Binary Mixtures of Permanganate and Chlorinated Volatile Organic Compounds in Groundwater Samples: Sample Preservation and Analysis

Groundwater samples collected at sites where in situ chemical oxidation (ISCO) has been deployed may contain binary mixtures of groundwater contaminants and permanganate (MnO₄^–), an oxidant injected into the subsurface to destroy the contaminant. Commingling of the oxidant and contaminant in aqueous samples may negatively impact the quality of the sample as well as the analytical instruments used to quantify contaminant concentrations. In this study, binary mixtures comprised of (1) a multicomponent standard with permanganate and (2) groundwater samples collected at two ISCO field sites were preserved with ascorbic acid. Ascorbic acid reacts rapidly with the MnO₄^– and limits the reaction between MnO₄^– and the organic compounds in the mixture. Consequently, most of the compounds in the multicomponent standard were within the control limit for quality assurance. However, despite timely efforts to preserve the samples, the rapid reaction between permanganate and contaminant caused the concentration of several sensitive compounds to fall significantly below the lower control limit. Concentrations of volatile organic compounds in the field‐preserved binary mixture groundwater samples were greater than in samples refrigerated in the field and preserved upon arrival at the laboratory, indicating the time‐dependency and benefit of field preservation. The molar ratio of ascorbic acid required to neutralize KMnO₄ was 1.64 (mol ascorbic acid/mol KMnO₄); this provided a baseline to estimate the volume of ascorbic acid stock solution and/or the weight of crystalline ascorbic acid required to neutralize MnO₄^–. Excess ascorbic acid did not negatively impact the quality of the aqueous samples, or analytical instruments, used in the analyses.     

Release of Chromium from Soils with Persulfate Chemical Oxidation

An important part of the evaluation of the effectiveness of persulfate in situ chemical oxidation (ISCO) for treating organic contaminants is to identify and understand its potential impact on metal co‐contaminants in the subsurface. Chromium is a redox‐sensitive and toxic metal the release of which poses considerable risk to human health. The objective of this study was to investigate the impact of persulfate chemical oxidation on the release of chromium from three soils varying in physical‐chemical properties. Soils were treated with unactivated and activated persulfate [activated with Fe(II), Fe(II)‐EDTA, and alkaline pH] at two different concentrations (i.e., 41 mM and 2.1 mM persulfate) for 48 h and 6 months and were analyzed for release of chromium. Results show that release of chromium with persulfate chemical oxidation depends on the soil type and the activation method. Sandy soil with low oxidant demand released more chromium compared to soils with high oxidant demand. More chromium was released with alkaline pH activation. Alkaline pH and high Eh conditions favor oxidation of Cr(III) to Cr(VI), which is the main mechanism of release of chromium with persulfate chemical oxidation. Unactivated and Fe(II)‐activated persulfate decreased pH and at low pH in absence of EDTA chromium release is not a concern. These results indicate that chromium release can be anticipated based on the given site and treatment conditions, and ISCO system can be designed to minimize potential chromium release when treating soils and groundwater contaminated with both organic and metal contaminants.     

Preserving Ground Water Samples With Hydrochloric Acid Does Not Result in the Formation of Chloroform

Water samples collected for the determination of volatile organic compounds (VOCs) are often preserved with hydrochloric acid (HCl) to inhibit the biotransformation of the analytes of interest until the chemical analyses can he performed. However, it is theoretically possible that residual free chlorine in the HCl can react with dissolved organic carbon (DOC) to form chloroform via the haloform reaction. Analyses of 1501 ground water samples preserved with HCl from the U.S. Geological Survey's National Water-Quality Assessment Program indicate that chloroform was the most commonly detected VOC among 60 VOCs monitored. The DOC concentrations were not significantly larger in samples with detectable chloroform than in those with no delectable chloroform, nor was there any correlation between the concentrations of chloroform and DOC. Furthermore, chloroform was detected more frequently in shallow ground water in urban areas (28.5% of the wells sampled) than in agricultural areas (1.6% of the wells sampled), which indicates that its detection was more related to urban land-use activities than to sample acidification. These data provide strong evidence that acidification with HCl does not lead to the production of significant amounts of chloroform in ground water samples. To verify these results, an acidification study was designed to measure the concentrations of all trihalomethanes (THMs) that can form as a result of HCl preservation in ground water samples and to determine if ascorbic acid (C₆H₈O₆) could inhibit this reaction if it did occur. This study showed that no THMs were formed as a result of HCl acidification, and that ascorbic acid had no discernible effect on the concentrations of THMs measured.     

Field Investigation of Vapor‐Phase‐Based Groundwater Monitoring

The use of in‐field analysis of vapor‐phase samples to provide real‐time volatile organic compound (VOC) concentrations in groundwater has the potential to streamline monitoring by simplifying the sample collection and analysis process. A field validation program was completed to (1) evaluate methods for collection of vapor samples from monitoring wells and (2) evaluate the accuracy and precision of field‐portable instruments for the analysis of vapor‐phase samples. The field program evaluated three vapor‐phase sample collection methods: (1) headspace samples from two locations within the well, (2) passive vapor diffusion (PVD) samplers placed at the screened interval of the well, and (3) field vapor headspace analysis of groundwater samples. Two types of instruments were tested: a field‐portable gas chromatograph (GC) and a photoionization detector (PID). Field GC analysis of PVD samples showed no bias and good correlation to laboratory analysis of groundwater collected by low‐flow sampling (slope = 0.96, R² = 0.85) and laboratory analysis of passive water diffusion bag samples from the well screen (slope = 1.03; R² = 0.96). Field GC analysis of well headspace samples, either from the upper portion of the well or at the water‐vapor interface, resulted in higher variability and much poorer correlation (consistently biased low) relative to laboratory analysis of groundwater samples collected by low‐flow sample or passive diffusion bags (PDBs) (slope = 0.69 to 0.76; R² = 0.60 to 0.64). These results indicate that field analysis of vapor‐phase samples can be used to obtain accurate measurements of VOC concentrations in groundwater. However, vapor samples collected from the well headspace were not in equilibrium with water collected from the well screen. Instead, PVD samplers placed in the screened interval represent the most promising approach for field‐based measurement of groundwater concentrations using vapor monitoring techniques and will be the focus of further field testing.     

Utility of Compound‐Specific Isotope Analysis for Vapor Intrusion Investigations

Different types of data can be collected to evaluate whether or not vapor intrusion is a concern at sites impacted with volatile organic compound (VOC) contamination in the subsurface. Typically, groundwater, soil gas, or indoor air samples are collected to determine VOC concentrations in the different media. Sample results are evaluated using a “multiple lines of evidence” approach to interpret whether vapor intrusion is occurring. Data interpretation is often not straightforward because of many complicating factors, particularly in the evaluation of indoor air. More often than not, indoor air sample results are affected by indoor or other background sources making interpretation of concentration‐based data difficult using conventional sampling approaches. In this study, we explored the practicality of compound‐specific isotope analysis (CSIA) as an additional type of evidence to distinguish between indoor sources and subsurface sources (i.e., vapor intrusion). We developed a guide for decision‐making to facilitate data interpretation and applied the guidelines at four different test buildings. To evaluate the effectiveness of the CSIA method for vapor intrusion applications, we compared the interpretation from CSIA to interpretations based on data from two different investigation approaches: conventional sampling and on‐site GC/MS analysis. Interpretations using CSIA were found to be generally consistent with the other approaches. In one case, CSIA provided the strongest line of evidence that vapor intrusion was not occurring and that a VOC source located inside the building was the source of VOCs in indoor air.     

Relative Vulnerability of Public Supply Wells to VOC Contamination in Hydrologically Distinct Regional Aquifers

A process-based methodology was used to compare the vulnerability of public supply wells tapping seven study areas in four hydrologically distinct regional aquifers to volatile organic compound (VOC) contamination. This method considers (1) contributing areas and travel times of groundwater flowpaths converging at individual supply wells, (2) the oxic and/or anoxic conditions encountered along each flowpath, and (3) the combined effects of hydrodynamic dispersion and contaminant- and oxic/anoxic-specific biodegradation. Contributing areas and travel times were assessed using particle tracks generated from calibrated regional groundwater flow models. These results were then used to estimate VOC concentrations relative to an unspecified initial concentration (C/C₀) at individual public supply wells. The results show that the vulnerability of public supply wells to VOC contamination varies widely between different regional aquifers. Low-recharge rates, long travel times, and the predominantly oxic conditions characteristic of Basin and Range aquifers in the western United States leads to lower vulnerability to VOCs, particularly to petroleum hydrocarbons such as benzene and toluene. On the other hand, high recharge rates and short residence times characteristic of the glacial aquifers of the eastern United States leads to greater vulnerability to VOCs. These differences lead to distinct patterns of C/C₀ values estimated for public supply wells characteristic of each aquifer, information that can be used by resource managers to develop monitoring plans based on relative vulnerability, to locate new public supply wells, or to make land-use management decisions.     

GC/MS-Nontargetanalytik zur Aufklärung einer organischen Grundwasserkontamination. Teil I: Probennahme – Analytik – Identifikation der organischen Verbindungen

GC/MS Nontarget Analysis to Examine an Organic Groundwater Contamination. Part I: Sampling – Analysis – Identification GC/MS nontarget analysis is a combination of an extraction sequence and a GC/MS analysis without standards. The extraction sequence should enrich a wide range of organic substances with different chemical and physical properties. The GC/MS analysis without standards evaluates the total chromatogram whereas the possibilities of compound identification are limited. This kind of view is suited very well if the task of examinations are unknown organic contaminations and the conventional target analysis has to be expanded to a large number of compounds with the uncertainty of detecting the main contaminants. The extraction sequence is similar to the EPA 625 analysis of base/neutral and acid extractable organic compounds. Basis are liquid extraction and solid-phase extraction at different pH values. This extraction procedure covers approximately 30 % of total organic carbon of these groundwater samples from a contaminated area near a low temperature carbonization plant. Relevant groups of organic compounds analyzed in the contaminated groundwater or in the reference sample are substituted aromatics, phenols, benzoamines (anilines), and derivates of benzothiophene. Differences in the trace substance mixtures between the contaminated samples and the reference sample are demonstrated by applying modern graphical methods.     

Nature and Estimated Human Toxicity of Polar Metabolite Mixtures in Groundwater Quantified as TPHd/DRO at Biodegrading Fuel Release Sites

Polar metabolites resulting from petroleum biodegradation are measured in groundwater samples as TPHd unless a silica gel cleanup (SGC) is used on the sample extract to isolate hydrocarbons. Even though the metabolites can be the vast majority of the dissolved organics present in groundwater, SGC has been inconsistently applied because of regulatory concern about the nature and toxicity of the metabolites. A two‐step approach was used to identify polar compounds that were measured as TPHd in groundwater extracts at five sites with biodegrading fuel sources. First, gas chromatography with mass spectrometry (GC‐MS) was used to identify and quantify 57 individual target polar metabolites. Only one of these compounds—dodecanoic acid, which has low potential human toxicity—was detected. Second, nontargeted analysis was used to identify as many polar metabolites as possible using both GC‐MS and GC×GC‐MS. The nontargeted analysis revealed that the mixture of polar metabolites identified in groundwater source areas at these five sites is composed of approximately equal average percentages of organic acids, alcohols and ketones, with few phenols and aldehydes. The mixture identified in downgradient areas at these five sites is dominated by acids, with fewer alcohols, far fewer ketones, and very few aldehydes and phenols. A ranking system consistent with systems used by USEPA and the United Nations was developed for evaluating the potential chronic oral toxicity to humans of the different classes of identified polar metabolites. The vast majority of the identified polar metabolites have a “Low” toxicity profile, and the mixture of identified polar metabolites present in groundwater extracts at these five sites is unlikely to present a significant risk to human health.     

Removal of Volatile Organic Compounds in Vertical Flow Filters: Predictions from Reactive Transport Modeling

Vertical flow filters are containers filled with porous medium that are recharged from top and drained at the bottom, and are operated at partly saturated conditions. They have recently been suggested as treatment technology for groundwater containing volatile organic compounds (VOCs). Numerical reactive transport simulations were performed to investigate the relevance of different filter operation modes on biodegradation and/or volatilization of the contaminants and to evaluate the potential limitation of such remediation mean due to volatile emissions. On the basis of the data from a pilot‐scale vertical flow filter intermittently fed with domestic waste water, model predictions on the system’s performance for the treatment of contaminated groundwater were derived. These simulations considered the transport and aerobic degradation of ammonium and two VOCs, benzene and methyl tertiary butyl ether (MTBE). In addition, the advective‐diffusive gas‐phase transport of volatile compounds as well as oxygen was simulated. Model predictions addressed the influence of depth and frequency of the intermittent groundwater injection, degradation rate kinetics, and the composition of the filter material. Simulation results show that for unfavorable operation conditions significant VOC emissions have to be considered and that operation modes limiting VOC emissions may limit aerobic biodegradation. However, a suitable combination of injection depth and composition of the filter material does facilitate high biodegradation rates while only little VOC emissions take place. Using such optimized operation modes would allow using vertical flow filter systems as remediation technology suitable for groundwater contaminated with volatile compounds.     

Evaluating TCE Abiotic and Biotic Degradation Pathways in a Permeable Reactive Barrier Using Compound Specific Isotope Analysis

A pilot‐scale zero valent iron (ZVI) Permeable Reactive Barrier (PRB) was installed using an azimuth‐controlled ‐vertical hydrofracturing at an industrial facility to treat a chlorinated Volatile Organic Compound (VOC) plume. Following ZVI injection, no significant reduction in concentration was observed to occur with the exception of some multilevel monitoring wells, which also showed high levels of total organic carbon (TOC). These patterns suggested that the zero valent iron was not well distributed in the PRB creating leaky conditions. The geochemical data indicated reducing conditions in these areas where VOC reduction was observed, suggesting that biotic processes, associated to the guar used in the injection of the iron, could be a major mechanism of VOC degradation. Compound‐Specific Isotope Analysis (CSIA) using both carbon and chlorine stable isotopes were used as a complementary tool for evaluating the contribution of abiotic and biotic processes to VOC trends in the vicinity of the PRB. The isotopic data showed enriched isotope values around the PRB compared to the isotope composition of the VOC source confirming that VOC degradation is occurring along the PRB. A batch experiment using site groundwater collected near the VOC source and the ZVI used in the PRB was performed to evaluate the site‐specific abiotic isotopic fractionation patterns. Field isotopic trends, typical of biodegradations were observed at the site and were different from those obtained during the batch abiotic experiment. These differences in isotopic trends combined with changes in VOC concentrations and redox parameters suggested that biotic processes are the predominant pathways involved in the degradation of VOCs in the vicinity of the PRB.     

Influence of Fluctuating Groundwater Table on Volatile Organic Chemical Emission Flux at a Dissolved Chlorinated-Solvent Plume Site

Groundwater elevation fluctuation has been recognized as one mechanism causing temporal indoor air volatile organic chemical (VOC) impacts in vapor intrusion risk assessment guidance. For dissolved VOC sources, groundwater table fluctuation shortens/lengthens the transport pathway, and delivers dissolved contaminants to soils that are alternating between water saturated and variably saturated conditions, thereby enhancing volatilization potential. To date, this mechanism has not been assessed with field data, but enhanced VOC emission flux has been observed in lab-scale and modeling studies. This work evaluates the impact of groundwater elevation changes on VOC emission flux from a dissolved VOC plume into a house, supplemented with modeling results for cyclic groundwater elevation changes. Indoor air concentrations, air exchange rates, and depth to groundwater (DTW) were collected at the study house during an 86-d constant building underpressurization test. These data were used to calculate changes in trichloroethylene (TCE) emission flux to indoor air, during a period when DTW varied daily and seasonally from about 3.1 to 3.4 m below the building foundation (BF). Overall, TCE flux to indoor air varied by about 50% of the average, without any clear correlation to changes in DTW or its change rate. To complement the field study, TCE surface emission fluxes were simulated using a one-dimensional model (HYDRUS 1D) for conditions similar to the field site. Simulation results showed time-averaged surface TCE fluxes for cyclic water-table elevations were greater than for stationary water-table conditions at an equivalent time-averaged water-table position. The magnitudes of temporal TCE emission flux changes were generally less than 50% of the time-averaged flux, consistent with the field site observations. Simulation results also suggested that TCE emission flux changes due to groundwater fluctuation are likely to be significant at sites with shallow groundwater (e.g., < 0.5 m BF) and permeable soil types (e.g., sand).     

Interactions between groundwater seepage and sediment porewater sulphate concentration profiles in lake anna,Virginia

Most sulphur diagenesis models predict that SO₄^2- concentrations decrease exponentially with increasing sediment depth and are lower than that of the overlying water throughout the sediments. Low SO₄^2- concentrations (less than 0.2 mM) are common in the sediments of Lake Anna that receive acid mine drainage; however, sediment with as much as 20 mM SO₄^2- at about 20cm below the sediment surface is also seen in this section of the lake. A decision tree was proposed to investigate the cause of the high SO₄^2- concentrations at depth (HSD) in the sediment. The first possibility proposed was that an increase in the quantity of groundwater flowing through Lake Anna sediments may increase groundwater advection of SO₄^2- or oxygen which would induce sulphide oxidation. This hypothesis was tested by measuring groundwater flow. HSD profiles were found in a discrete region of the lake; however, stations having these profiles did not have higher groundwater flow than other sites sampled. Alternate explanations for the HSD profiles were that the region in which they occurred had: (1) unusual sediment chemical compositions; (2) a different source of regional groundwater, or (3) a lateral intrusion of high SO₄^2- groundwater. There were no differences in sulphide and organic matter concentrations between the two regions. The area which has HSD in the sediment covers a large area in the middle of the lake, so it is unlikely that it has a unique source of regional groundwater. The third alternative was supported by the fact that in all three sample years, HSD stations were located in the preimpoundment stream channel, which is a likely lateral flow path for groundwater containing high SO₄^2- concentrations.     

Field Application of the Combined Membrane‐Interface Probe and Hydraulic Profiling Tool (MiHpt)

The Membrane‐Interface Probe and Hydraulic Profiling Tool (MiHpt) is a direct push probe that includes both the membrane interface probe (MIP) and hydraulic profiling tool (HPT) sensors. These direct push logging tools were previously operated as separate logging systems for subsurface investigation in unconsolidated formations. By combining these two probes into one logging system the field operator obtains useful data about the distribution of both volatile organic contaminants (VOCs) and relative formation permeability in a single boring. MiHpt logging was conducted at a chlorinated VOC contaminated site in Skuldelev, Denmark, to evaluate performance of the system. Formation cores and discrete interval slug tests are used to assess use of the HPT and electrical conductivity (EC) logs for lithologic and hydrostratigraphic interpretation. Results of soil and groundwater sample analyses are compared to the adjacent MiHpt halogen specific detector (XSD) logs to evaluate performance of the system to define contaminant distribution and relative concentrations for the observed VOCs. Groundwater profile results at moderate to highly contaminated locations were found to correlate well with the MiHpt‐XSD detector responses. In general, soil sample results corresponded with detector responses. However, the analyses of saturated coarse‐grained soils at the site proved to be unreliable as demonstrated by high RPDs for duplicate samples. The authors believe that this is due to pore water drainage observed from these cores during sampling. Additionally, a cross section of HPT pressure and MiHpt‐XSD detector logs provides insight into local hydrostratigraphy and formation control on contaminant migration.     

Activation of Persulfate by Surfactants under Acidic and Basic Conditions

Activated persulfate is a commonly used oxidant source used for in situ chemical oxidation (ISCO) for remediation of subsurface contamination. Surfactants are sometimes used in ISCO to desorb contaminants and dissolve nonaqueous phase liquids (NAPLs). The potential activation of persulfate by such surfactants was investigated, and the reactive oxygen species generated by persulfate in the presence of anionic, nonionic, and cationic surfactants were determined. Twenty surfactants were screened; most activated persulfate to generate reductants + nucleophiles at acidic and basic pH. The most reactive anionic, nonionic, and cationic surfactants (Lankropol 4500, polyethylene glycol 400, and Ethoduomeen T/25) were investigated in more detail. All three surfactants activated persulfate; however, the cationic surfactant showed the most potential for persulfate activation with high fluxes of hydroxyl radical and reductants + nucleophiles. The results of this research demonstrate that surfactants added to ISCO systems often activate persulfate to generate reductants at both acidic and basic pH, and hydroxyl radical at basic pH. These findings provide a new paradigm for persulfate activation in surfactant in situ chemical oxidation (SISCO) systems; pH regimes >11 may not be necessary for persulfate activation resulting in cost savings and potentially more effective activation of persulfate.     

Negative Bias and Increased Variability in VOC Concentrations Using the HydraSleeve in Monitoring Wells

The HydraSleeve is a sampling device for collecting groundwater from the screened interval of a monitoring well without purging that uses a check valve to take in water over the first 3 to 5 feet of an upward pulling motion. If the check valve does not perform as expected, then the HydraSleeve has the potential to collect water from an incorrect depth interval, possibly above the screened interval of the well. We have evaluated volatile organic chemical (VOC) results from groundwater samples collected with the HydraSleeve sampler compared to other methods for sampling monitoring wells at three sites. At all three sites, lower VOC concentration results were observed for samples collected using the HydraSleeve. At two of these three sites, the low concentration sample results were most strongly associated with monitoring wells with more than 10 feet of water above the monitoring well‐screened interval. At the site with the largest dataset, the median bias for samples collected with HydraSleeve was ?20% (p < 0.001). At this site, a bias of ?26% (p < 0.001) was observed for the subset of monitoring wells with greater than 10 feet of water above the screened interval compared to a bias of ?7% (p = 0.21) for wells screened across the top of the water table. In addition to lower VOC concentrations, the monitoring records obtained using the HydraSleeve were more variable compared to monitoring records obtained using purge sampling methods, a characteristic that would make it more difficult to determine the long‐term concentration trend in the well.     

Influence of Shallow Geology on Volatile Organic Chemical Attenuation from Groundwater to Deep Soil Gas

Vapor intrusion pathway evaluations commonly begin with a comparison of volatile organic chemical (VOC) concentrations in groundwater to generic, or Tier 1, screening levels. These screening levels are typically quite low reflecting both a desired level of conservatism in a generic risk screening process as well as limitations in understanding of physical and chemical processes that impact vapor migration in the subsurface. To study the latter issue, we have collected detailed soil gas and groundwater vertical concentration profiles and evaluated soil characteristics at seven different sites overlying chlorinated solvent contaminant plumes. The goal of the study was to evaluate soil characteristics and their impacts on VOC attenuation from groundwater to deep soil gas (i.e., soil gas in the unsaturated zone within 2 feet of the water table). The study results suggest that generic screening levels can be adjusted by a factor of 100× at sites with fine‐grained soils above the water table, as identified by visual observations or soil air permeability measurements. For these fine‐grained soil sites, the upward‐adjusted screening levels maintain a level of conservatism while potentially eliminating the need for vapor intrusion investigations at sites that may not meet generic screening criteria.     

Evaluation of Extensive Secondary Maximum Contaminant Level Exceedances Following Remediation by In Situ Chemical Oxidation

In situ chemical oxidation (ISCO) with activated persulfate is commonly used for the remediation of petroleum impacted soil and groundwater because of its proven efficiency and the perception that reaction end products are completely innocuous. While the reaction products are less hazardous compared to the contaminants being treated, they may inadvertently prolong site closure in areas that have adopted the U.S. Environmental Protection Agency (EPA) Secondary Maximum Contaminant Levels (SMCLs) as enforceable standards. This study examines the occurrence and persistence of iron, manganese, sulfate, sodium, and total dissolved solids (TDS) in groundwater following persulfate ISCO. The concentrations of these chemicals were observed remaining above their respective regulatory criteria almost 3 years following the chemical application. Background concentrations and mobilization due to the petroleum contamination and ISCO application are also evaluated. Baseline sampling revealed substantially higher iron and manganese concentrations inside the plume area compared to the upgradient and downgradient wells suggesting mobilization due to redox reactions occurring inside of the plume. Iron was not a component in the applied chemical formula, yet the iron concentration spiked by 366% in the key monitoring well during the first post-remediation monitoring event. Ionic interactions between the ISCO amendment and native soils are believed to be responsible for displacing significant quantities of iron from the soil. Sulfate, sodium, and TDS exceedances are primarily associated with decomposition products of the ISCO amendments. The iron, manganese, sulfate, sodium, and TDS concentrations are trending downward over time, but still exceed regulatory criteria or pre-ISCO concentrations.     

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

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

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.     

Estimating the Impact of Vadose Zone Sources on Groundwater to Support Performance Assessment of Soil Vapor Extraction

Soil vapor extraction (SVE) is a prevalent remediation remedy for volatile organic compound (VOC) contaminants in the vadose zone. To support selection of an appropriate condition at which SVE may be terminated for site closure or for transition to another remedy, an evaluation is needed to determine whether vadose zone VOC contamination has been diminished sufficiently to keep groundwater concentrations below threshold values. A conceptual model for this evaluation was developed for VOC fate and transport from a vadose zone source to groundwater when vapor‐phase diffusive transport is the dominant transport process. A numerical analysis showed that, for these conditions, the groundwater concentration is controlled by a limited set of parameters, including site‐specific dimensions, vadose zone properties, and source characteristics. On the basis of these findings, a procedure was then developed for estimating groundwater concentrations using results from the three‐dimensional multiphase transport simulations for a matrix of parameter value combinations and covering a range of potential site conditions. Interpolation and scaling processes are applied to estimate groundwater concentrations at compliance (monitoring) wells for specific site conditions of interest using the data from the simulation results. The interpolation and scaling methodology using these simulation results provides a far less computationally intensive alternative to site‐specific three‐dimensional multiphase site modeling, while still allowing for parameter sensitivity and uncertainty analyses. With iterative application, the approach can be used to consider the effect of a diminishing vadose zone source over time on future groundwater concentrations. This novel approach and related simulation results have been incorporated into a user‐friendly Microsoft® Excel®‐based spreadsheet tool entitled SVEET (Soil Vapor Extraction Endstate Tool), which has been made available to the public.