Diffusion Samplers as an Inexpensive Approach to Monitoring VOCs in Ground Water

Diffusion samplers installed in observation wells were found to be capable of yielding polyethylene to transmit other volatile compounds, such as benzene and toluene, indicates that the samplers can be used for a variety of volatile organic compounds. In wells at the study area, the volatile organic compound concentrations in water samples obtained using the samplers without prior purging were similar to concentrations in water samples obtained from the respective wells using traditional purging and sampling approaches. The low cost associated with this approach makes it a viable option for monitoring large observation-well networks for volatile organic compounds.     

Comparison of Temporal Trends in VOCs as Measured with PDB Samplers and Low-Flow Sampling Methods

The effectiveness of passive diffusion bag (pdb) samplers in the measurement of selected volatile organic compounds (VOCs) is dependent on a number of factors. At some sites and wells, pdb sampling methods provide an attractive alternative to other sampling methods. In this discussion, I provide two examples of comparisons of temporal trends in tetrachloroethylene (PCE) concentrations from passive and low-flow sampling methods. At the example field site, large changes in PCE concentrations occurred over the deployment period(s) of the pdb samplers, yet the concentrations from the pdb samples are similar to the low-flow samples and the overall trends are the same.     

On‐Site Vapor‐Phase Analysis as a Novel Approach for Monitoring Groundwater Wells

The results of comprehensive field testing of on‐site vapor‐phase‐based groundwater monitoring methods are presented to demonstrate their utility as a robust and cost‐effective approach for rapidly obtaining volatile organic compounds (VOCs) concentration data from a monitoring well. These methods—which rely on sensitive, commercially available field equipment to analyze vapor in equilibrium with groundwater—proved easy to implement and can be tailored to site‐specific needs, including multilevel sampling. During field testing, low‐flow groundwater concentrations could be reasonably estimated using submerged passive vapor diffusion samplers or field equilibration of collected groundwater (R² = 0.85 to 0.96). These two methods are not as reliant on in‐well mixing to overcome vertical stratification within wells as simpler headspace methods. The importance of well and aquifer‐specific factors on concentration data (and therefore method selection) is highlighted, including the effect of changing in‐well patterns due to seasonal temperature gradients. Results indicated that vertical stratification was relatively limited within the set of wells included in these studies, resulting in similar performance for short depth‐discrete passive vapor diffusion samplers (constructed from 40‐mL vials) and longer samplers (2.5 to 5 feet in length) designed to cover a larger portion of the screened interval. A year‐long, multi‐event evaluation demonstrated that vapor‐phase‐based monitoring methods are no more variable than conventional groundwater monitoring methods, with both types subject to similar spatial and temporal variability that can be difficult to reduce. Vapor sampling methods represent a promising approach for estimation of groundwater concentrations by reducing the cost liabilities associated with monitoring while providing a more sustainable approach.     

Field Investigation of Vapor‐Phase‐Based Groundwater Monitoring

The use of in‐field analysis of vapor‐phase samples to provide real‐time volatile organic compound (VOC) concentrations in groundwater has the potential to streamline monitoring by simplifying the sample collection and analysis process. A field validation program was completed to (1) evaluate methods for collection of vapor samples from monitoring wells and (2) evaluate the accuracy and precision of field‐portable instruments for the analysis of vapor‐phase samples. The field program evaluated three vapor‐phase sample collection methods: (1) headspace samples from two locations within the well, (2) passive vapor diffusion (PVD) samplers placed at the screened interval of the well, and (3) field vapor headspace analysis of groundwater samples. Two types of instruments were tested: a field‐portable gas chromatograph (GC) and a photoionization detector (PID). Field GC analysis of PVD samples showed no bias and good correlation to laboratory analysis of groundwater collected by low‐flow sampling (slope = 0.96, R² = 0.85) and laboratory analysis of passive water diffusion bag samples from the well screen (slope = 1.03; R² = 0.96). Field GC analysis of well headspace samples, either from the upper portion of the well or at the water‐vapor interface, resulted in higher variability and much poorer correlation (consistently biased low) relative to laboratory analysis of groundwater samples collected by low‐flow sample or passive diffusion bags (PDBs) (slope = 0.69 to 0.76; R² = 0.60 to 0.64). These results indicate that field analysis of vapor‐phase samples can be used to obtain accurate measurements of VOC concentrations in groundwater. However, vapor samples collected from the well headspace were not in equilibrium with water collected from the well screen. Instead, PVD samplers placed in the screened interval represent the most promising approach for field‐based measurement of groundwater concentrations using vapor monitoring techniques and will be the focus of further field testing.     

A Diffusive Sampler for Passive Monitoring of Underground Storage Tanks

Passive measurements of volatile organic compounds (VOCs) provide a method for early detection and long-term monitoring of potential leaks from underground storage tanks (USTs) and associated fuel service lines. A diffusive sampler was constructed of a sorbent tube that fits inside a specially designed sampling chamber. VOCs in the soil enter the chamber by molecular diffusion and are collected by the sorbent. The sorbent is easily retrieved for laboratory analyses by thermally desorbing into a gas chromatograph/mass spectrometer (GC/MS), or qualitative concentrations can be determined directly in the field with specific-indicator detectors.
The diffusive samplers were evaluated in an exposure chamber under controlled conditions. Laboratory measurements of the sorbed mass of organic vapor were found to be in close agreement with theoretical values and indicate the passive sampling approach is viable for detecting relatively low concentrations of organic vapors in the vadose zone over a one-day sampling period, as well as providing relatively long-term monitoring periods up to 58 days. A field test found the sampling approach successful in identifying an area where the vadose zone was contaminated by leaking petroleum USTs.     

Screening of Ground Water Samples for Volatile Organic Compounds Using a Portable Gas Chromatograph

A portable gas chromatograph was used to screen 32 ground water samples for volatile organic compounds. Seven screened samples were positive; four of the seven samples had volatile organic substances identified by second-column confirmation. Four of the seven positive, screened samples also tested positive in laboratory analyses of duplicate samples. No volatile organic compounds were detected in laboratory analyses of samples that headspace screening indicated to be negative. Samples that contained volatile organic compounds, as identified by laboratory analysis, and that contained a volatile organic compound present in a standard of selected compounds were correctly identified by using the portable gas chromatograph. Comparisons of screened-sample data with laboratory data indicate the ability to detect selected volatile organic compounds at concentrations of about 1 microgram per liter in the headspace of water samples by use of a portable gas chromatograph.     

Organic Contamination of Ground Water at Gas Works Park, Seattle, Washington

Gas Works Park, in Seattle, Washington, is located on the site of a coal and oil gasification plant that ceased operation in 1956. During operation, many types of wastes, including coal, tar, and oil, accumulated on-site. The park soil is currently (1986) contaminated with compounds such as polynuclear aromatic hydrocarbons, volatile organic compounds, trace metals, and cyanide. Analyses of water samples from a network of observation wells in the park indicate that these compounds are also present in the ground water.
Polynuclear aromatic hydrocarbons and volatile organic compounds were identified in ground water samples in concentrations as large as 200 mg/L. Concentrations of organic compounds were largest where ground water was in contact with a non-aqueous phase liquid in the soil. Where no non-aqueous phase liquid was present, concentrations were much smaller, even if the ground water was in contact with contaminated soils. This condition is attributed to weathering processes in which soluble, low-molecular-weight organic compounds are preferentially dissolved from the non-aqueous phase liquid into the ground water. Where no non-aqueous phase liquid is present, only stained soils containing relatively insoluble, high-molecular-weight compounds remain. Concentrations of organic contaminants in the soils may still remain large.     

The Use of Industrial Hygiene Samplers for Soil-Gas Surveying

Soil-gas surveying by the use of a passive sampler which allows quantitative determination of concentrations of volatile organic compounds and remote analysis of samples is described. The results of a survey using the sampler above a chloroform ground water plume are compared to ground water analysis results and to results from a previous soil-gas study above the same plume. Chloroform concentrations measured with passive samplers correlate well (r = 0.79, n = 6; r = 0.93, n = 7) with the other two techniques. The short-range variability of the technique is characterized by a coefficiet of variation of 12 percent over a 27-foot distance for nine samplers, and compares favorably with grab-sample results at the same location.     

Effects of Selected Sampling Equipment and Procedures on the Concentrations of Trichloroethylene and Related Compounds in Ground Water Samples

Variations in concentrations of trichloroethylene and related compounds in ground water obtained from seven ground water samplers were used to compare the performance of three submersible pumps, a centrifugal pump, two peristaltic pumps, and a bailer. Two- and 4-inch diameter submersible pumps and a centrifugal pump produced samples whose trichloroethylene concentrations, on the average, did not differ significantly from each other. Ground water samples collected by using a peristaltic pump and silicone tubing had significantly lower trichloroethylene concentrations than samples from the submersible pumps. Concentrations of 1,2-dichloroethylene and trichloroethylene in ground water samples collected by using a bailer were indistinguishable from those in samples taken by a submersible pump when the concentrations were as much as 96 and 76 micrograms per liter, respectively, but were 15 and 12 percent lower when concentrations were as low as 29 and 23 micrograms per liter, respectively. Tests of different configurations of sampler placement in observation wells indicate that pump placement, rate of pumping, duration of pumping, and the uniformity of the vertical and lateral distribution of trichloroethylene in ground water near the well screen have a potentially significant influence on trichloroethylene concentrations in ground water samples and that these factors can have a greater effect than the type of sampler used.     

Computer Modeling of Scale Formation During Treatment of Ground Water in Air Strippers

During treatment to remove volatile organic compounds from contaminated ground water, inorganic scale sometimes precipitates in an air stripper tower. This leads to increased costs and down-time associated with tower media replacement. In order to determine the kind, quantity, and rate of scale formation, the ground water from five locations in Florida was simulated using an aqueous equilibrium chemistry and flow process model. In all cases the pH of the outflow water is higher than that of the inflow water because of degassing of CO₂. This often results in the precipitation of calcium carbonate. The addition of air to reduced ground water results in the oxidation of iron and the precipitation of ferric hydroxides. Model estimates of scale formation are about a factor of two to five too high. This indicates that the precipitation reactions do not reach equilibrium within the air stripper. Future work will require the inclusion of biological fouling and a kinetic expression to account for the observed non-equilibrium.     

Long-Term Evaluation of Mulch Biowall Performance to Treat Chlorinated Solvents

Permeable reactive barriers (PRBs), such as mulch biowalls, have been installed at numerous groundwater cleanup sites, and laboratory and field studies have demonstrated biotic and abiotic processes that degrade chlorinated volatile organic compounds (CVOCs) in groundwater passing through these engineered remedies. However, the longevity of mulch biowalls remains a fundamental research question. Soil and groundwater sampling at seven mulch biowalls at Altus Air Force Base (AFB) approximately 10 years after installation demonstrated the ongoing degradation of CVOCs. Trichloroethene was not detected in five of seven groundwater samples collected from the biowall despite upgradient detections above federal drinking water standards. Microbial sampling established the presence of key dechlorinating bacteria and the abundance of genes encoding specific enzymes for degradation, high methane concentrations, low sulfate concentrations, and negative oxidation-reduction potential, all indicative of highly reducing conditions within the biowalls and favorable conditions for CVOC destruction via microbial reductive dechlorination. High cellulose content (>79%) of the mulch, elevated total organic carbon (TOC) content in groundwater, and elevated potentially bioavailable organic carbon (PBOC) measurements in soil samples further supports an ongoing, long-lived source of carbon. These results demonstrate the ongoing and long-term efficacy of the mulch biowalls at Altus AFB. In addition, concentrations of bacteria, TOC, PBOC, and other geochemical parameters suggest a modest impact of the biowalls downgradient. The continued presence of CVOCs downgradient may be attributable to back diffusion from low-permeability shale. However, the biowalls continue to provide benefits by removing CVOCs in groundwater, thus reducing further CVOC loading to the downgradient, low-permeability strata.     

Evidence for Instantaneous Oxygen-Limited Biodegradation of Petroleum Hydrocarbon Vapors in the Subsurface

Petroleum hydrocarbon vapors biodegrade aerobically in the subsurface. Depth profiles of petroleum hydrocarbon vapor and oxygen concentrations from seven locations in sandy and clay soils across four states of Australia are summarized. The data are evaluated to support a simple model of biodegradation that can be used to assess hydrocarbon vapors migrating toward built environments. Multilevel samplers and probes that allow near‐continuous monitoring of oxygen and total volatile organic compounds (VOCs) were used to determine concentration depth profiles and changes over time. Collation of all data across all sites showed distinct separation of oxygen from hydrocarbon vapors, and that most oxygen and hydrocarbon concentration profiles were linear or near linear with depth. The low detection limit on the oxygen probe data and because it is an in situ measurement strengthened the case that little or no overlapping of oxygen and hydrocarbon vapor concentration profiles occurred, and that indeed oxygen and hydrocarbon vapors were largely only coincident near the location where they both decreased to zero. First‐order biodegradation rates determined from all depth profiles were generally lower than other published rates. With lower biodegradation rates, the overlapping of depth profiles might be expected, and yet such overlapping was not observed. A model of rapid (instantaneous) reaction of oxygen and hydrocarbon vapors compared to diffusive transport processes is shown to explain the important aspects of the 13 depth profiles. The model is simply based on the ratio of diffusion coefficients of oxygen and hydrocarbon vapors, the ratio of the maximum concentrations of oxygen and hydrocarbon vapors, the depth to the maximum hydrocarbon source concentration, and the stoichiometry coefficient. Whilst simple, the model offers the potential to incorporate aerobic biodegradation into an oxygen‐limited flux‐reduction approach for vapor intrusion assessments of petroleum hydrocarbon compounds.     

The Effect of Air Bubbles and Headspace on the Aqueous Concentrations of Volatile Organic Compounds in Sampling Vials

The presence of headspace and air bubbles in volatile organic analysis sampling vials lowers the actual aqueous concentration of these compounds due to the partitioning of solutes into the gaseous phase. This could make the sample invalid for analysis.
In this work, the effects of air bubbles and headspace on the aqueous concentration of 60 volatile organic compounds listed in U.S.Environmental Protection Agency (U.S. EPA) Method 8260 were evaluated experimentally and theoretically. The results showed that for air to water ratios of 1 to 20 and less, there was no significant effect on the aqueous concentrations of target organic solutes in the sampling vials. When the air to water ratio was increased to 1 to 10, the recovery rates of four organic compounds were lower than the control. Laboratory experiments on sampling vials showed that the presence of air bubbles or headspace with the volumetric air to water ratios of 1 to 20 and less do not produce any significant effect on the original concentrations for most targeted volatile organic compounds.
The experimental results also indicated that in 40 mL sampling vials with headspace range of 2 to 8 mL, the recovery rates of most volatile organic compounds with high values of Henry's law constant (> 0.01 Atm m³/mol. at 25°C) were larger than the calculated rates.     

Effects of land use on ground water quality in the Anoka Sand Plain Aquifer of Minnesota

We began a study, in 1996, to compare ground water quality under irrigated and nonirrigated agriculture, sewered and nonsewered residential developments, industrial, and nondeveloped land uses. Twenty-three monitoring wells were completed in the upper meter of an unconfined sand aquifer. Between 1997 and 2000, sampling occurred quarterly for major ions, trace inorganic chemicals, volatile organic compounds (VOCs), herbicides, and herbicide degradates. On single occasions, we collected samples for polynuclear aromatic hydrocarbons (PAHs), perchlorate, and coliform bacteria. We observed significant differences in water chemistry beneath different land uses. Concentrations of several trace inorganic chemicals were greatest under sewered urban areas. VOC detection frequencies were 100% in commercial areas, 52% in sewered residential areas, and <10% for other land uses. Median nitrate concentrations were greatest under irrigated agriculture (15,350 microg/L) and nonsewered residential areas (6080 microg/L). Herbicides and degradates of acetanilide and triazine herbicides were detected in 86% of samples from irrigated agricultural areas, 68% of samples from nonirrigated areas, and <10% of samples from other land uses. Degradates accounted for 96% of the reported herbicide mass. We did not observe seasonal differences in water chemistry, but observed trends in water chemistry when land use changes occurred. Our results show land use is the dominant factor affecting shallow ground water quality. Trend monitoring programs should focus on areas where land use is changing, while resource managers and planners must consider potential impacts of land use changes on ground water quality.     

A Discrete Point Sampler for Ground Water Monitoring Wells

A discrete point sampler has been developed that overcomes disadvantages inherent in several current small-volume samplers. It is designed to obtain ground water samples after a well has been purged with a pump. It consists of a sample chamber, two ports, and a stopcock for withdrawing sample aliquots. After lowering the sampler into a well, sampling is initiated by pulling on a line that sequentially removes the plugs in the lower and the upper level ports. The sample chamber fills from the bottom port and vents air from the top port. The device is suitable for sampling for volatile organic compounds in ground waters that are not subject to spontaneous bubble degassing. The upper port is sufficiently far above the lower port that none of the water that is sampled is exposed to the vented air. The sample chamber fills in such a way that the water that is taken from the chamber for analysis is not exposed to the headspace in the chamber.     

Observed Spatial and Temporal Distributions of CVOCs at Colorado and New York Vapor Intrusion Sites

The vapor intrusion impacts associated with the presence of chlorinated volatile organic contaminant plumes in the ground water beneath residential areas in Colorado and New York have been the subject of extensive site investigations and structure sampling efforts. Large data sets of ground water and indoor air monitoring data collected over a decade-long monitoring program at the Redfield, Colorado, site and monthly ground water and structure monitoring data collected over a 19-month period from structures in New York State are analyzed to illustrate the temporal and spatial distributions in the concentration of volatile organic compounds that one may encounter when evaluating the potential for exposures due to vapor intrusion. The analysis of these data demonstrates that although the areal extent of structures impacted by vapor intrusion mirrors the areal extent of chlorinated volatile organic compounds in the ground water, not all structures above the plume will be impacted. It also highlights the fact that measured concentrations of volatile organic compounds in the indoor air and subslab vapor can vary considerably from month to month and season to season. Sampling results from any one location at any given point in time cannot be expected to represent the range of conditions that may exist at neighboring locations or at other times. Recognition of this variability is important when designing sampling plans and risk management programs to address the vapor intrusion pathway.     

Binary Mixtures of Permanganate and Chlorinated Volatile Organic Compounds in Groundwater Samples: Sample Preservation and Analysis

Groundwater samples collected at sites where in situ chemical oxidation (ISCO) has been deployed may contain binary mixtures of groundwater contaminants and permanganate (MnO₄^–), an oxidant injected into the subsurface to destroy the contaminant. Commingling of the oxidant and contaminant in aqueous samples may negatively impact the quality of the sample as well as the analytical instruments used to quantify contaminant concentrations. In this study, binary mixtures comprised of (1) a multicomponent standard with permanganate and (2) groundwater samples collected at two ISCO field sites were preserved with ascorbic acid. Ascorbic acid reacts rapidly with the MnO₄^– and limits the reaction between MnO₄^– and the organic compounds in the mixture. Consequently, most of the compounds in the multicomponent standard were within the control limit for quality assurance. However, despite timely efforts to preserve the samples, the rapid reaction between permanganate and contaminant caused the concentration of several sensitive compounds to fall significantly below the lower control limit. Concentrations of volatile organic compounds in the field‐preserved binary mixture groundwater samples were greater than in samples refrigerated in the field and preserved upon arrival at the laboratory, indicating the time‐dependency and benefit of field preservation. The molar ratio of ascorbic acid required to neutralize KMnO₄ was 1.64 (mol ascorbic acid/mol KMnO₄); this provided a baseline to estimate the volume of ascorbic acid stock solution and/or the weight of crystalline ascorbic acid required to neutralize MnO₄^–. Excess ascorbic acid did not negatively impact the quality of the aqueous samples, or analytical instruments, used in the analyses.     

Comparison of Stainless Steel vs. PTFE Miniwells for Monitoring Halogenated Organic Solute Transport

Field tests of organic solute transport behavior have often been monitored using small-diameter wells (miniwells). To determine if experimental results could be significantly biased by sorption to, desorption from, or diffusion through sampling lines, dissolved concentrations of tetrachloroethene and carbon tetrachloride were measured in ground water samples collected simultaneously from the same spatial location during a forced-gradient test in the Borden aquifer using polytetrafluoroethene (PTFE) and stainless steel miniwells (1/8-inch O.D.).
A semiautomated organic analytical system was used on-site to obtain real-time results, which avoided sample holding problems and permitted optimizing sampling times. The breakthrough curves (plots of concentration vs. time) for both organic compounds indicate that under the conditions of this experiment (low organic solute concentrations, short exposure time of sampling lines to the plume, adequate flushing of sampling lines) there is no significant difference between concentration histories (breakthrough curves) collected using a polytetrafluoroethene sampling line and those collected using a stainless steel sampling line. This suggests that organic solute tailing seen in this and also in a similar transport experiment previously conducted at the site is the result of transport processes in the aquifer rather than an artifact introduced by the PTFE miniwells.     

Volatile Organic Sulfur Compounds in a Meromictic Alpine Lake

The full spectrum of volatile sulfur compounds was detected in the water column of the permanently stratified meromictic Lake Cadagno. Besides hydrogen sulfide it included methanethiol, carbonyl sulfide, dimethyl sulfide, carbon disulfide, and dimethyl disulfide. Their distribution in the water column suggests that these compounds are of biogenic origin. Except for carbon disulfide which is present in all layers of Lake Cadagno, these volatile organic sulfur compounds are restricted to the anoxic part of the lake. For methanethiol, dimethyl sulfide, and carbon disulfide maximum concentrations were observed in the redox transition zone and in the sediment porewater. Carbon disulfide is the most abundant volatile organic sulfur compound with concentrations of up to 60 μmol L^–1. The concentrations of the methylated sulfides are in the nmolar range. Although their concentrations varied during the summer months, seasonal trends of the concentrations of volatile organic sulfur compounds did not follow a consistent pattern. The restriction of most sulfur species to the anoxic layers of the lake indicates that their production originates from anaerobic microbial degradation of biomass and not from its release from a specific precursor like dimethylsulfoniumpropionate as in marine environments.     

Temporal Changes in VOC Discharge to Surface Water from a Fractured Rock Aquifer During Well Installation and Operation, Greenville, South Carolina

Analysis of the vapor in passive vapor samplers retrieved from a streambed in fractured rock terrain implied that volatile organic carbon (VOC) discharge from ground water to surface water substantially increased following installation of a contaminant recovery well using air rotary drilling. The air rotary technique forced air into the aquifer near the stream. The injection produced an upward hydraulic gradient that appears to have transported water and contaminants from deeper parts of the aquifer through fractures into shallow parts of the aquifer. Once in the shallow flow regime, the contamination was transported to the stream, where it discharged during the next several weeks following well installation. After the recovery well was activated and began continuously pumping contaminated ground water to a treatment facility, the VOC concentrations in the stream bottom passive vapor samplers decreased to below detectable concentrations, suggesting that the withdrawal had captured the contaminated ground water that previously had discharged to the stream.