The Application of Petroleum Hydrocarbon Fingerprint Characterization in Site Investigation and Remediation

Tremendous resources have been and continue to be spent investigating and remediating petroleum hydrocarbon compounds (PHCs) in soil and ground water. Investigating and planning a remedial strategy for sites affected by PHCs is often a challenging task because of the complex chemical nature of the PHCs. the complex regulatory environment related to PHC cleanup, and the use of analytical methods that provide quantitation but not identification of PHCs. From a technical standpoint, the PHC impacting soil and/or ground water is frequently inadequately characterised, both in identification as well as in is general properties (solubility, toxicity). From a regulatory standpoint, promulgated or recommended total petroleum hydrocarbon (TPH) cleanup levels generally relate to assumed properties of specific unweathered products and are inconsistent among different agencies and regions. This produces a prime situation for unwillingly spending more resources on investigation or remediation than may be necessary, especially when the PHC in the subsurface has different properties from unweathered products such as gasoline or diesel.
Accurately identifying the PHC and its nature, a process known as fingerprint characterization, is critical to the determination of appropriate regulatory goals and design of cost-effective remedial approaches. This paper presents several case studies in which fingerprint characterization made a significant difference in the project outcome. In each instance the nature of the organic material was better understood, the regulatory cleanup levels were negotiated based on the nature of the material, and a remedial approach was implemented that differed significantly from and was generally less costly than what would have been required without fingerprint characterization data.     

Progress in Remediation of Groundwater at Petroleum Sites in California

Quantifying the overall progress in remediation of contaminated groundwater has been a significant challenge. We utilized the GeoTracker database to evaluate the progress in groundwater remediation from 2001 to 2011 at over 12,000 sites in California with contaminated groundwater. This paper presents an analysis of analytical results from over 2.1 million groundwater samples representing at least $100 million in laboratory analytical costs. Overall, the evaluation of monitoring data shows a large decrease in groundwater concentrations of gasoline constituents. For benzene, half of the sites showed a decrease in concentration of 85% or more. For methyl tert‐butyl ether (MTBE), this decrease was 96% and for TBE, 87%. At remediation sites in California, the median source attenuation rate was 0.18/year for benzene and 0.36/year for MTBE, corresponding to half‐lives of 3.9 and 1.9 years, respectively. Attenuation rates were positive (i.e., decreasing concentration) for benzene at 76% of sites and for MTBE at 85% of sites. An evaluation of sites with active remediation technologies suggests differences in technology effectiveness. The median attenuation rates for benzene and MTBE are higher at sites with soil vapor extraction or air sparging compared with sites without these technologies. In contrast, there was little difference in attenuation rates at sites with or without soil excavation, dual phase extraction, or in situ enhanced biodegradation. The evaluation of remediation technologies, however, did not evaluate whether specific systems were well designed or implemented and did not control for potential differences in other site factors, such as soil type.     

A Diffusive Sampler for Passive Monitoring of Underground Storage Tanks

Passive measurements of volatile organic compounds (VOCs) provide a method for early detection and long-term monitoring of potential leaks from underground storage tanks (USTs) and associated fuel service lines. A diffusive sampler was constructed of a sorbent tube that fits inside a specially designed sampling chamber. VOCs in the soil enter the chamber by molecular diffusion and are collected by the sorbent. The sorbent is easily retrieved for laboratory analyses by thermally desorbing into a gas chromatograph/mass spectrometer (GC/MS), or qualitative concentrations can be determined directly in the field with specific-indicator detectors.
The diffusive samplers were evaluated in an exposure chamber under controlled conditions. Laboratory measurements of the sorbed mass of organic vapor were found to be in close agreement with theoretical values and indicate the passive sampling approach is viable for detecting relatively low concentrations of organic vapors in the vadose zone over a one-day sampling period, as well as providing relatively long-term monitoring periods up to 58 days. A field test found the sampling approach successful in identifying an area where the vadose zone was contaminated by leaking petroleum USTs.     

Investigation and Remediation of a 1,2–Dichloroethane Spill Part I: Short and Long-Term Remediation Strategies

Release of an estimated 150,000 gallons (568,000 L).of 1.2–dichloroethane (EDC) from a buried pipeline into a ditch and surrounding soil resulted in shallow subsurface contamination of a Gulf Coast site. Short-term remediation included removal of EDC DNAPI. (dense nonaqueous phase liquid) by dredging and vacuuming the ditch, and by dredging the river where the ditch discharged. EDC saturation in shallow impacted sediments located beneath the ditch was at or below residual saturation and these sediments were therefore left in place. The ditch was lined, backfilled, and capped. Long-term remediation includes EDC DNAPL recovery and hydraulic containment from the shallow zone with long-term monitoring of the shallow, intermediate, and deep (200 foot) aquifers. Ground water, DNAPL., and dissolved phase models were used to guide field investigations and the selection of an effective remedial action strategy. The DNAPL. modeling was conducted for a two-dimensional vertical cross section of the site, and included the three aquifers separated by two aquitards with microfractures. These aquitards were modeled using a dual porosity approach. Matrix and fracture properties of the aquitards used for DNAPL modeling were determined from small-scale laboratory properties. These properties were consistent with effective hydraulic conductivity determined from ground water flow modeling. A sensitivity analysis demonstrated that the vertical migration of EDC was attenuated by dissolution of EDC into the matrix of the upper aquitard. When the organic/water entry pressure of the aquitard matrix, or the solubility of EDC were decreased to unrealislically low values. EDC DNAPL. accumulated in the aquifer below the upper aquitard.
EDC DNALM, did not reach the regional (deepest) aquifer in any of the cases modeled. The limited extent of vertical EDC migration predicted is supported by ground water monitoring conducted over the four years since the spill.     

A New Pumping Strategy for Petroleum Product Recovery from Contaminated Hydrogeologic Systems: Laboratory and Field Evaluations

More than 200,000 gallons of automatic transmission fluid (ATF) leaked from an underground storage tank system and contaminated an area of about 64,000 ft² of a soil and ground water system. A pumping strategy for improved drainage and recovery of free oil was developed, tested in a laboratory model aquifer, and implemented and evaluated at the field site. This pumping strategy differs from conventional approaches in two important ways: (1) The oil recovery rate is carefully controlled to maximize the pumping rate while maintaining continuity between the oil layer in the soil and the recovery well, to avoid isolation of the oil in the subsurface; and (2) The rate of ground water pumping is controlled to maintain the depressed oil/water interface at its prepumped position. This approach prevents further spread of oil into the ground water, prevents reduction in the volume of recoverable oil due to residual retention, and maintains a gradient for oil flow toward the recovery well. In a model aquifer study, nearly 100 percent of the recoverable volume of ATF was pumped from the system, and about 56,000 gallons of the ATF has been recovered from the field site.     

Remediation of Dissolved BTEX Through Surface Application: A Prototype Field Investigation

The feasibility of surface application for remediating monoaromatic hydrocarbons (benzene, toluene, ethylbenzene, and xylenes — termed BTEX as a croup) dissolved in ground water under field conditions was investigated at a site within Canadian Forces Base. Borden. Ontario. The surface area was 25 m² and underlain by 3 to 3.5 m of unsaturated sands soil. For periods of at least 216 hours, between 43 and 72 cm/d of water containing BTEX at concentrations that averaged between 8 and 11 mg/L were continuously applied by drip irrigation. Nitrogen was added to the soil as a nutrient for the final third of the investigation.
Before the applied water reached the water table. BTEX mass losses ranged from of to essentially KM) percent. Less than 6 percent of the BTEX mass losses could be attributed to volatilization from the unsaturated soil. The remaining BTEX mass losses were attributed to biodegradation, mostly in the top 50 cm of the soil, which contained more inorganic nitrogen and organic carbon than the deeper soil. Biodegradation rates increased with applied concentration, nitrogen addition, and exposure to BTEX. Benzene concentrations in ground water attained compliance with Canadian and American drinking water standards only after nitrogen application.     

Evaluation of the Effectiveness of Different Methods for the Remediation of Contaminated Groundwater by Determining the Petroleum Hydrocarbon Content

The effectiveness of different remediation procedures for decreasing the amount of TPH (total petroleum hydrocarbons) in contaminated groundwater was evaluated at the site of a former refinery. The investigations were carried out on samples taken from several gravel based HSSF (horizontal subsurface flow) constructed wetlands (CW) which differed in relation to their filter material additives (no additive, charcoal, and ferric oxides additives) and examined the potential effect of these additives on the overall treatment efficiency. Samples of the following gravel based HSSF CW were investigated. No filter additive (system A), 0.1% activated carbon (system B), 0.5% iron(III) hydroxide (system C), and the reference (system D). Systems A–C were planted with common reed (Phragmites australis), whereas system D remained unplanted. In addition, the influence of seasonal conditions on the reduction of these hydrocarbons and the correlation between the amounts of TPH and BTEX (benzene, toluene, ethylbenzene, and xylene isomers), on the one hand, and methyl tert‐butyl ether, on the other, was investigated. The study was carried out by using a modified GC‐FID approach and multivariate methods. The investigations carried out in the first year of operation demonstrated that the effectiveness of the petroleum hydrocarbon removal was highest and reached a level of 93 ± 3.5% when HSSF filters with activated carbon as a filter additive were used. This remediation method allowed the petroleum hydrocarbon content to be reduced independently of seasonal conditions. The correlation between the reduction of TPH and BTEX was found to be R = 0.8824. Using this correlation coefficient, the time‐consuming determination of the BTEX content was no longer necessary.     

Investigation and Remediation of a 1,2-Dichloroethane Spill Part II: Documentation of Natural Attenuation

A release of 1,2-dichloroethane. also known as ethylene dichloride (EDC), resulted in shallow subsurface freephase contamination of a Gulf Coast site in the southern United States. The site stratigraphy consists primarily of a low permeability, surficial peat. silt, and clay zone underlain by fractured clay; a confined 12 in deep sand ground water flow zone; a confined 21 m deep fine sand zone of limited ground water flow, followed by a deep aquitard. The Gumbo clay and sandy clay aquitard below the release area overlies and protects the 61 m deep Upper Chicot Aquifer, which is a confined regional aquifer. An ongoing recovery and hydraulic containment program from the primary impacted and laterally and vertically restricted shallow 40-foot sand zone has effectively recovered dense nonaqueous phase liquid (DNAPL) and contained dissolved phase EDC.
Natural attenuation of EDC was demonstrated through (1) a laboratory microcosm study substantiating the ability of the native microbial population in the deeper aquifer lo degrade EDC under anaerobic environmental conditions found at the site. (2) field investigations showing reductions in EDC concentrations over time in many of the wells on site, and (3) an evaluation of the ground water for EDC and its degradation products and oilier geo-chemical parameters such as dissolved oxygen, redox potential, and pH. Degradation products of EDC found in the field investigations included 2-chloroeihanol, ethanol. ethene, and ethane. Dissolved EDC concentrations in selected wells between the first recorded samples and the fourth quarter of 1997 ranged from greater than 4% to 99% reductions. First-order exponential decay half-lives ranged from 0.21 to 4.2 years for wells showing decreases in FDC concentrations over time. Elevated methane concentrations indicated carbon dioxide to be the major terminal electron acceptor.     

Analysis of Radionuclide Releases from the Fukushima Dai-ichi Nuclear Power Plant Accident Part II

The present part of the publication (Part II) deals with long range dispersion of radionuclides emitted into the atmosphere during the Fukushima Dai-ichi accident that occurred after the March 11, 2011 tsunami. The first part (Part I) is dedicated to the accident features relying on radionuclide detections performed by monitoring stations of the Comprehensive Nuclear Test Ban Treaty Organization network. In this study, the emissions of the three fission products Cs-137, I-131 and Xe-133 are investigated. Regarding Xe-133, the total release is estimated to be of the order of 6 × 10¹⁸ Bq emitted during the explosions of units 1, 2 and 3. The total source term estimated gives a fraction of core inventory of about 8 × 10¹⁸ Bq at the time of reactors shutdown. This result suggests that at least 80 % of the core inventory has been released into the atmosphere and indicates a broad meltdown of reactor cores. Total atmospheric releases of Cs-137 and I-131 aerosols are estimated to be 10¹⁶ and 10¹⁷ Bq, respectively. By neglecting gas/particulate conversion phenomena, the total release of I-131 (gas + aerosol) could be estimated to be 4 × 10¹⁷ Bq. Atmospheric transport simulations suggest that the main air emissions have occurred during the events of March 14, 2011 (UTC) and that no major release occurred after March 23. The radioactivity emitted into the atmosphere could represent 10 % of the Chernobyl accident releases for I-131 and Cs-137.     

Analysis of Radionuclide Releases from the Fukushima Dai-Ichi Nuclear Power Plant Accident Part I

Part I of this publication deals with the analysis of fission product releases consecutive to the Fukushima Dai-ichi accident. Reactor core damages are assessed relying on radionuclide detections performed by the CTBTO radionuclide network, especially at the particulate station located at Takasaki, 210 km away from the nuclear power plant. On the basis of a comparison between the reactor core inventory at the time of reactor shutdowns and the fission product activities measured in air at Takasaki, especially ⁹⁵Nb and ¹⁰³Ru, it was possible to show that the reactor cores were exposed to high temperature for a prolonged time. This diagnosis was confirmed by the presence of ¹¹³Sn in air at Takasaki. The ¹³³Xe assessed release at the time of reactor shutdown (8 × 10¹⁸ Bq) turned out to be in the order of 80 % of the amount deduced from the reactor core inventories. This strongly suggests a broad meltdown of reactor cores.     

Isotopic Characterization of Radioiodine and Radioxenon in Releases from Underground Nuclear Explosions with Various Degrees of Fractionation

Both radioxenon and radioiodine are possible indicators for a nuclear explosion. Therefore, they will be, together with other relevant radionuclides, globally monitored by the International Monitoring System in order to verify compliance with the Comprehensive Nuclear-Test-Ban Treaty once the treaty has entered into force. This paper studies the temporal development of radioxenon and radioiodine activities with two different assumptions on fractionation during the release from an underground test. In the first case, only the noble gases are released, in the second case, radioiodine is released as well while the precursors remain underground. For the second case, the simulated curves of activity ratios are compared to prompt and delayed atmospheric radioactivity releases from underground nuclear tests at Nevada as a function of the time of atmospheric air sampling for concentration measurements of ¹³⁵I, ¹³³I and ¹³¹I. In addition, the effect of both fractionation cases on the isotopic activity ratios is shown in the four-isotope-plot (with ¹³⁵Xe, ^133mXe, ¹³³Xe and ^131mXe) that can be utilized for distinguishing nuclear explosion sources from civilian releases.