compiled a national retrospective data set of analyses of volatile organic compounds (VOCs) in ground water of the United States. The data are from Federal, State, and local nonpoint‐source monitoring programs, collected between 1985–95. This data set is being used to augment data collected by the USGS National Water‐Quality Assessment (NAWQA) Program to ascertain the occurrence of VOCs in ground water nationwide. Eleven attributes of the retrospective data set were evaluated to determine the suitability of the data to augment NAWQA data in answering occurrence questions of varying complexity. These 11 attributes are the VOC analyte list and the associated reporting levels for each VOC, well type, well‐casing material, type of openings in the interval (screened interval or open hole), well depth, depth to the top and bottom of the open interval(s), depth to water level in the well, aquifer type (confined or unconfined), and aquifer lithology. VOCs frequently analyzed included solvents, industrial reagents, and refrigerants, but other VOCs of current interest were not frequently analyzed. About 70 percent of the sampled wells have the type of well documented in the data set, and about 74 percent have well depth documented. However, the data set generally lacks documentation of other characteristics, such as well‐casing material, information about the screened or open interval(s), depth to water level in the well, and aquifer type and lithology. For example, only about 20 percent of the wells include information on depth to water level in the well and only about 14 percent of the wells include information about aquifer type. The three most important enhancements to VOC data collected in nonpoint‐source monitoring programs for use in a national assessment of VOC occurrence in ground water would be an expanded VOC analyte list, recording the reporting level for each analyte for every analysis, and recording key ancillary information about each well. These enhancements would greatly increase the usefulness of VOC data in addressing complex occurrence questions, such as those that seek to explain the reasons for VOC occurrence and nonoccurrence in ground water of the United States.     

Bioreactors for treatment of VOCs and odours – A review

Volatile organic compounds (VOCs) and odorous compounds discharged into the environment create ecological and health hazards. In the recent past, biological waste air treatment processes using bioreactors have gained popularity in control of VOCs and odour, since they offer a cost effective and environment friendly alternative to conventional air pollution control technologies. This review provides an overview of the various bioreactors that are used in VOC and odour abatement, along with details on their configuration and design, mechanism of operation, insights into the microbial biodegradation process and future R&D needs in this area.     

The Atmosphere can be a Source of Certain Water Soluble Volatile Organic Compounds in Urban Streams

Surface water and air volatile organic compound (VOC) data from 10 U.S. Geological Survey monitoring sites were used to evaluate the potential for direct transport of VOCs from the atmosphere to urban streams. Analytical results of 87 VOC compounds were screened by evaluating the occurrence and detection levels in both water and air, and equilibrium concentrations in water (C_w^s) based on the measured air concentrations. Four compounds (acetone, methyl tertiary butyl ether, toluene, and m‐ & p‐xylene) were detected in more than 20% of water samples, in more than 10% of air samples, and more than 10% of detections in air were greater than long‐term method detection levels (LTMDL) in water. Benzene was detected in more than 20% of water samples and in more than 10% of air samples. Two percent of benzene detections in air were greater than one‐half the LTMDL in water. Six compounds (chloroform, p‐isopropyltoluene, methylene chloride, perchloroethene, 1,1,1‐trichloroethane, and trichloroethene) were detected in more than 20% of water samples and in more than 10% of air samples. Five VOCs, toluene, m‐ & p‐xylene, methyl tert‐butyl ether (MTBE), acetone, and benzene were identified as having sufficiently high concentrations in the atmosphere to be a source to urban streams. MTBE, acetone, and benzene exhibited behavior that was consistent with equilibrium concentrations in the atmosphere.     

Characterization of total volatile organic compound emissions from paints

Recently, Homeswest in Western Australia and Murdoch University developed a project to construct low allergen houses (LAH) in a newly developed suburb. All potential volatile organic compound (VOC) emission materials used in LAH are required to be measured before the construction of LAH, to ensure they are low VOCs emission materials. To protect people sensitive to exposure to VOCs it is important to evaluate and select low VOCs emitting paints. In this paper, therefore, twelve different paints provided by local manufacturers were selected for analysis to characterize total volatile organic compounds (TVOC) emissions. Emissions of TVOCs from six organic solvent-soluble paints and six water-soluble paints were evaluated using a small test chamber under controlled temperature, relative humidity and air exchange rates. The major volatile organic compounds in these paints were also identified. The time dependence of TVOC emissions from paint products in the chamber was evaluated. TVOC emissions from organic solvent-soluble and water-soluble paints were compared. The influence of air exchange rate on the TVOC concentrations emitted from organic solvent-soluble and water-soluble paints was also investigated. A double-exponential equation was used to evaluate emission characteristics of TVOC from paint products. With this double-exponential model, the physical processes of TVOC emissions can be explained. A variety of emission parameters can be calculated and used to estimate real indoor TVOCs concentrations.     

罐采样-GC/MS法测定环境空气中挥发性有机物

采用SUMMA罐采样,空气预浓缩与气相色谱/质谱联用技术,建立了39种常见挥发性有机物的分析方法。选取攀枝花市不同功能区的5个测点,采集了4个季度的环境空气样品220个,定性检出挥发性有机物54种,其中烃类占24%,卤代烃类占52%,含氧化合物占22%,其它化合物占2%。苯系物的检出率最高。定量的挥发性有机物最大浓度和平均浓度最高的项目均为苯,平均浓度4.59μg/m3,最大浓度29.8μg/m3。苯系物时间分布呈现出旱季高,雨季低的特点;日变化特征为早晨最高,整体呈下降趋势。     

A polymer-ceramic composite membrane for recovering volatile organic compounds from wastewaters by pervaporation

A composite membrane was constructed on a porous ceramic support from a block copolymer of styrene and butadiene (SBS). It was tested in a laboratory pervaporation apparatus for recovering volatile organic compounds (VOCs) such as 1,1,1-trichloroethane (TCA) and trichloroethylene (TCE) from dilute aqueous solutions. This polymer-ceramic composite membrane yielded significantly higher VOC selectivity than an SBS membrane without the ceramic support, for comparable fluxes. At VOC concentrations near 100 ppm, fluxes and selectivities of VOCs were essentially independent of the number of VOCs in solution. The liquid-side boundary layer resistance dominated mass transport. The experimental data fitted the resistance-in-series model and yielded reliable membrane permeability values. This method using this high-performing membrane offers potentially cleaner and cost-effective means of recovering VOCs from contaminated streams.     

电子束辐照处理挥发性有机化合物研究进展

大气中挥发性有机化合物（VOC）的污染对人体健康和生态环境会造成严重的危害,电子束辐照处理有机气体是较有前途的治理低浓度VOC技术。本文在介绍电子束辐照VOC机理的基础上,综述了国外关于电子束辐照处理VOC中典型的氯代烃、苯系物以及多环芳烃类污染物的研究进展,阐述了影响VOC去除率的各种因素,介绍了为降低能耗、提高分解效率而采用的加入催化剂、添加剂等方法,并讨论了利用电子束处理VOC的进一步研究方向及应用前景。     

Correlation of human olfactory responses to airborne concentrations of malodorous volatile organic compounds emitted from swine effluent

Direct multicomponent analysis of malodorous volatile organic compounds (VOCs) present in ambient air samples from 29 swine (Sus scrofa) production facilities was used to develop a 19-component artificial swine odor solution that simulated olfactory properties of swine effluent. Analyses employing either a human panel consisting of 14 subjects or gas chromatography were performed on the air stream from an emission chamber to assess human olfactory responses or odorant concentration, respectively. Analysis of the olfactory responses using Fisher's LSD statistics showed that the subjects were sensitive to changes in air concentration of the VOC standard across dilutions differing by approximately 16%. The effect of chemical synergisms and antagonisms on human olfactory response magnitudes was assessed by altering the individual concentration of nine compounds in artificial swine odor over a twofold concentration range while maintaining the other 18 components at a constant concentration. A synergistic olfactory response was observed when the air concentration of acetic acid was increased relative to the concentration of other VOC odorants in the standard. An antagonistic olfactory response was observed when the air concentration of 4-ethyl phenol was increased relative to the other VOC odorants in the standard. The collective odorant responses for nine major VOCs associated with swine odor were used to develop an olfactory prediction model to estimate human odor response magnitudes to swine manure odorants through measured air concentrations of indicator VOCs. The results of this study show that direct multicomponent analysis of VOCs emitted from swine effluent can be applied toward estimating perceived odor intensity.     

Functional classification of swine manure management systems based on effluent and gas emission characteristics

Gaseous emissions from swine (Sus scrofa) manure storage systems represent a concern to air quality due to the potential effects of hydrogen sulfide, ammonia, methane, and volatile organic compounds on environmental quality and human health. The lack of knowledge concerning functional aspects of swine manure management systems has been a major obstacle in the development and optimization of emission abatement technologies for these point sources. In this study, a classification system based on gas emission characteristics and effluent concentrations of total phosphorus (P) and total sulfur (S) was devised and tested on 29 swine manure management systems in Iowa, Oklahoma, and North Carolina in an effort to elucidate functional characteristics of these systems. Four swine manure management system classes were identified that differed in effluent concentrations of P and S, methane (CH4) emission rate, odor intensity, and air concentration of volatile organic compounds (VOCs). Odor intensity and the concentration of VOCs in air emitted from swine manure management systems were strongly correlated (r2 = 0.88). The concentration of VOC in air samples was highest with outdoor swine manure management systems that received a high input of volatile solids (Type 2). These systems were also shown to have the highest odor intensity levels. The emission rate for VOCs and the odor intensity associated with swine manure management systems were inversely correlated with CH4 and ammonia (NH3) emission rates. The emission rates of CH4, NH3, and VOCs were found to be dependent upon manure loading rate and were indirectly influenced by animal numbers.     

Determination of VOC source signature of vehicle exhaust in a traffic tunnel

This study describes the methodology used to obtain the volatile organic compound (VOC) source signature of vehicle exhaust. To accomplish this, C(2)-C(9) VOCs were measured in a traffic tunnel located in Seoul, South Korea. The effect of VOC concentrations from the outside ambient air was considered in the determination of the source signature. To examine the effects of ambient air on VOC concentrations inside the tunnel, the ratio of propane to the total VOC concentrations was compared between the entrance and middle sites in the tunnel. Propane was used as a standard not only because of its insignificant contribution to vehicle exhaust gas, but also the fact that propane is the most abundant VOC in the atmosphere of Seoul. The ratio of propane to the total VOC concentrations was higher at the entrance site than at the middle location by, on average, 60%. This suggests that ambient air affects the inside tunnel air to a greater extent at the entrance site as compared to the middle site. The contribution of ambient air to the air inside the tunnel at the entrance location varied from 30% to 67%, with an average of 55%. This is 1.5 times higher than the value measured at the middle location, which ranged from 20% to 48%, with an average of 36%. This shows that ambient air substantially affects the inside air of the tunnel. Excluding the effects of ambient air on the air inside the tunnel can provide an improved chemical composition for vehicle exhaust using tunnel measurements. We believe that the concentration difference between the two sites within the tunnel provides a more accurate chemical composition of vehicle exhaust as compared to that obtained from a measurement taken at only one point inside the tunnel.     

Determination of volatile organic compound emissions and ozone formation from spraying solvent-based pesticides

Large-scale agricultural activities have come under scrutiny for possible contributions to the emission of ozone precursors. The San Joaquin Valley (SJV) of California is an area with intense agricultural activity that exceeds the federal ozone standards for more than 30 to 40 d yr(-1) and the more stringent state standards for more than 100 d yr(-1). Pesticides are used widely in both agricultural and residential subregions of the SJV, but the largest use, by weight of "active ingredient," is in agriculture. The objective of the study was to determine the role of pesticide application on airborne volatile organic compounds (VOC) concentrations and ozone formation in the SJV. The ozone formation from the pesticide formulation sprayed on commercial orchards was studied using two transportable smog chambers at four application sites during the summers of 2007 and 2008. In addition to the direct measurements of ozone formation, airborne VOC concentrations were measured before and after pesticide spraying using canister and sorbent tube sampling techniques. Soil VOC concentrations were also measured to understand the distribution of VOCs between different environmental compartments. Numerous VOCs were detected in the air and soil samples throughout the experiment but higher molecular weight aromatic hydrocarbons were the primary compounds observed in elevated concentrations immediately after pesticide spraying. Measurements indicate that the ozone concentration formed by VOC downwind of the orchard may increase up to 15 ppb after pesticide application, with a return back to prespray levels after 1 to 2 d.     

Pesticide fate and transport throughout unsaturated zones in five agricultural settings, USA

Pesticide transport through the unsaturated zone is a function of chemical and soil characteristics, application, and water recharge rate. The fate and transport of 82 pesticides and degradates were investigated at five different agricultural sites. Atrazine and metolachlor, as well as several of the degradates of atrazine, metolachlor, acetochlor, and alachlor, were frequently detected in soil water during the 2004 growing season, and degradates were generally more abundant than parent compounds. Metolachlor and atrazine were applied at a Nebraska site the same year as sampling, and focused recharge coupled with the short time since application resulted in their movement in the unsaturated zone 9 m below the surface. At other sites where the herbicides were applied 1 to 2 yr before sampling, only degradates were found in soil water. Transformations of herbicides were evident with depth and during the 4-mo sampling time and reflected the faster degradation of metolachlor oxanilic acid and persistence of metolachor ethanesulfonic acid. The fraction of metolachlor ethanesulfonic acid relative to metolachlor and metolachlor oxanilic acid increased from 0.3 to >0.9 at a site in Maryland where the unsaturated zone was 5 m deep and from 0.3 to 0.5 at the shallowest depth. The flux of pesticide degradates from the deepest sites to the shallow ground water was greatest (3.0-4.9 micromol m(-2) yr(-1)) where upland recharge or focused flow moved the most water through the unsaturated zone. Flux estimates based on estimated recharge rates and measured concentrations were in agreement with fluxes estimated using an unsaturated-zone computer model (LEACHM).     

Abundances and flux estimates of volatile organic compounds from a dairy cowshed in Germany

Animal husbandry and manure treatment have been specifically documented as significant sources of methane, ammonia, nitrous oxide, and particulate matter. Although volatile organic compounds (VOCs) are also produced, much less information exists concerning their impact. We report on chemical ionization mass spectrometry and photo-acoustic spectroscopy measurements of mixing ratios of VOCs over a 2-wk measurement period in a large cowshed at the Federal Agricultural Research Centre (FAL) in Mariensee, Germany. The high time resolution of these measurements enables insight into the sources of the emissions in a typical livestock management setting. During feeding hours and solid manure removal, large mixing ratio spikes of several VOCs were observed and correlated with simultaneous methane, carbon dioxide, and ammonia level enhancements. The subsequent decay of cowshed concentration due to passive cowshed ventilation was used to model emission rates, which were dominated by ethanol and acetic acid, followed by methanol. Correlations of VOC mixing ratios with methane or ammonia were also used to calculate cowshed emission factors and to estimate potential nationwide VOC emissions from dairy cows. The results ranged from around 0.1 Gg carbon per year (1 Gg = 10(9) g) for nonanal and dimethylsulfide, several Gg carbon per year for volatile fatty acids and methanol, to over 10 Gg carbon per year of emitted ethanol. While some estimates were not consistent between the two extrapolation methods, the results indicate that animal husbandry VOC emissions are dominated by oxygenated compounds and may be a nationally but not globally significant emission to the atmosphere.     

Phosphorus leaching under a restored tallgrass prairie and corn agroecosystems

Most studies of phosphorus (P) movement in soil have based their conclusions on patterns of extractable soil P as a function of depth, which has led to the assumption that no substantial leaching loss occurs because of high P-fixation capacity in mineral soils. Few studies have involved high-quality leachate samples collected below the root zone; rather, most have involved tile drainage systems. Equilibrium-tension lysimeters installed at a depth of 1.4 m were used to evaluate and compare P leaching from a restored tallgrass prairie and corn (Zea mays L.) agroecosystems on Plano silt loam soil (fine-silty, mixed, superactive, mesic Typic Argiudoll) in southcentral Wisconsin during a 5-yr period. The corn agroecosystem treatments included nitrogen (N)-fertilized (f) or N-unfertilized (nf) and no-tillage (NT) or chisel-plowed (CP). Mean volume-weighted molybdate-reactive phosphorus (MRP) and total dissolved phosphorus (TDP) concentrations were similar within replicate samples, but always higher in NTf corn than in the prairie or CPf corn systems, though drainage from the CPf corn was always higher than from the NTf corn system. Water-extractable soil P concentrations at any given depth were not positively correlated with leachate concentrations, suggesting that macropore flow causes infiltrating runoff to preferentially bypass the bulk of the soil matrix. Leachate-P concentrations from the natural and managed agroecosystems exceeded 0.01 mg P L(-1) and leaching losses were significantly higher from N-fertilized corn, regardless of tillage, than from the prairie or N-unfertilized corn systems, from which leachate-P concentrations and loads were similar. Increased root growth from N fertilization could cause more macropore formation, preferential flow, and P mineralization from decaying roots compared with N-unfertilized systems, which could contribute to a N-fertilization effect on P leaching.     

Non-conventional gas phase remediation of volatile halogenated compounds by dehydrated bacteria

Traditional biological removal processes are limited by the low solubility of halogenated compounds in aqueous media. A new technology appears very suitable for the remediation of these volatile organic compounds (VOCs). Solid/gas bio-catalysis applied in VOC remediation can transform halogenated compounds directly in the gas phase using dehydrated cells as a bio-catalyst.     

Identification and quantitation of volatile organic compounds emitted from dairy silages and other feedstuffs

High ground-level ozone continues to be an important human, animal, and plant health impediment in the United States and especially in California's San Joaquin Valley (SJV). According to California state and regional air quality agencies, dairies are one of the major sources of volatile organic compounds (VOCs) in the SJV. A number of recently conducted studies reported emissions data from different dairy sources. However, limited data are currently available for silage and otherfeed storages on dairies, which could potentially contribute to ozone formation. Because the impact of different VOCs on ozone formation varies significantly from one molecular species to another, detailed characterization of VOC emissions is essential to include all the important contributors to atmospheric chemistry and especially atmospheric reactivity. The present research study identifies and quantifies the VOCs emitted from various silages and other feedstuffs. Experiments were conducted in an environmental chamber under controlled conditions. Almost 80 VOCs were identified and quantified from corn (Zea mays L.), alfalfa (Medicago sativa L.),and cereal (wheat [Triticum aestivum L.] and oat [Avena sativava L.] grains) silages, total mixed ration (TMR), almond (Amygdalus communis L.) shells and hulls using gas chromatography-mass spectrometry and high performance liquid chromatography. The results revealed high concentrations of emitted alcohols and other oxygenated species. Lower concentrations of highly reactive alkenes and aldehydes were also detected. Additional quantitation and monitoring of these emissions are essential for assessment of and response to the specific needs of the regional air quality in the SJV.