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.     

Suggested Modifications to Ground Water Sampling Procedures Based on Observations from the Colloidal Borescope

Observations of colloidal movement under natural conditions and during pumping were conducted at several field sites. Results indicate that several modifications to present sampling protocols may improve the representativeness and cost effectiveness of obtaining ground water samples for assessing the total mobile contaminant load. These modifications include the installation of dedicated sampling devices, limited purging of the well prior to sampling, sampling at a flow rate of 100 mL/min, and no filtering of samples. This sampling approach can result in significant cost savings while providing the best possible water samples.     

Sampling Strategies for Estimation of Parameters Related to Ground Water Quality

Multiple theoretical sampling designs are studied to determine whether sampling designs can be identified that will provide for characterization of ground water quality in rural regions of developing nations. Sampling design in this work includes assessing sampling frequency, analytical methods, length of sampling period, and requirements of sampling personnel. The results answer a set of questions regarding whether using innovative sampling designs can allow hydrogeologists to take advantage of a range of characterization technologies, sampling strategies, and available personnel to develop high-value, water-quality data sets. Monte Carlo studies are used to assess different sampling strategies in the estimation of three parameters related to a hypothetical chemical observed in a ground water well: mean concentration (MeanC), maximum concentration (MaxC), and total mass load (TML). Five different scenarios are simulated. These scenarios are then subsampled using multiple simulated sampling instruments, time periods (ranging from 1 to 10 years), and sampling frequencies (ranging from weekly to semiannually to parameter dependent). Results are analyzed via the statistics of the resulting estimates, including mean square error, bias, bias squared, and precision. Results suggest that developing a sampling strategy based on what may be considered lower quality instruments can represent a powerful field research approach for estimating select parameters when applied at high frequency. This result suggests the potential utility of using a combination of lower quality instrument and local populations to obtain high frequency data sets in regions where regular monitoring by technicians is not practical.     

Nickel and Chromium in Ground Water Samples as Influenced by Well Construction and Sampling Methods

An investigation of elevated concentrations of nickel and chromium in certain ground water samples collected at Williams Air Force Base (AFB) indicated that type 304 stainless steel well materials are the source. Chloride in the ground water has apparently caused crevice corrosion of the stainless steel well screens installed during site characterization. An evaluation of site geochemistry suggested that chromium released from the well screen would precipitate, while nickel would remain dissolved. Thus, low-flow purging and sampling significantly reduces the chromium found in the ground water samples because such sampling minimizes the collection of artificially entrained particulates. In contrast to chromium, nickel concentrations did not decrease during low-flow purging and sampling, indicating that it is dissolved. Nickel and chromium concentrations are both low following high-volume purging when turbidity levels are stabilized below 10 nephelometric turbidity units prior to sampling. In the latter case, chromium concentration is low because particulate collection is minimized, and nickel concentration is low because of increased dilution. Based on these results, it is recommended that elevated levels of nickel and chromium in ground water samples collected from stainless steel monitoring wells be carefully evaluated, because well materials may be the source. In addition, although low-volume purging is increasingly becoming the sampling method of choice, high-volume purging may be a useful means of determining whether the well materials influence nickel and chromium concentrations.     

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.     

The Effects of Ground Water Sampling Devices on Water Quality: A Literature Review

This paper reviews both field and laboratory studies that tested or compared the ability of various types of sampling devices to deliver representative ground water samples. Several types of grab samplers, positive displacement devices, and suction-lift devices were evaluated, Gas-lift and inertial-lift pumps were also evaluated. This study found that most of these devices can. under certain circumstances, alter the chemistry of ground water samples, das-lift pumps, older types of submersible centrifugal pumps, and suction-lift devices are not recommended when sampling for sensitive constituents such as volatile organics and inorganics, or inorganics that are subject to oxidation/precipitation reactions. In general, of the devices reviewed in this paper, bladder pumps gave the best recovery of sensitive constituents. However, better performance could be achieved for several devices if improved operational guidelines were developed by additional testing, especially at lower flow rates. Clearly, further research is warranted. Future studies should focus on pumping rate, flow control mechanisms, and dedication or decontamination of sampling devices.     

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.     

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.     

Equipment Decontamination Procedures for Ground Water and Vadose Zone Monitoring Programs: Status and Prospects

A major portion of the work effort and, therefore, the money spent during investigations of ground water and the vadose zone at hazardous waste sites is associated with collecting chemical data. To that end, effective decontamination of reusable drilling equipment, sampling apparatus, and tools is critical to the credibility of chemical data. Samples representative of the site under study are essential.
Several state and federal regulatory agencies have established guidelines for procedures that should be considered when developing decontamination protocols. These agencies were contacted and asked to furnish copies of their decontamination guidelines. The information received was reviewed, and comparisons were made to assess the status of standards of decontamination practices for ground water and vadose zone monitoring programs at hazardous waste sites. Summaries of a variety of decontamination protocols were prepared. From this review, it is apparent that there is a need to standardize, to the extent possible, procedures for the field decontamination of equipment.
Two ASTM Subcommittees, D18.14 on Waste Management and D18.21 on Ground Water and Vadose Zone Monitoring, are currently working on developing standards for decontamination procedures. They, in cooperation with state and federal agencies and other interested technical groups, will develop standards for the field decontamination of equipment used to study ground water and the vadose zone.     

Oxygen Transfer Through Flexible Tubing and Its Effects on Ground Water Sampling Results

A model for the diffusion of gases through polymeric tubing was derived which predicts that the amount of gas transferred is proportional to the tubing length and inversely proportional to the pumping rate. The model was experimentally tested and confirmed for oxygen transfer through fluorinated ethylene-propylene copolymer (FEP) tubing using tubing lengths and flow rates typical of ground water sampling. Diffusion can introduce measurable concentrations of oxygen into initially anoxic water. Diffusive loss of carbon dioxide from water that is oversaturated with respect to atmospheric CO₂ does not measurably affect pH under similar usage conditions.     

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.     

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.     

The Effect of Sampling Frequency on Ground Water Quality Characterization

There is an implicit relationship between the frequency of sampling and the value of information obtained. This relationship is briefly explored by a study of nitrates in aquifers of the Quaternary age and fluorides and sulfates in aquifers of the Cambro-Ordovician age in Iowa. The ambient distribution of these chemicals, in general, is positively skewed with a significant number of observations in the lower end of the feasible range. It is shown that a much broader perspective of the distribution of these chemicals in ground water can be obtained by studying a whole spectrum of parameters (quantiles) ranging from the minimum to the maximum, rather than just the mean or the median alone. Simple random samples of varying sizes drawn from the available data base revealed that many parameters of location, such as the quantiles, of nitrates, fluorides, and sulfates in selected aquifers can be estimated closely by samples of sizes 50, 100 and 250. Results based on such hindsight warrant further investigation of the behavior of sampling distributions of a set of high priority chemicals in different hydrogeological environments.     

Determination of Selected Endocrine Disrupter Compounds at Trace Levels in Sewage Sludge Samples

Simultaneous determination of endocrine disrupter compounds (EDCs), namely diltiazem, progesterone, benzylbutylphthalate (BBP), estrone, and carbamazepine (Cbz) were performed by using high performance LC–electrospray tandem MS. The ultrasound‐aided sequential extraction of sludge samples was optimized to increase extraction efficiencies of the analytes; ranging between 93.0–98.3% recovery. The limit of detection values for diltiazem, progesterone, BBP, estrone, and Cbz were found as 0.78, 0.72, 0.24, 0.75, and 0.72 µg/kg, respectively. Sludge samples taken from Ankara Tatlar; Hurma, Lara and Kemer of Antalya, and Middle East Technical University‐vacuum rotating membrane wastewater treatment plant (WWTP) aeration tanks were analyzed for their EDCs contents under optimized conditions. Diltiazem was found in all the samples in the range between 116.4–180.8 ng/g while progesterone and estrone were not detected in any of the samples analyzed with the exception of Tatlar WWTP. The BBP concentration was between beyond detection and 9195.5 ng/g. In addition, Cbz was found in all the samples ranging from 25.6 to 118.8 ng/g.     

Low-Flow Purging and Sampling of Ground Water Monitoring Wells with Dedicated Systems

A field study was conducted to assess purging requirements for dedicated sampling systems in conventional monitoring wells and for pumps encased in short screens and buried within a shallow sandy aquifer. Low-flow purging methods were used, and wells were purged until water quality indicator parameters (dissolved oxygen, specific conductance, turbidity) and contaminant concentrations (chromate, trichloroethylene, dichloroethylene) reached equilibrium. Eight wells, varying in depth from 4.6 to 15.2 m below ground surface, were studied. The data show that purge volumes were independent of well depth or casing volumes. Contaminant concentrations equilibrated with less than 7.5 I. of purge volume in all wells. Initial contaminant concentration values were generally within 20 percent of final values. Water quality parameters equilibrated in less than 10 L in all wells and were conservative measures for indicating the presence of adjacent formation water. Water quality parameters equilibrated faster in dedicated sampling systems than in portable systems and initial turbidity levels were lower.