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.     

The Effect of Bottle Fill Rate and Pour Technique on the Recovery of Volatile Organics

This field study was conducted to examine whether the method or the flow rate (fill rate) used to fill a sample vial affects recovery of volatile organics (VOCs). To our knowledge, there have not been any systematic studies that have examined this issue. For this field study, three fill rates (50 mL/min, 250 mL/min, and ~1 L/min) and three filling methods (top‐pour, side‐pour, and bottom‐fill) were used to fill sample vials. We found that the bottom‐fill method, with the tubing submerged in the sample as it fills, yielded the greatest recovery (i.e., highest concentrations) of VOCs. Little improvement was observed by pouring down the side of a vial vs. simply pouring straight down from the top. We also found that filling the vials at the fastest fill rate (~1 L/min) yielded higher recovery than the slowest fill rate (50 mL/min) using all three filling methods. These results are counter to prevailing guidance and conventional wisdom that slower filling is preferable to faster filling and that pouring down the side of a sample vial is the best practice for VOC sampling. However, because we were unable to randomize the order the samples were collected with respect to fill rate, we recommend a follow‐on study be conducted that will allow us to confirm our findings and better determine which fill rates minimize losses of VOCs     

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.     

Subsurface Transport of Inorganic and Organic Solutes from Experimental Road Spreading of Oil-Field Brine

A study designed to evaluate ground water quality changes resulting from spreading oil-field brine on roads for ice and dust control was conducted using a gravel roadbed that received weekly applications of brine eight times during the winter phase and 11 times during the summer phase of the study. A network of 11 monitoring wells and five pressure-vacuum lysimeters was installed to obtain ground water and soil water samples. Thirteen sets of water- quality samples were collected and analyzed for major ions, trace metals, and volatile organic compounds. Two sets of samples were taken prior to brine spreading, four sets during winter-phase spreading, five sets during summer- phase spreading, and two sets during the interim between the winter and summer phases. A brine plume delineated by elevated specific-conductance values and elevated chloride concentrations developed downgradient of the roadbed during both the winter and summer phases. The brine plume caused chloride concentrations in ground water samples to exceed U.S. EPA public drinking-water standards by two-fold during the winter phase and five-fold during the summer phase. No other major ions, trace metals, or volatile organic compounds exceeded the standards during the winter or summer phases. More than 99 percent dilution of the solutes in the brine occurred between the roadbed surface and the local ground water flow system. Further attenuation of calcium, sodium, potassium, and strontium resulted from adsorption, whereas further attenuation of benzene resulted from volatilization and adsorption.     

Effect of Different Sampling Methodologies on Measured Methane Concentrations in Groundwater Samples

Analysis of dissolved light hydrocarbon gas concentrations (primarily methane and ethane) in water supply wells is commonly used to establish conditions before and after drilling in areas of shale gas and oil extraction. Several methods are currently used to collect samples for dissolved gas analysis from water supply wells; however, the reliability of results obtained from these methods has not been quantified. This study compares dissolved methane and ethane concentrations measured in groundwater samples collected using three sampling methods employed in pre‐ and post‐drill sampling programs in the Appalachian Basin. These include an open‐system collection method where 40 mL volatile organic analysis (VOA) vials are filled directly while in contact with the atmosphere (Direct‐Fill VOA) and two alternative methods: (1) a semi‐closed system method whereby 40 mL VOA vials are filled while inverted under a head of water (Inverted VOA) and (2) a relatively new (2013) closed system method in which the sample is collected without direct contact with purge water or the atmosphere (IsoFlask^®). This study reveals that, in the absence of effervescence, the difference in methane concentrations between the three sampling methods was relatively small. However, when methane concentrations equaled or exceeded 20 mg/L (the approximate concentration at which effervescence occurs in the study area), IsoFlask^® (closed system) samples yielded significantly higher methane concentrations than Direct‐Fill VOA (open system) samples, and Inverted VOA (semi‐closed system) samples yielded lower concentrations. These results suggest that open and semi‐closed system sample collection methods are adequate for non‐effervescing samples. However, the use of a closed system collection method provides the most accurate means for the measurement of dissolved hydrocarbon gases under all conditions.     

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.     

Comparison of Two Integrated Methods for the Collection and Analysis of Volatile Organic Compounds in Ground Water

The principal difficulties with determinations of volatile organic compounds (VOCs) in ground water are the reliability of sampling procedures and analytical methods. Two integrated methods have been developed for routine sampling, processing, and analysis of VOCs in ground water. These methods involve in situ collection of ground water using a modified syringe sampler from PVC piezometers or using dedicated glass syringes from stainless steel multilevel bores. The samples are processed in the syringe using purge and trap or microsolvent extraction and analyzed by GC/MSD.
The modified purge-and-trap method is time-consuming and limited to volatile organic compounds. However, it is extremely sensitive and flexible: the volume of sample used can be varied by the use of different-size glass syringes (sample volumes from 1 to 100 mL).
In cases where extremely low sensitivity (<10 mg 1⁻¹) is not critical, the microextraction technique is a more cost-effective method, allowing twice as many samples to be analyzed in the same time as the purge-and-trap method. It enables less volatile compounds such as polynuclear aromatic hydrocarbons, phenol, and cresols to be analyzed in the same GC run. Also, the microextraction method can be used in the field to avoid delays associated with transportation of ground water samples to the laboratory.     

Intercomparison of Waterborne 222Rn Collection Methods: Professional Vs. Homeowner Collection

An intercomparison between trained professional and homeowner water collection techniques was conducted to assess the validity of using both inexperienced homeowner water collectors and mail-in return of point-of-use water samples. The findings indicate that homeowner-collected water samples obtained at the point of use inside the home and professionally collected water samples collected at an outside tap are comparable, especially if confounders, such as air bubbles in the sampling vials, are minimized.     

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.     

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.     

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.     

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.     

Some Biases in Sampling Multilevel Piezometers for Volatile Organics

Multilevel piezometers are cost-effective monitoring devices for determining the three-dimensional distribution of solutes in ground water. Construction includes flexible tubing (plastic or Teflon®). Their sampling is subject to a number of'potential biases, particularly: (1) losses of volatile organic solutes via volatilization, (2) sorption onto the flexible tubing of the piezometers, (3) leaching of organics from this tubing, and (4) collection of unrepresentative samples due to inadequate piezometer flushing. It is shown that these biases are minimal or are easily controlled in most situations.
Another source of bias has been recognized. Organic solutes present in ground water above the screened level can penetrate the flexible plastic or Teflon tubing and contaminate the sampled water being drawn through this tubing. Laboratory tests and field results indicate this transmission causes low organic contaminant concentrations to be erroneously attributed to ground water which is free of such contaminants. The transmitted organics apparently desorb from the plastic tubing during flushing of even 40 piezometer volumes.
Recognition of this transmission problem provides for a better interpretation of existing organic contaminant distribution data. Caution is advised when considering the use of these monitoring devices in organic solute contaminant studies.     

Indoor Air Background Levels of Volatile Organic Compounds and Air-Phase Petroleum Hydrocarbons in Office Buildings and Schools

A background indoor air study has been completed which includes the collection of indoor air samples from office buildings and schools. The anonymous study was designed with input from the U.S. Environmental Protection Agency and the Massachusetts Department of Environmental Protection. The sampling was implemented in 2013, 2014, and 2015 and included the collection of 25 school building samples and 61 office building samples. The study generated 14,668 new indoor air background data points, with samples collected from buildings located in 26 cities in 18 states, including Arizona, California, Connecticut, Indiana, Kansas, Maine, Massachusetts, Minnesota, Montana, New Hampshire, New Jersey, New York, Nevada, North Carolina, Ohio, Texas, Utah, and Washington. Indoor air background concentrations of target compound volatile organic compounds (VOCs) ranged from less than the laboratory method reporting limit of 0.044 μg/m³ to concentrations up to 1190 μg/m³, with hydrocarbon ranges from less than the reporting method limit of 10 μg/m³ to concentrations up to 3000 μg/m³. Some VOCs were identified ubiquitously in indoor air background, and some were identified at concentrations which exceeded risk-based regulatory screening levels. These study results provide useful and updated information on indoor air background and air quality in offices and schools and can be used in future regulatory guidance update considerations, for further examination of relationships between these data and residential study data, in human health risk assessments and risk communication, and in planning future studies.     

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.     

Complexation of aqueous elements by DOC in a clay aquitard

The extent of partitioning of several elements (Cu, Mn, Mo, Ni, Sr, U, and Zn) on dissolved organic carbon (DOC) was investigated in pore water samples collected from a clay-rich aquitard. High DOC concentrations in the aquitard, ranging from 21 to 143 mg C/L, and natural aqueous metal concentrations higher than in most ground water environments facilitated complexation studies at this site. Analyses were conducted using on-line coupling of asymmetrical flow field-flow fractionation with ultraviolet, total organic carbon, and inductively coupled plasma-mass spectrometry detectors. Of the elements investigated, only U and Zn were complexed with all DOC samples, ranging from 2.2 to 60 microg U/g DOC (0.4% to 3% of the total U in the pore water) and 0.04 to 0.5 microg Zn/g DOC (0.1% to 0.9% of the total Zn in the pore water), respectively. Laboratory experiments conducted over a range in pH (1.3 to 9.7) and geochemical modeling supported the measured complexation of U and Zn on the DOC. The in situ association constant, K(d), for U decreased with depth from 76 mL/g C for pore water samples at 2.2 m below ground (BG) to 24 mL/g C at 9.7 m BG. The decrease was attributed to a decrease in aromaticity of the DOC with depth. Zn K(d)constants ranged from 2 to 12 mL/g C and exhibited no trend with depth. Results of the current study suggest minor masses of U and Zn (less than or equal to 4% of total) complex with this DOC under in situ pH conditions. Our data suggest that competitive complexation by other ligands may limit the importance of DOC-facilitated transport of the elements studied in water of similar chemical composition.     

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.     

Optimization of the Sampling Technique for the Determination of Dissolved Hydrogen in Groundwater

In this study a field‐sampling technique for dissolved hydrogen (H₂) in groundwater will be presented which allows the transport of gaseous samples into the laboratory for further analysis. The method consists of transferring the headspace trapped in a gas‐sampling bulb which is continuously purged by groundwater into previously evacuated vials using a gas‐tight syringe. Three transfer steps with preceding evacuation of the vial led to a H₂‐recovery of 100 % in laboratory experiments. The method has been applied to determine H₂ concentrations in an aquifer contaminated with chlorinated solvents. Tests concerning the effect of different pumping techniques on H₂ concentrations revealed that most reliable values were obtained with a bladder pump, while an electrically driven submersible pump generated considerable amounts of hydrogen due to electrochemical interactions with the sampled water. Concentrations of dissolved hydrogen in field and laboratory samples were about two orders of magnitude higher when sampling was performed with the electrically driven submersible pump compared to sampling with the bladder pump and a peristaltic pump. Lab experiments with a Plexiglas reservoir to produce H₂‐enriched water were used to study the effect of two tubing materials (PVC, polyamide) on H₂ losses. PVC tubing turned out to allow transfer of H₂‐enriched water over 25 m without significant losses, while PA‐tubing was not suitable for sampling of H₂.     

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.     

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.