Quantitative Risk Assessment of Trichloroethylene for a Former Chemical Works in Shanghai,China

Assessment of the potential risks posed by chlorinated solvents in groundwater is the key to establish the extent of the contamination and derive achievable remedial targets should remediation deems necessary. This article first presents the application of the American Society for Testing and Materials (ASTM) Risk Based Corrective Actions (RBCA) Guidance to quantitatively evaluate human health and environmental risk for a former chemical works in Shanghai, China. The observed maximum trichloroethylene (TCE) concentration in groundwater at the site reached 1220 mg/l that exceeded its solubility of 1070 mg/l at 10°C (Soil annual average temperature is 10°C in Shanghai). The maximum concentration for cis-1, 2-DCE (DCE) was also found to be elevated at 264 mg/l. A critical exposure pathway was considered to be indoor vapor intrusion of TCE into the buildings with excess lifetime cancer risk for children being 1.7 × 10^?3. This cancer risk exceeded regulatory limits of 1 × 10^?4 to 1 × 10^?6 for The Netherlands, the United Kingdom, and the United States. The calculated groundwater remedial targets for TCE and DCE are 7 mg/l and 904 mg/l, respectively, in order to protect child residents from inhalation of indoor vapors within the close proximity of the source area.     

Capillary Effects on Natural Remobilization of Pools of Dense Non-Aqueous Phase Liquid Mixtures in Porous Media

The natural remobilization of an initially static mixed dense non-aqueous phase liquid (DNAPL) pool due to dissolution was demonstrated by (Roy et al. 2002 Roy, J. W., Smith, J. E. and Gillham, R. W. 2002. Natural remobilization of multicomponent DNAPL pools due to dissolution. J. Contam. Hydrol., 59: 163–186. [Crossref], [PubMed], [Web of Science ®] [Google Scholar], 2004 Roy, J. W., Smith, J. E. and Gillham, R. W. 2004. Laboratory evidence of natural remobilization of multicomponent DNAPL pools due to dissolution. J. Contam. Hydrol., 74: 145–161. [Crossref], [PubMed], [Web of Science ®] [Google Scholar]) using a compositional mathematical model and laboratory experiments with open pools over a porous medium. The purposes of this study were to: a) demonstrate natural remobilization for a pool within porous media (as opposed to an open pool); and b) analyze the capillary effects associated with residual formation, a changing saturation profile, hysteresis, and aging, as these processes may reduce the potential for natural remobilization of pools in porous media. DNAPL pools comprised of tetrachloroethene and benzene were created within a zone of larger glass beads overlying smaller glass beads, in a water-saturated 2-D flow cell. In one case, remobilization occurred in the form of a DNAPL finger, after 56 days of flushing. In another case, no remobilization had occurred after 64 days of flushing, though the density increased by 430 kg m ^?3 and remobilization was predicted by the compositional model. Comparison of observations with model predictions suggest that contact angle hysteresis, related to an observed change in wettability, was the most significant contributing factor causing overprediction of the potential for natural remobilization.     

Evaluation of Whey for Bioremediation of Trichloroethene Source Zones

The effectiveness of whey as an electron donor that stimulates bioremediation and enhances dissolution of trichloroethene (TCE) dense non-aqueous phase liquid (DNAPL) was investigated. Laboratory experiments were conducted to evaluate increased mass transfer of TCE from the DNAPL to the aqueous phase in abiotic batch microcosms amended with several concentrations of whey, and in abiotic columns using high- and low-concentration whey mixtures. The effective solubility of TCE was a factor of 6 higher in microcosms amended with 10% w/w whey compared to 1% w/w whey or nanopure water. Increased aqueous-phase concentrations of TCE were a function of both the concentration of whey and time. In the columns, a factor of 5 increase in TCE concentrations was observed in the effluent during amendment with 10% w/w whey compared to potable water and 1% w/w whey. A field study involving three whey injections was performed at a site that had been actively undergoing bioremediation in a residual source area using lactate for 5 years. Results of the field test show a factor of 3 increase in total molar concentrations of chloroethenes and ethene following injection of 10% w/w whey compared to 5% lactate. In addition, complete dechlorination of TCE to ethene continued.     

Bacterial diversity of an acidic Louisiana groundwater contaminated by dense nonaqueous-phase liquid containing chloroethanes and other solvents

Bacterial concentration and diversity was assessed in a moderately acidic (pH 5.1) anaerobic groundwater contaminated by chlorosolvent-containing DNAPL at a Superfund site located near Baton Rouge, Louisiana. Groundwater analysis revealed a total aqueous-phase chlorosolvent concentration exceeding 1000 mg L(-1), including chloroethanes, vinyl chloride, 1,2-dichloropropane, and hexachloro-1,3-butadiene as the primary contaminants. Direct counting of stained cells revealed more than 3 x 10(7) cells mL(-1) in the groundwater, with 58% intact and potentially viable. Universal and 'Dehalococcoides'-specific 16S rRNA gene libraries were created and analyzed. Universal clones were grouped into 18 operational taxonomic units (OTUs), which were dominated by low-G+C Gram-positive bacteria (62%) and included several as yet uncultured or undescribed organisms. Several unique 16S rRNA gene sequences closely related to Dehalococcoides ethenogenes were detected. Anaerobically grown isolates (168 in total) were also sequenced. These were phylogenetically grouped into 18 OTUs, of which only three were represented in the clone library. Phylogenetic analysis of isolates and the clone sequences revealed close relationships with dechlorinators, fermenters, and hydrogen producers. Despite acidic conditions and saturation or near-saturation chlorosolvent concentrations, the data presented here demonstrate that large numbers of novel bacteria are present in groundwater within the DNAPL source zone, and the population appears to contain bacterial components necessary to carry out reductive dechlorination.     

Vapor Pressure Characterization to Predict Contaminant Releases from MGP Site Source Area Soils

Risk-based management of contaminated sites often requires timely screening and identification of source areas that release contaminants to groundwater and other reception of concern. Over-reliance on total concentrations often results in costly site characterization, delays in remediation, and overestimation of the soil volumes targeted for removal or treatment. Advances in diagnostic tools to accelerate source area characterization will improve the reliability of management decisions. The objective of this work was to determine the potential of using vapor pressure measurements as a rapid indicator of the mass release potential of suspected source area soils.

The current work has focused on determining the relationship between partial pressure and mobility for monoaromatic and polycyclic aromatic hydrocarbon (PAH) contaminants in source area soils. This work ascertained that for a wide spectrum of non-ionized, aromatic contaminants in MGP soils, total vapor pressure and benzene partial pressure could be measured with good repeatability. Under controlled conditions, photoionization detector (PID) measurements on 16 soil samples from two MGP sites were found to correlate well to laboratory measurements of equilibrium partitioning and resin-mediated soil contaminant desorption with R² values of over 0.9. Results indicate that vapor pressure correlates well to contaminant mobility in soils.     

Three-Dimensional Multifluid Flow and Transport at the Brooklawn Site near Baton Rouge,LA: A Case Study

Disposal quantities of organic wastes at the Brooklawn Site in Louisiana are suspected to equal nearly 1.45 × 10⁸Kg, making this site one of the most contaminated dense nonaqueous phase liquid (DNAPL) sites in the world. Remedial activities at the site include groundwater and DNAPL extraction from recovery wells. DNAPL recovery has markedly declined in recent years, with many of the peripheral wells showing negligible recovery of organic liquids. Three-dimensional simulations of DNAPL movement in the subsurface were conducted using the STOMP simulator, including a new coupled-well model. The objectives of this modeling effort were to (1) determine the fate and transport of infiltrated DNAPL, and (2) measure the effects of active recovery through DNAPL pumping. A detailed three-dimensional geologic model of the Brooklawn primary DNAPL disposal area was developed and used as the framework for DNAPL simulations. Additionally, site-specific data were obtained to determine the most important hydraulic properties of the subsurface related to DNAPL movement and formation of entrapped DNAPL in the laboratory. In addition to a simulation using the best available subsurface information, several sensitivity simulations were conducted to assess the effects on DNAPL migration. These simulations include DNAPL pumping, well screen extension, an alternative geology, increased DNAPL density, lower DNAPL viscosity, and more-permeable sand and silt deposits.

Results of the simulations were compared to field data that define the extent of DNAPL movement based on where DNAPL has been extracted in the site recovery wells. The model simulations show that pumping has a negligible effect on subsurface DNAPL saturations and movement. Pumped DNAPL volumes diminish rapidly due to the limited radius of influence of the wells and movement of the DNAPL out of the zone of influence of the wells with a maximum radius of influence of about 6 m. The numerical analysis also demonstrates that it is impractical to extend existing wells or install new wells to retrieve enough DNAPL to affect the overall extent of DNAPL movement.     

Literature Review of 2-D Laboratory Experiments in NAPL Flow,Transport, and Remediation

The migration of nonaqueous phase liquid (NAPL) contaminants in the subsurface results in a complex multiphase environment due in part to heterogeneity in both the soil and fluid saturations. To accurately predict the flow, transport, and remediation of NAPL contaminants, research has focused on laboratory and numerical modeling of the subsurface environment. Within this research, 2-D laboratory model are advantageous due to the fact that the capillary, viscous, and buoyancy forces found in the subsurface environment can be reproduced. Thus, they can be used to study flow and transport, test and develop remediation technologies, and verify numerical models. However, to date a comprehensive review of the 2-D experimental work has not been compiled. The review presented in this article should be of interest to geohydrologists, engineers and scientists involved in both applied and research aspects of NAPL-contaminated aquifers.     

Numerical Modeling to Assess DNAPL Movement and Removal at the Scenic Site Operable Unit Near Baton Rouge,Louisiana: A Case Study

Detailed three-dimensional multifluid flow modeling was conducted to assess movement and removal of dense nonaqueous phase liquid (DNAPL) movement at a waste site in Louisiana. The site's subsurface consists of several permeable zones separated by (semi) confining clays. In the upper subsurface, the two major permeable zones are, starting with the uppermost zone, the +40- and +20-MSL (mean sea level) zones. At the site, a total of 23,000 m³ of DNAPL was emplaced in an open waste pit between 1962 and 1974. In this period, considerable amounts of DNAPL moved into the subsurface. By 1974 a portion of the DNAPL was removed and the waste site was filled with low-permeability materials and closed. During this process, some of the DNAPL was mixed with the fill material and remained at the site. Between 1974 and 2000, no additional DNAPL recovery activities were implemented. In an effort to reduce the DNAPL source, organic liquid has been pumped through a timed-pumping scheme from a total of 7 wells starting in calendar year 2000. The recovery wells are screened in the lower part of the waste fill material. In site investigations, DNAPL has been encountered in the +40-MSL but not in the +20-MSL zone. The following questions are addressed: (1) Where has the DNAPL migrated vertically and laterally? (2) How much further is DNAPL expected to move in the next century? (3) How effective is the current DNAPL pumping in reducing the DNAPL source? The computational domains for the simulations were derived from 3-D interpolations of borehole logs using a geologic interpretation software (Earthvision?). The simulation results show that DNAPL primarily entered the subsurface in the period 1962–1974, when the waste site was operational. After 1974, the infiltration rates dropped dramatically as a result of the infilling of the waste pit. The simulation results indicate that DNAPL moved from the pit into the underlying +40-MSL zone through two contact zones at the west side of the pit. Lateral movement of the DNAPL body has been relatively slow as a result of the high viscosity and the rapidly decreasing driving force after the waste pit was filled in. For all simulations, lateral movement of DNAPL in the period 1962–2001 is predicted to be less than 60 m from the two contact areas, while additional movement in the next century is expected to be less than 30 m. No DNAPL is predicted to enter the +20-MSL zone, which agrees with site information. The simulations also clearly demonstrate the minimal effect of the current pumping scheme on source reduction and DNAPL movement.     

Complex NAPL Site Characterization Using Fluorescence Part 3: Detection Capabilities for Specific Excitation Sources

Non-aqueous phase liquid (NAPL) contaminants comprised of polycyclic aromatic hy drocarbons (PAHs) can be detected using fluorescence spectroscopic methods. Dense non-aqueous phase liquid (DNAPL) contaminant source zones can be delineated us ing commercially available cone penetrometer (CPT)devices by detecting commingled oils fuels, and naturally occurring organic materials entrained by DNAPLs and carried to depths below the water table. It has been demonstrated that commercially avail able CPT based fluorescence detection systems can be ranked based on how effectively their excitation source wavelengths induce fluorescence using excitation emission ma trices (EEMs). Several neat NAPLs and dilutions with selected DNAPLs were analyzed for specific fluorescence characteristics to determine the optimal excitation source for site characterization efforts. A comprehensive spectral library and corresponding opti mization matrix were generated for complex petroleum mixtures. Based onfield results documenting successful indirect CPT fluorescence detection of a DNAPL source zone, aviation and dieselfuels were selected from this library, diluted with chlorinated sol vents, and evaluated for fluorescence characteristics. Dilution of these complex NAPL mixtures led to changes in the corresponding EEMs. The optimal excitation source for aviationfuel remained relatively constantf or each dilution. However, sensitivityf or each of the commercially available CPT excitation sources was strongly dependent on diesel concentration, whereby higher energy (lowerwavelength) sources yielded improved sen-sitivityfor lower concentrations. Since field concentrations can be highly variable, these observations support the need for multiple wavelength excitation sources for optimal detection capabilities, particularly when diesel fuel ispresent.     

Complex NAPL Site Characterization Using Fluorescence Part 2: Analysis of Soil Matrix Effects on the Excitation/Emission Matrix

Commercially available cone penetrometer (CPT)fluorescence based sensor platforms have been used to detect non-aqueous phase liquids (NAPLs), such as petroleum oils and lubricants, in situf or more than a decade. These approaches have also been used to detect dense non-aqueous phase liquid (DNAPL) source zones by detecting commingled oilsfuels, and naturally occurring organic materials entrained by DNAPLs and carried to depths below the water table. Several neat NAPLs and mixtureswere added to various soil types and analyzedfor specific fluorescence characteristics to determine the optimal excitation source for site characterization efforts. Using excitationlemission matrices (EEMs), we demonstrate that an optimized excitation wavelength can be determinedfor specific fiuowphores within the NAPL mixtures, and that available systems can be ranked based on the specific contaminant and site soil types. An optimal excitation wavelength yields the maximum fluorescence within an EEM spectrum. We ranked commercially available cone penetrometer fluorescence detection systems according to the potential for ease of detection based on maximum fluorescence response. When soils were added tocomplexNAPLmixtures,analytefluorescence emissionwasattenuatedinpreferential portions of the EEM, leading to differences in the optimal excitation source wavelength. Furthermore, impure silica-containing minerals impact the emission signal, potentially leading to incorrect conclusionsf or several commercially available systems. Our find ings suggest that afrequency-agile (e.g., tunable excitation source) probe system would be superior to any other system commercially available, provided the system would be relatively easy to operate and would have rapid in-situ EEM generating capabilitiesfo r optimization in the field.