Rapid Assessment of Trichloroethylene in Ground Water

On-site analysis of trichloroethylene (TCE) in aqueous samples by head- space sample preparation and gas chromatography (HS/GC) provides for quick and precise concentration estimates. This analytical approach is well suited for the on-site determination of volatile organic compounds (VOCs) in a variety of sample matrices, including ground water and saturated and unsatured soils. For these reasons, HS/GC can be used to establish analyte concentrations on a near real time basis to help select appropriate casing material during monitoring well installation. This application and the collection of multiple well samples during sampling events facilitates the hydrogeological site interpretation and the formulation of remediation strategies.     

Sampling of VOCs with the BAT Ground Water Sampling System

In the BAT ground water sampling system, a stainless steel probe with a porous filter element is pushed vertically to the desired sampling depth. An evacuated glass sampling tube is then lowered down the penetration rods where it makes contact with the filter via a hypodermic needle and draws a pore fluid sample.
An investigation of the system was carried out at a number of sites contaminated by leaking underground gasoline storage tanks. Ground water samples obtained using the BAT system and adjacent monitoring wells were analyzed for volatile organic compounds (VOCs).
Because the BAT system is an in situ penetration device with a small filter length, it is possible to determine variations in contaminant concentration with depth. BAT samples in general exhibited higher recovery of VOCs than did bailer samples from adjacent monitoring wells screened over large intervals.
Much higher levels of VOCs were recovered when the probe was used with its 316 stainless steel filter than when using the high-density polyethylene (HDPE) filter. Significant sorption apparently occurred on the latter filter.
Because the BAT sample tubes are sealed and remain a closed system, the in situ water pressure is maintained. No significant loss of VOCs was found in sampling tubes containing headspace. Samples from the upper tube in the cascaded setup with headspace recovered levels of VOCs as high, or in a few cases higher, than the lower, no-headspace tubes.     

A Syringe and Cartridge Method for Down-Hole Sampling for Trace Organics in Ground Water

A newly developed technique which allows the down-hole sampling and subsequent analysis of ground water for trace organic contaminants was tested during an investigation of contaminant migration at an inactive landfill site in Burlington, Ontario, Canada. The sampling device, which is lowered down piezometers with a tube, consists of a small cylindrical cartridge of sorbent material attached to a syringe. Vacuum or pressure applied at the surface controls the movement of the plunger in the syringe. The volume of the syringe determines the volume of sample water that passes through the cartridge. The cartridge is removed from the syringe at the surface. One cartridge is used for each sampling; the syringe is reusable. The residual water in the cartridge is removed in the laboratory, and the cartridge is desorbed to a fused silica capillary column for analysis by gas chromatography (GC). The analyses discussed here were performed on a GC/mass spectrometer/data system (GC/MS/DS). Of the many organic compounds that were identified in the samples, three compounds were clearly landfill-related: 1,1,1-trichloroethane, chlorobenzene, and para-dichlorobenzene. The three compounds were found at levels substantially above blank levels in 9, 5, and 5 piezometers, respectively. The average concentrations were 14., 5.3, and 0.88μg/1 (ppb), respectively. The pooled coefficients of variation for the analyses for the three compounds were 27., 6.9, and 6.4%, respectively. The volatility of 1,1,1-trichloroethane was probably the cause of the greater variability in its analytical data. The main advantages of the technique over most conventional sampling methods include: (1) down-hole sampling in a manner which minimizes the potential for volatilization losses; (2) avoidance of passage of the sample through long sections of tubing that may contaminate the sample or cause adsorptive losses; (3) convenience of sample handling, storage, and shipping; and (4) high sensitivity.     

Comparison of Downhole and Surface Sampling for the Determination of Volatile Organic Compounds (VOCs) in Ground Water

The relative precision and accuracy of sampling and analysis methods for the determination of trace concentrations of volatile organic compounds (VOCs) in ground water were compared. Samples were collected from a well containing nanogram-per-liter (ng/L) to microgram-per-liter (μg/L) levels of VOCs. A Keck helical rotor submersible pump was used to collect samples at the surface for analysis by purge and trap (P&T) and for analysis by adsorption/thermal desorption (ATD). Downhole samples were collected by passing water through an ATD cartridge. Although slight spontaneous bubble outgassing occurred when the water was brought to the surface, the relative precisions and comparabilities of the surface and downhole methods were generally found to be equivalent from a statistical point of view. A main conclusion of this study is that bringing sample water to the surface for placement in VOC vials (and subsequent analysis by P&T) can be done reliably under many circumstances. However, care must still be taken to prevent adsorption losses and cross contamination. Samples subject to strong bubble outgassing will need to be handled in a special fashion (e.g., by downhole ATD) to minimize volatilization losses. Additionally, the higher sensitivity of the ATD method allows lower detection limits than are possible with P&T. For example, several compounds present at the ng/L level could be determined with confidence by ATD, but not by P&T.     

Use of Total Organic Carbon as an Indicator of Contamination from an Oil Refinery, South-Central Kansas

Water samples collected from 26 sites at an abandoned oil refinery in south-central Kansas were analyzed for total organic carbon (TOC) and specific volatile and semivolatile organic compounds by gas-chromatography/mass-spectrometric methods. Results from a Spearman-rho correlation analysis between TOC concentration and the number of compounds (correlation coefficient = 0.71) and TOC concentration and total concentration of compounds identified (correlation coefficient = 0.83) indicate correlations significant at the 0.01 level.
Although TOC data alone would not be sufficient to evaluate hazards posed by oil-refinery wastes, results of the correlation analysis performed using data collected from the site in Kansas indicate that TOC data can be used effectively to delineate petroleum-related ground water contamination and to help identify sources of ground water contaminants. TOC data collected from a large number of temporary sampling points during the initial phases of an investigation will provide an estimate of the extent of hydrocarbon contamination and allow placement of monitoring wells and more detailed sampling in appropriate areas.     

Design, Installation, and Uses of Combination Ground Water and Gas Sampling Wells

Waste disposal sites with volatile organic compounds (VOCs) frequently contain contaminants that are present in both the ground water and vadose zone. Vertical sampling is useful where transport of VOCs in the vadose zone may effect ground water and where steep vertical gradients in chemical concentrations are anticipated. Designs for combination ground water and gas sampling wells place the tubing inside the casing with the sample port penetrating the casing for sampling. This physically interferes with pump or sampler placement. This paper describes a well design that combines a ground water well with gas sampling ports by attaching the gas sampling tubing and ports to the exterior of the casing. Placement of the tubing on the exterior of the casing allows exact definition of gas port depth, reduces physical interference between the various monitoring equipment, and allows simultaneous remediation and monitoring in a single well. The usefulness and versatility of this design was demonstrated at the Idaho National Engineering and Environmental Laboratory (INEEL) with the installation of seven wells with 53 gas ports, in a geologic formation consisting of deep basalt with sedimentary interbeds at depths from 7.2 to 178 m below land surface. The INEEL combination well design is easy to construct, install, and operate.     

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.     

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.     

A Method to Evaluate the Vertical Distribution of VOCs in Ground Water in a Single Borehole

Volatile organic compounds (VOCs) are present in multiple water-bearing zones beneath and downgradient of Lawrence Livermore National Laboratory. This area is composed of interfingering unconsolidated alluvial sediments with hydraulic conductivities ranging over four orders of magnitude. The more permeable sediments exhibit moderate hydraulic interconnection horizontally and less interconnection vertically, and appear to consist largely of interconnected stream channel deposits. To optimize selection of monitoring well screened intervals in this complex environment, a technique that enables collection of saturated formation samples from each water-bearing zone without contamination from other VOC-containing zones was developed, tested, and implemented. The technique utilizes a wireline punch-coring system that allows the drill bit to be replaced with a core barrel without removing the drill rod from the borehole. To help ensure that a sample from one water-bearing zone is not contaminated by VOCs from another zone, the drilling fluid is replaced with new fluid before each sampling run. Overnight chemical analysis by gas chromatography enables field personnel to know the vertical distribution of VOCs as drilling proceeds. Since its first use in 1985, the technique has successfully characterized the presence or absence of VOCs in ground water in 123 of 140 wells, many with concentrations in ground water in the low parts-per-billion range. Our sampling technique is a cost-effective and rapid method of evaluating the vertical distribution of VOCs in ground water in a complex hydrogeologic environment.     

Laboratory Comparison of Polyethylene and Dialysis Membrane Diffusion Samplers

The ability of diffusion samplers constructed from regenerated cellulose dialysis membrane and low density, lay flat polyethylene tubing to collect volatile organic compounds and inorganic ions was compared in a laboratory study. Concentrations of vinyl chloride, cis -1, 2-dichloroethene, bromochloromethane, trichloroethene, bromodichloromethane, and tetrachloroethene collected by both types of diffusion samplers reached equilibrium with the concentrations of these compounds in test solution within three days. Concentrations of bromide and iron collected by the dialysis membrane diffusion samplers reached equilibrium with the concentrations of these compounds in a test solution within three to seven days. No detectable concentrations of bromide or iron were found in polyethylene diffusion samplers even after 21 days. No measurable concentrations of aluminum, arsenic, barium, cadmium, chromium, iron, mercury, manganese, nickel, and lead, or sulfide, were leached out of dialysis membrane samplers over seven days. Compared with using a gas-tight syringe to sample the diffusion sampler, clipping the bag and pouring the water sample into a sample vial resulted in only a small 6.2% average loss of volatile organic compounds. Dialysis membrane diffusion samplers offer promise for use in sampling ground water for inorganic constituents as well as volatile organic compounds.     

An Evaluation of Some Systems for Sampling Gas-Charged Ground Water for Volatile Organic Analysis

Loss of volatile organics during sampling is a well-recognized source of bias in ground water monitoring; sampling protocols attempt to minimize such loss. Such bias could be enhanced for ground water highly charged with dissolved gases such as methane. Such ground water was the object of this study. A positive-displacement bladder pump, a momentum-lift pump and a suction-lift, peristaltic pump were employed in sampling both methane-charged ground water for volatile aromatic hydrocarbons and a CO₂-charged reservoir water for volatile chlorinated hydrocarbons. In both cases, the suction-lift pump produced samples with a significant negative bias (9 to 33 percent) relative to the other methods. Little difference between samples produced by the other pump Systems was noted at the field site, but in sampling the reservoir, the bladder pump produced samples that were 13 to 19 percent lower in halocarbon concentration than were samples from the momentum-lift pump.
These negative biases are tentatively interpreted as losses due to volatilization during sampling. Slightly greater negative biases occur for compounds of higher volatility as estimated from their Henry's law constants. Additional studies appear to be warranted in order to adequately establish the scientific basis for recommending protocols for sampling ground water in which degassing could enhance the loss of volatile organics during sampling.     

Cone Penetrometer Tests and HydroPunch® Sampling: A Screening Technique for Plume Definition

Cone penetrometer tests and HydroPunch® sampling were used to define the extent of volatile organic compounds in ground water. The investigation indicated that the combination of these techniques is effective for obtaining ground water samples for preliminary plume definition. HydroPunch samples can be collected in unconsolidated sediments and the analytical results obtained from these samples are comparable to those obtained from adjacent monitoring wells. This sampling method is a rapid and cost-effective screening technique for characterizing the extent of contaminant plumes in soft sediment environments. Use of this screening technique allowed monitoring wells to be located at the plume boundary, thereby reducing the number of wells installed and the overall cost of the plume definition program.     

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.     

Sampling VOCs with Porous Suction Samplers in the Presence of Ethanol: How Much Are We Losing?

Porous suction samplers have been widely used to obtain ground water samples from the vadose zone. However, previous studies identified different mechanisms that may compromise the sample's representativeness, such as volatilization and sorption. This issue is particularly important when dealing with volatile organic compounds (VOCs) as in gasoline spills. Ethanol is common in modern fuels and so may be present in ground water contamination from fuel releases. The objective of this work was to evaluate the losses of VOCs in the presence of ethanol when using porous suction samplers. Laboratory experiments were performed using a ceramic porous suction sampler to sample test solution containing benzene, toluene, xylenes, trimethylbenzenes, naphthalene, and different volumetric fractions of ethanol. Significant losses were found up to 30% for ethylbenzene. Ethanol was found to affect the accuracy of the readings by two main mechanisms: first, negatively, by increasing the headspace in the sampling tube, and second, positively, increasing partition to the aqueous phase due to the cosolvent effect and therefore decreasing the mass loss by volatilization. As a consequence, the highest losses of VOCs were found at intermediate ethanol volume fractions: 10% and 20% (v/v). The losses can be anticipated by measuring the ratio of gas to water in the sampling line and then by applying simple partition models considering cosolvency by ethanol. The importance of adequate purging when using porous suction samplers was also shown.     

Groundwater Sampling at ISCO Sites: Binary Mixtures of Volatile Organic Compounds and Persulfate

In situ chemical oxidation involves the introduction of a chemical oxidant into the subsurface for the purpose of transforming groundwater contaminants into harmless by‐products. Owing to oxidant persistence, groundwater samples collected at hazardous waste sites may contain both the contaminant(s) and the oxidant in a “binary mixture.” Binary mixtures composed of sodium persulfate (2.5 g/L; 10.5 mM) and volatile organic compounds (VOCs) (benzene, toluene, m‐xylene, perchloroethylene, trichloroethylene) were analyzed to assess the impact on the quality of the sample. A significant decline (49 to 100%) in VOC concentrations was measured in binary mixtures using gas chromatography (GC) purge and trap, and GC mass spectroscopy headspace methods. Preservation of the binary mixture samples was achieved through the addition of ascorbic acid (99 to 100% VOC average recovery). High concentrations of ascorbic acid (42 to 420 mM) did not interfere in the measurement of the VOCs and did not negatively impact the analytical instruments. High concentrations of ascorbic acid favored the reaction between persulfate and ascorbic acid while limiting the reaction between persulfate and VOCs. If an oxidant is detected and the binary sample is not appropriately preserved, the quality of the sample is likely to be compromised.     

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.     

Screening of Emerging Volatile Organic Contaminants in Shallow Groundwater in East China

In order to collect baseline information on the environmental occurrence of volatile organic compounds (VOCs) in groundwater in East China, shallow groundwater samples were collected from five alluvial plains in East China in 2008 to 2009. All samples were analyzed for 54 VOCs representing a wide variety of uses and origins. Sampling sites were mainly selected in the areas to be susceptible to contamination from human activities in terms of previous hydrogeological survey. The data of all samples showed a variety of different hydrogeological systems with potential sources of VOCs, with 36 of the 54 VOCs being found. The most frequently detected compounds include naphthalene (56.9%), chloroform (16.9%), 1,2‐dichloroethane (16.2%), 1,2‐dichloropropane (13.1%), and 1,2,3‐trichlorobenzene (12.3%). The concentrations of methylene chloride, 1,2‐dichloroethane, carbon tetrachloride, trichloroethene, 1,2‐dichloropropane, and tetrachloroethene exceeded the relating drinking water standards. Future work will be needed to identify those factors that are most important in determining the occurrence and concentrations of VOCs in groundwater in China.     

Field Trapping of Subsurface Vapor Phase Petroleum Hydrocarbons

Soil gas samples from intact soil cores were collected on adsorbents at a field site, then thermally desorbed and analyzed by laboratory gas chromatography (GC). Vertical concentration profiles of predominant vapor phase petroleum hydrocarbons under ambient conditions were obtained for the zone directly above the capillary fringe. Water and residual phase weathered aviation gasoline were present in this region of the profile.
The sampling, trapping, and GC methodology was effective in most respects. Reproducibility, trapping, and desorption efficiency were generally satisfactory, and different sorbent tubes gave similar results. A minor shortcoming of the method occurred with the most volatile compound, 2,3-dimcthylbutane, which was poorly retained during several weeks of storage lime and was also poorly desorbed.
Vapor phase concentrations of predominant hydrocarbon compounds all increased with depth at one sampling location. At a more highly contaminated location, concentrations of highly volatile compounds increased with depth while concentrations of less volatile compounds remained constant or decreased, possibly indicating distillation effects. Scatier in the data was attributed to heterogeneities in water and residual phase distribution.     

Decontaminating Materials Used in Ground Water Sampling Devices: Organic Contaminants

In these studies, the efficiency of various decontamination protocols was tested on small pieces of materials commonly used in ground water sampling devices. Three materials, which ranged in ability to sorb organic solutes, were tested: stainless steel (SS), rigid polyvinyl chloride (PVC), and polytetrafluoroethylene (PTFE). The test pieces were exposed to two aqueous test solutions: One contained three volatile organic compounds (VOCs) and one nitroaromatic compound, and the other contained four pesticides. Also, three types of polymeric tubing were exposed to pesticide solutions. Generally, the contact times were 10 minutes and 24 hours for sorption and desorption.
The contaminants were removed from the nonpermeable SS and the less-sorptive rigid PVC test pieces simply by washing with a hot detergent solution and rinsing with hot water. Additional treatment was required for the PTFE test pieces exposed to the VOCs and for the low-density polyethylene (LDPE) tubing exposed to the pesticide test solution. Solvent rinsing did not improve removal of the three VOCs from the PTFE and only marginally improved removal of the residual pesticides from the LDPE. However, a hot water and detergent wash and rinse followed by oven drying at approximately 105°C was effective for removing the VOCs from the PTFE and substantially reduced pesticide contamination from the LDPE.     

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.