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.     

Sampling for Purgeable Organic Compounds Using Positive-Displacement Piston and Centrifugal Submersible Pumps: A Comparative Study

Positive-displacement piston pumps that minimize sample agitation have no apparent advantage over centrifugal submersible pumps when used to collect ground water samples for analysis of low concentrations of purge-able organic compounds. Analytical uncertainties inherent in laboratory environments appear to influence analytical results of low-concentration purgeable organic compound samples more than either pump type or sampling team. Centrifugal submersible pumps are at least equally efficient as positive-displacement piston pumps in the recovery of carbon tetrachloride, 1,1,1-trichloroethane, trichloroethylene, and chloroform after sampling and analytical influences are made constant.     

The Sensitivity of Four Monitoring Well Sampling Systems to Low Concentrations of Three Volatile Organics

Four state-of-the-art ground water sampling systems were analyzed to determine their reliability in providing representative samples of the volatile chlorinated hydrocarbons trichloroethylene (TCE), perchloroethylene (PCE), and 1,1,1-trichloroethane (TCA) from a simulated monitoring well. The sampling systems studied represent four commonly used devices, including a stainless steel and Teflon® piston pump, a Teflon bailer, a Teflon bladder pump, and a PVC air-lift pump.
Controlled laboratory sampling experiments were conducted in a tank and well test chamber designed to approximate field conditions. A well purging and sampling procedure was used in the test apparatus to determine the accuracy and precision of each device for detecting low concentrations of the compounds in ground water. The compounds selected are some of the most ubiquitous hazardous contaminants found in shallow aquifers near hazardous waste sites throughout the United States.
No significant statistical difference was found among the four sampling systems in detecting the compounds.     

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.     

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.     

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.     

Occurrence of volatile organic compounds (VOCs) in Liverpool Bay, Irish Sea

Surface seawater samples were collected in the Irish Sea and Liverpool Bay area from the R.V. Prince Madog during the period of 25-31 of March 2006. VOCs were purged with nitrogen, pre-concentrated on a SPME fibre and analysed immediately on a GC-MS. Target compounds quantified were halogenated (0.2-1400 ng L(-1)), BTEXs and mono-aromatics (1.5-2900 ng L(-1)), aliphatic hydrocarbons and others (0.6-15,800 ng L(-1)). Day and night sampling was performed at a single station and suggested that factors such as sunlight and tide affect the presence of many of these compounds. Sample variability was high due to the variable weather conditions at the station. Poor correlations were found between marine phytopigments and selected VOCs. Principal component analysis (PCA) analysis showed that chlorinated compounds such as 1,2-dichloroethane, 1,1,1-trichloroethane, trichloroethene, tetrachloroethene and carbon tetrachloride, predominantly from anthropogenic sources, originated from the River Mersey. Other brominated and iodinated compounds quantified were more likely to be from biogenic sources including novel marine compounds such as 2-chloropropane, 1-bromoethane and 1-chlorobutane.     

Vitamin B12 and Reduced Titanium for Remediation of Residual Chlorinated Solvents: Field Experiment

A first pilot-scale field experiment using vitamin B₁₂ and reduced titanium was conducted in an in situ vertical circulation column at CFB Borden. The objective of the experiment was to test the applicability of the technology for restoring aquifer source zones contaminated by chlorinated solvents—tetrachloroethene (PCE) and 1,1,1-trichloroethane (1,1,1-TCA)—in a mixture of dense nonaqueous phase liquids (DNAPLs). Vitamin B₁₂ promotes the reductive dechlorination of chlorinated organics. A highly reducing and slightly alkaline environment must be maintained (Eh < - 480 mV and 7 < pH < 9) to maximize the rate of degradation. In this field test, PCE and 1,1,1-TCA degraded to a limited extent under experimental conditions, with 1,1,1-TCA degrading more readily. Indigenous bacteria were found to metabolize citrate, which caused titanium to precipitate, limiting degradation. The addition of glucose at the end of a second field season effectively limited citrate degradation and helped recover the optimal redox potential by keeping reduced titanium in solution. A laboratory column was used to confirm field results. The column also produced a significant biomass, which provided an additional source of organic carbon onto which the solvents sorbed.     

A Multilevel Ground Water Monitoring System for Casing Advance and Bedrock Drilling Methods

A single-hole multilevel sampling piezometer system (MLSPS) has been designed by the Geological Survey of Canada (GSC) to be installed using drilling systems that continuously core (e.g., Rotosonic) or continuously sample (e.g., hollow-stem auger, Becker hammer) overburden and that have the flexibility of allowing additional coring (diamond drilling) or sampling (hammer drilling) of bedrock. The GSC-MLSPS (under license to Solinst Canada Ltd.) uses a patented GSC dry injection system for accurate emplacement of filter packs and seals. This system permits (a) the use of variable screen lengths; (b) the complete evacuation of piezometers before introduction of new ground water (no bailing); (c) the use of a number of types of hydraulic tests (e.g., slug, withdrawal/recovery, vacuum, pressure-pulse); (d) ground water sampling under a nitrogen atmosphere; (e) dissolved gas sampling; (f) a great deal of flexibility in the use of design materials; and (g) the elimination of bridging and collapse of filter packs and seals.     

Fate of DDT-related compounds in Bohai Bay and its adjacent Haihe Basin, North China

Concentrations of ten DDTs (2,2-bis-(chlorophenyl)-1,1,1-trichloroethane) of which p,p'-DDA (2,2-bis(chlorophenyl)acetic acid), p,p'-DDM (bis(chlorophenyl)methane) and p,p'-DBP (dichlorobenzophenone) are often neglected, were measured in 25 water and 25 sedimentary samples from Bohai Bay and its adjacent Haihe Basin. The ratio of o,p'-DDX/p,p'-DDX in the upper reaches of Yongdingxin River ranged from 0.71 to 2.44, suggesting that the potential source of pollution would be the manufacturing or use of dicofol near this river. While DDA accounted for 52-93% of the SigmaDDT concentration in water, DDA was only detected in three sedimentary samples. And DDM was found to be an important degradation product of DDT in water following DDA. It should be noted that DBP (0.60-3.30 ng/g) is a major metabolite comparable with DDE (2,2-bis(chlorophenyl)-1,1-dichloroethylene, nondetectable-1.80 ng/g) and DDD (2,2-bis-(chlorophenyl)-1,1-dichloroethane, nondetectable-2.86 ng/g) in sediment in Bohai Bay. Finally, the SigmaDDT concentration in sedimentary sample from Bohai Bay was found to be dependent on the TOC (total organic carbon) value.     

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.     

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.     

A Comparison of Sampling Mechanisms Available for Small-Diameter Ground Water Monitoring Wells

The objective of most ground water quality monitoring programs is to obtain samples that are "representative" or that retain the physical and chemical properties of the ground water in an aquifer. Many factors can influence whether or not a particular sample is representative, but perhaps the most critical factor is the method or type of sampling device used to retrieve the sample.
The sampling equipment available today ranges from simple to highly sophisticated, and includes bailers, syringe devices, suction-lift pumps, gas-drive devices, bladder (Middelburg-type) pumps, gear-drive and helical rotor electric submersible pumps and gas-driven piston pumps. New devices are continually being developed for use in small-diameter wells in order to meet the needs of professionals engaged in implementing elaborate ground water monitoring programs.
In selecting a sampling device for a monitoring program, the professional must consider a number of details. Among the considerations are: the outside diameter of the device, the overall impact of the device on ground water sample integrity (including the materials from which the sampling device and associated equipment are made and the method by which the device delivers the sample), the capability of the device to purge the well of stagnant water, the rate and the ability to control the rate at which the sample is delivered, the depth limitations of the device, the ease of operating, cleaning and maintaining the device, the portability of the device and required accessory equipment, the reliability and durability of the device, and the initial and operational cost of the device and accessory equipment. Based on these considerations, each of the devices available for sampling ground water from small-diameter wells has its own unique set of advantages and disadvantages that make it suitable for sampling under specific sets of conditions. No one sampling device is applicable to all sampling situations.     

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.     

Comparison of Fiberglass and Other Polymeric Well Casings Part II. Sorption and Leaching of Trace-Level Organics

This paper contains the results of a laboratory study that was designed to compare sorption of low (mg/L) concentrations of 11 organic solutes by six polymeric materials (acrylonitrile butadiene styrene [ABS], fluorinated ethylene propylene [FEP], fiberglass-reinforced epoxy [FRE] and fiberglass-reinforced plastic [FRP], polyvinyl chloride [PVC], and poly-tetrafluoroethylene [PTFE]).
During this six-week study, ABS sorbed analytes much more rapidly and to a greater extent than did the other materials, and PVC and FRE sorbed analytes more slowly and to a lesser extent than the other materials tested.
As the study progressed, an increasing number of spurious peaks were found in the high performance liquid chromatography (HPLC) chromatograms of some of our samples, indicating that leaching of some consituents had occurred. By the end of the study, there were 11 additional peaks in the ABS samples, five in the FRP samples, and one in the FRE samples. Analysis by purge and trap gas chromatography/mass spectrometry (GC/MS) of those samples and of well water samples that were exposed to the casings for 500 hours revealed the identity of some of the leached constituents; acrylonitrile and styrene (components of ABS), chloroform and ethylbenzene (an intermediate in the production of styrene) from the ABS pipe, and toluene, 1,1,1-trichloroethane, and ethylbenzene from the FRP casing.     

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.     

Contamination of an Unconfined Sand Aquifer by Waste Pulp Liquor: A Case Study

A zone of contaminated ground water has been identified in an unconfined sand aquifer adjacent to a pit into which spent pulp liquor was intermittently discharged from 1970 to 1979. A network of multilevel sampling, bundle-type piezometers was installed. Up to seven depthspecific sampling points were incorporated into each piezometer providing a cost-effective means for three-dimensional mapping of hydraulic head and water quality in the unconfined sand aquifer. Ground-water samples retrieved from this network showed an area of contamination 900 m long, 400 m wide, and more than 25 m deep. This plume is dispersed about the ground-water flow lines passing beneath the waste disposal pit, and it terminates at a vigorous ground-water discharge area located 800 m from the pit. The contaminated ground water is characterized by elevated concentrations of sodium (3,000 mg/1), chloride (590 mg/1), alkalinity (2,700 mg/1), total organic carbon (2,000 mg/1), chemical oxygen demand (10,800 mg/1), biological oxygen demand (2,000 mg/1), tannin and lignin (780 mg/1), and lower sulphate (1 mg/1) compared to background ground waters in the area. The apparent rate of sodium migration is more than 50 m/yr and is close to the average linear ground-water velocity. Removal of some organic matter by biological transformation has produced the increased alkalinity in the contaminated ground water and somewhat reduced pH. Tannin and lignin are relatively inert compared to other organic compounds found in the waste liquor. Extremely low sulphate levels occurring in the highly contaminated ground waters indicate the existence of conditions favorable for microbially-mediated sulphate reduction.     

Bestimmung von Pflanzenbehandlungsmitteln in Wasser durch Online-Fest-Flüssig-Extraktion und HPLC-DAD

Determination of Pesticides in Water by On-line Solid-phase Extraction and HPLC-DAD This paper describes an HPLC on-line procedure for the determination of 29 relevant pesticides in water by diode-array detection using a compact HPLC-system with integrated column-switching. The sample – 5 mL – is injected with a large volume injection system on a precolumn cartridge (RP-C18). Enriched compounds are eluted in frontflush mode by columnswitching to a microbore column and separated with a gradient water/acetonitrile. During desorption the precolumn cartridge is heated at 80°C resulting in a comparable efficiency to the separation with direct injection. The procedure is fully automated for continuous monitoring of drinking-, ground-, and surface water with low contamination levels. Sample preparation is limited to a filtration step with an anion-exchange membrane filter to reduce natural contaminations e.g. humic acids simultaneously. For a concentration of 50 ng/L, the signal to noise ratio varies from 3:1 (Ethidimuron) up to 25:1 (Chloridazon). The standard deviations compare to the standardized HPLC-method DIN EN ISO 11369; the recovery rates are 100% and reproducible. The method was successfully tested on ruggedness with several sequences from a monitoring program. The precolumn cartridge needs replacement after 100 sample injections. Finally, this method was coupled with a benchtop mass-spectrometer (electrospray mode) without changing the chromatographic conditions. With selected ion monitoring (SIM) selectivity and detection sensitivity could be improved considerably compared to DAD-detection.     

TABLE DES MATIÈRES DU BULLETIN DE 1956 A 1960 / CONTENTS OF THE BULLETIN 1956–1960

Abstract

Piezometers and wells installed for water quality monitoring are frequently used to assess the saturated hydraulic conductivity (K) in the surrounding formation. A series of recovery tests was conducted to evaluate how purging, required to obtain representative water quality samples, affected measured values of hydraulic conductivity in 15 newly installed and undeveloped piezometers placed to between 2 and 15 m depth (in oxidized and unoxidized material) in a loamy glacial till (K range from 10^?6 to 10^?9 m s^?1). Piezometers were purged between 9 and 11 times for sampling over a period of five months. The effect of the purgings on piezometer development was evaluated by changes in slope of the water level recovery curves which were used to calculate hydraulic conductivity. The first five purgings following piezometer installation increased K in the 15 piezometers by an average of 34%. The average increase in a value of K after 10 purgings was 44%. Values measured for hydraulic conductivity in a 75 mm diameter auger hole appeared stable after four purgings but piezometers installed in larger diameter boreholes (100 mm to 280 mm) snowed increases in K with up to 10 purgings. The hydraulic conductivity determined for piezometers installed at a 30° angle to the vertical showed greater variability than was observed in the adjacent vertically installed piezometers at the same depth.     

Zur Adsorption von Dichlormethan und 1,1,1-Trichlorethan aus Modellabwässern mit Adsorberpolymeren und Aktivkohlen

Adsorption of Dichloromethane and 1,1,1-Trichloroethane from Synthetic Wastewaters with Polymeric Adsorbents and Activated Carbons Isotherms, kinetics, and dynamics of adsorption of dichloromethane and 1,1,1-trichloroethane from synthetic wastewaters onto novel polymeric adsorbents were investigated in comparison to traditional polymeric adsorbents and activated carbons. The polymeric adsorbents and the activated carbons showed no large differences in adsorption kinetics, whereas the novel, crosslinked polymeric adsorbents exhibited at times higher adsorption capacities than the traditional, not crosslinked polymeric adsorbents and activated carbons.