An Analysis of Low-Flow Ground Water Sampling Methodology

Low-flow ground water sampling methodology can minimize well disturbance and aggravated colloid transport into samples obtained from monitoring wells. However, in low hydraulic conductivity formations, low-flow sampling methodology can cause excessive drawdown that can result in screen desaturation and high ground water velocities in the vicinity of the well, causing unwanted colloid and soil transport into ground water samples taken from the well. Ground water velocities may increase several fold above that of the natural setting. To examine the drawdown behavior of a monitoring well, mathematical relationships can be developed that allow prediction of the steady-state drawdown for constant low-flow pumping rates based on well geometry and aquifer properties. The equations also estimate the time necessary to reach drawdown equilibrium. These same equations can be used to estimate the relative contribution of water entering a sampling device from either the well standpipe or the aquifer. Such equations can be useful in planning a low-flow sampling program and may suggest when to collect a water sample. In low hydraulic conductivity formations, the equations suggest that drawdown may not stabilize for well depths, violating the minimal drawdown requirement of the low-flow technique. In such cases, it may be more appropriate to collect a slug or passive sample from the well screen, under the assumption that the water in the well screen is in equilibrium with the surrounding aquifer.     

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.     

A Laboratory Evaluation of Ground Water Sampling Mechanisms

The reliability of ground water monitoring information can be assured by careful selection of sample handling and analytical procedures. Sampling mechanism selection has been studied far less than analytical methodologies (Scalf et al. 1981, Nacht 1983). This study has as its primary goal the identification of reliable sampling mechanisms for purgeable organic compounds and gas-sensitive chemical parameters in ground water. Carefully controlled sampling experiments were run to investigate the error contributed to chemical results due to sampling mechanism alone. Fourteen commercial sampling devices in five mechanistic categories were evaluated for their performance in sample collection for solution parameters, dissolved gases and purgeable organic compounds. Systematic errors related to sampling mechanism can reduce the accuracy of monitoring data by factors of two to three times that involved in analytical procedures.     

An Environmentally Friendly Decontamination Protocol for Ground Water Sampling Devices

Several detergent-washing/air-drying decontamination protocols were tested to determine their ability to remove residual contamination from two types of ground water sampling devices. We tested a relatively simply constructed device, a bailer, and a much more complex, and theoretically more difficult to decontaminate, bladder pump. The devices were decontaminated after sampling ground water that was contaminated with organics that varied in their hydrophobic nature and propensity to be sorbed by the materials in the devices. These studies showed that a hot-detergent wash, hot-water rinse, and hot-air drying protocol was effective.     

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.     

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.     

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.     

Sampling for Toxic Contaminants in Ground Water

In this paper, we relate recent developments in ground water sampling techniques to the practical application of sampling for toxic contaminants in ground water. We address the choices that must be made in choosing equipment for a particular project by going through a step-by-step procedure for collecting a ground water sample from a typical monitoring well. Ground water sampling topics that are discussed include: choice of equipment for purging and sampling a well, monitoring for purged ground water indicators and quality assurance/quality control.     

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.     

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.     

Modeling Ground Water Quality Sampling Decisions

Questions such as what, where, when, and how often to sample play a central role in the development of monitoring strategies. Limited resources will not permit sampling for many contaminants at the same frequency at all well sites. Therefore, a resource allocation strategy is necessary to arrive at answers for the preceding types of questions. Such a strategy for a ground water quality monitoring program is formulated as an integer programming model (an optimization model). The model will be of use in the process of deciding what constituents to sample and where to sample them so as to maximize a given objective, subject to a set of budget, sampling, and regulatory constraints. The maximization objective in the model is defined as a weighted function of population exposure to a scaled measure of observed chemical concentrations. The sampling constraints are based on the observed variability of contaminants in the aquifer, needed precision in estimates, a chosen level of significance, the available budget for implementing the program, and selected regulatory constraints. The model is tested with field data obtained for 10 selected constituents from more than 650 wells in the Cambrian-Ordovician aquifer in Iowa. Results from two alternative formulations of the model are compared, analyzed, and discussed. Further avenues for research are briefly outlined.     

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.     

Robowell: An Automated Process for Monitoring Ground Water Quality Using Established Sampling Protocols

Robowell is an automated process for monitoring selected ground water quality properties and constituents by pumping a well or multilevel sampler. Robowell was developed and tested to provide a cost-effective monitoring system that meets protocols expected for manual sampling. The process uses commercially available electronics, instrumentation, and hardware, so it can be configured to monitor ground water quality using the equipment, purge protocol, and monitoring well design most appropriate for the monitoring site and the contaminants of interest. A Robowell prototype was installed on a sewage-treatment plant infiltration bed that overlies a well-studied u neon fined sand and gravel aquifer at the Massachusetts Military Reservation, Cape Cod, Massachusetts, during a time when two distinct plumes of constituents were released. The prototype was operated from May 10 to November 13, 1996, and quality-assurance/quality-control measurements demonstrated that the data obtained by the automated method was equivalent to data obtained by manual sampling methods using the same sampling protocols. Water level, specific conductance, pH, water temperature, dissolved oxygen, and dissolved ammonium were monitored by the prototype as the wells were purged according to U.S. Geological Survey (LJSGS) ground water sampling protocols. Remote access to the data record, via phone modem communications, indicated the arrival of each plume over a few days and the subsequent geochemical reactions over the following weeks. Real-time availability of the monitoring record provided the information needed to initiate manual sampling efforts in response to changes in measured ground water quality, which proved the method and characterized the screened portion of the plume in detail through time. The methods and the case study described are presented to document the process for future use.