Petroleum Hydrocarbon Plume Research Articles

Application of novel nanobubble-contained electrolyzed catalytic water to cleanup petroleum-hydrocarbon contaminated soils and groundwater: A pilot-scale and performance evaluation study

Soil and groundwater contamination caused by petroleum hydrocarbons is a severe environmental problem. In this study, a novel electrolyzed catalytic system (ECS) was developed to produce nanobubble-contained electrolyzed catalytic (NEC) water for the remediation of petroleum-hydrocarbon-contaminated soils and groundwater. The developed ECS applied high voltage (220 V) with direct current, and titanium electrodes coated with iridium dioxide were used in the system. The developed ECS prototype contained 21 electrode pairs (with a current density of 20 mA/cm2), which were connected in series to significantly enhance the hydroxyl radical production rate. Iron-copper hybrid oxide catalysts were laid between each electrode pair to improve the radical generation efficiency. The electron paramagnetic resonance (EPR) and Rhodamine B (RhB) methods were applied for the generated radical species and concentration determination. During the operation of the ECS, high concentrations of nanobubbles (nanobubble density = 3.7 × 109 particles/mL) were produced due to the occurrence of the cavitation mechanism. Because of the negative zeta potential and nano-scale characteristics of nanobubbles (mean diameter = 28 nm), the repelling force would prevent the occurrence of bubble aggregations and extend their lifetime in NEC water. The radicals produced after the bursting of the nanobubbles would be beneficial for the increase of the radical concentration and subsequent petroleum hydrocarbon oxidation. The highly oxidized NEC water (oxidation-reduction potential = 887 mV) could be produced with a radical concentration of 9.5 × 10−9 M. In the pilot-scale study, the prototype system was applied to clean up petroleum-hydrocarbon polluted soils at a diesel-oil spill site via an on-site slurry-phase soil washing process. The total petroleum hydrocarbon (TPH)-contaminated soils were excavated and treated with the NEC water in a slurry-phase reactor. Results show that up to 74.4% of TPH (initial concentration = 2846 mg/kg) could be removed from soils after four rounds of NEC water treatment (soil and NEC water ratio for each batch = 10 kg: 40 L and reaction time = 10 min). Within the petroleum-hydrocarbon plume, one remediation well (RW) and two monitor wells (located 1 m and 3 m downgradient of the RW) were installed along the groundwater flow direction. The produced NEC water was injected into the RW and the TPH concentrations in groundwater (initial concentrations = 12.3–15.2 mg/L) were assessed in these three wells. Compared to the control well, TPH concentrations in RW and MW1 dropped to below 0.4 and 2.1 mg/L after 6 m3 of NEC water injection in RW, respectively. Results from the pilot-scale study indicate that the NEC water could effectively remediate TPH-contaminated soils and groundwater without secondary pollution production. The main treatment mechanisms included (1) in situ chemical oxidation via produced radicals, (2) desorption of petroleum hydrocarbons from soil particles due to the dispersion of nanobubbles into soil pores, and (3) enhanced TPH oxidation due to produced radicals and energy after nanobubble bursting.

Treatment of petroleum hydrocarbon-polluted groundwater with innovative in situ sulfate-releasing biobarrier

Petroleum hydrocarbons are commonly found pollutants in groundwater at industrial and gas station sites. Enhanced bioremediation is a cost-effective approach to cleanup petroleum hydrocarbon-polluted groundwater. The applicability of using sulfate-reducing biobarrier on the containment and control of petroleum-hydrocarbon plumes were assessed by batch and column studies. The innovative in situ biobarrier contained sulfate-releasing materials (SRMs) for a long-term sulfate release to enhance anaerobic petroleum hydrocarbons biodegradation with sulfate reduction mechanisms. SRMs were developed by blending rice husk powder (or starch) (used as permeability increment materials), magnesium sulfate (used as a source of sulfate), and polylactic acid (PLA) (used as a binder) together using a kneader. The mixed components were smelted to form pasty liquid at 190 °C, and it was transferred to a cylinder container to form SRMs. A column study was used to investigate the effectiveness of developed SRMs on the treatment of a methyl tert-butyl ether (MTBE) and toluene contaminated groundwater. The optimal sulfate release rate was achieved when the mass ratio of sulfate/starch/PLA was 0.5/0.5/2 [sulfate release rate (mg.d−1.g−1) = −0.009 × release period (d) + 3.4 (mg). Approximately 70% of MTBE and 92% of toluene could be remediated via sulfate reduction processes because the released sulfate from SRMs were served as electron acceptors, which promoted the growth of sulfate reducers. The next generation sequencing data suggest that bacterial strains with sulfate reduction and petroleum hydrocarbon biodegradation functions were detected after SRM supplement. Evidences of sulfate reduction of toluene and MTBE included (1) increased concentrations of sulfate and sulfide, (2) decreased concentrations of toluene and MTBE, (3) production of tert-butyl alcohol (degradation byproduct of MTBE), and (4) increased sulfate-reducing and petroleum-hydrocarbon bacteria. The biobarrier system containing the SRMs can be developed into a pragmatic technology for in situ remediation of petroleum-hydrocarbon plumes.

The in situ treatment of BTEX, MTBE, and TBA in saline groundwater

AbstractA pilot‐scale test was conducted in a saline aquifer to determine if a petroleum hydrocarbon (PHC) plume containing benzene (B), toluene (T), ethylbenzene (E), xylenes (X), methyl tert‐butyl ether (MTBE), and tert‐butyl alcohol (TBA) could be treated effectively using a sequential treatment approach that employed in situ chemical oxidation (ISCO) and enhanced bioremediation (EBR). Chemical oxidants, such as persulfate, have been shown to be effective in reducing dissolved concentrations of BTEX (B + T + E + X) and additives such as MTBE and TBA in a variety of geochemical environments including saline aquifers. However, the lifespan of the oxidants in saline environments tends to be short‐lived (i.e., hours to days) with their effectiveness being limited by poor delivery, inefficient consumption by nontargeted species, and back‐diffusion processes. Similarly, the addition of electron acceptors has also been shown to be effective at reducing BTEX and associated additives in saline groundwater through EBR, however EBR can be limited by various factors similar to ISCO. To minimize the limitations of both approaches, a pilot test was carried out in a saline unconfined PHC‐impacted aquifer to evaluate the performance of an engineered, combined remedy that employed both approaches in a sequence. The PHC plume had total BTEX, MTBE, and TBA concentrations of up to 4,584; 55,182; and 1,880 μg/L, respectively. The pilot test involved injecting 13,826 L of unactivated persulfate solution (19.4 weight percent (wt.%) sodium persulfate (Na2S2O8) solution into a series of injection wells installed within the PHC plume. Parameters monitored over a 700‐day period included BTEX, MTBE, TBA, sulfate, and sulfate isotope concentrations in the groundwater, and carbon and hydrogen isotopes in benzene and MTBE in the groundwater. The pilot test data indicated that the BTEX, MTBE, and TBA within the PHC plume were treated over time by both chemical oxidation and sulfate reduction. The injection of the unactivated persulfate resulted in short‐term decreases in the concentrations of the BTEX compounds, MTBE, and TBA. The mean total BTEX concentration from the three monitoring wells within the pilot‐test area decreased by up to 91%, whereas MTBE and TBA mean concentrations decreased by up to 39 and 58%, respectively, over the first 50 days postinjection in which detectable concentrations of persulfate remained in groundwater. Concentrations of the BTEX compounds, MTBE, and TBA rebounded at the Day 61 marker, which corresponded to no persulfate being detected in the groundwater. Subsequent monitoring of the groundwater revealed that the concentrations of BTEX continued to decrease with time suggesting that EBR was occurring within the plume. Between Days 51 and 487, BTEX concentrations decreased an additional 84% from the concentration measured on Day 61. Mean concentrations of MTBE showed a reduction during the EBR phase of remediation of 33% while the TBA concentration appeared to decrease initially but then increased as the sulfate concentration decreased as a result of MTBE degradation. Isotope analyses of dissolved sulfate (34S and 18O), and compound‐specific isotope analysis (CSIA) of benzene and MTBE (13C and 2H) supported the conclusions that ISCO and EBR processes were occurring at different stages and locations within the plume over time.

Emulsified polycolloid substrate biobarrier for benzene and petroleum-hydrocarbon plume containment and migration control – A field-scale study

The objective of this field-scale study was to assess the effectiveness of applying an emulsified polycolloid substrate (EPS; containing cane molasses, soybean oil, and surfactants) biobarrier in the control and remediation of a petroleum-hydrocarbon plume in natural waters. An abandoned petrochemical manufacturing facility site was contaminated by benzene and other petroleum products due to a leakage from a storage tank. Because benzene is a petroleum hydrocarbon with a high migration ability, it was used as the target compound in the field-scale study. Batch partition and sorption experiment results indicated that the EPS to water partition coefficient for benzene was 232 mg/mg at 25 °C. This suggests that benzene had a higher sorption affinity to EPS, which decreased the benzene concentrations in groundwater. The EPS solution was pressure-injected into three remediation wells (RWs; 150 L EPS in 800 L groundwater). Groundwater samples were collected from an upgradient background well, two downgradient monitor wells (MWs), and the three RWs for analyses. EPS injection increased total organic carbon (TOC) concentrations (up to 786 mg/L) in groundwater, which also resulted in the formation of anaerobic conditions. An abrupt drop in benzene concentration (from 6.9 to below 0.04 mg/L) was observed after EPS supplementation in the RWs due to both sorption and biodegradation mechanisms. Results show that the EPS supplement increased total viable bacteria and enhanced bioremediation efficiency, which accounted for the observed decrease in benzene concentration. The first-order decay rate in RW1 increased from 0.003 to 0.023 d−1 after EPS application. Injection of EPS resulted in significant growth of indigenous bacteria, and 23 petroleum-hydrocarbon-degrading bacterial species were detected, which enhanced the in situ benzene biodegradation efficiency. Results demonstrate that the EPS biobarrier can effectively contain a petroleum-hydrocarbon plume and prevent its migration to downgradient areas, which reduces the immediate risk presented to downgradient receptors.

Application of an emulsified polycolloid substrate biobarrier to remediate petroleum-hydrocarbon contaminated groundwater

Emulsified polycolloid substrate (EPS) was developed and applied in situ to form a biobarrier for the containment and enhanced bioremediation of a petroleum-hydrocarbon plume. EPS had a negative zeta potential (−35.7 mv), which promoted its even distribution after injection. Batch and column experiments were performed to evaluate the effectiveness of EPS on toluene containment and biodegradation. The EPS-to-water partition coefficient for toluene (target compound) was 943. Thus, toluene had a significant sorption affinity to EPS, which caused reduced toluene concentration in water phase in the EPS/water system. Groundwater containing toluene (18 mg/L) was pumped into the three-column system at a flow rate of 0.28 mL/min, while EPS was injected into the second column to form a biobarrier. A significant reduction of toluene concentration to 0.1 mg/L was observed immediately after EPS injection. This indicates that EPS could effectively contain toluene plume and prevent its further migration to farther downgradient zone. Approximately 99% of toluene was removed after 296 PVs of operation via sorption, natural attenuation, and EPS-enhanced biodegradation. Increase in total organic carbon and bacteria were also observed after EPS supplement. Supplement of EPS resulted in a growth of petroleum-hydrocarbon degrading bacteria, which enhanced the toluene biodegradation.

Hydrocarbon Assessment and Prediction due to the Gulf War Oil Disaster, North Kuwait.

Oil spill in the Gulf was the biggest disaster in history. The scale of damage was enormous, ranging from destruction caused by oil fires and oil spills, to economic decline for the Kuwaiti oil industry. The transport modelling of the freshwater aquifers in north Kuwait was undertaken to assess potential remediation scenarios using the MODFLOW-SURFACT numerical code. Three interlinked models were calibrated: flow, density (salinity), and transport. The model domain is a subregional area encompassing the Al-Raudhatain and Umm Al-Aish Basins. The time-variant salinity transport model was calibrated simultaneously with the transient groundwater flow system and this includes variably saturated flow and transport. This was done prior to proceeding to simulate contaminant hydrocarbon transport, as the hydraulic gradients and flow directions (and storage volume) are significant controls on contaminant migration. The results depicted after 23 years and with respect to the total area of the freshwater body at Al-Raudhatain (55.2 km2) and Umm Al-Aish (37 km2); the areal extent of the total petroleum hydrocarbon plume is estimated to be 7.3 and 8.7 km2 for the 0.1 mg/L contour, respectively. This equates to total petroleum hydrocarbon impacting 13 and 24% of the Al-Raudhatain and Umm Al-Aish freshwater bodies, respectively. The simulation indicated that even though total petroleum hydrocarbon loading was negligible in the center of the Al-Raudhatain depression up until the recent past, what has entered the groundwater system earlier from the contamination sources (pits, fringes, and lakes) is still moving toward the freshwater lenses or is potentially undetected due to lack of optimal existing monitoring bore screen and depth installations (plume diving). This implies that the environment is be the victim of war (the Gulf Crisis). The ecological and economic full impact probably will not be realized in the near future.

Geochemistry of Dissolved Organic Matter in a Spatially Highly Resolved Groundwater Petroleum Hydrocarbon Plume Cross-Section.

At numerous groundwater sites worldwide, natural dissolved organic matter (DOM) is quantitatively complemented with petroleum hydrocarbons. To date, research has been focused almost exclusively on the contaminants, but detailed insights of the interaction of contaminant biodegradation, dominant redox processes, and interactions with natural DOM are missing. This study linked on-site high resolution spatial sampling of groundwater with high resolution molecular characterization of DOM and its relation to groundwater geochemistry across a petroleum hydrocarbon plume cross-section. Electrospray- and atmospheric pressure photoionization (ESI, APPI) ultrahigh resolution mass spectrometry (FT-ICR-MS) revealed a strong interaction between DOM and reactive sulfur species linked to microbial sulfate reduction, i.e., the key redox process involved in contaminant biodegradation. Excitation emission matrix (EEM) fluorescence spectroscopy in combination with Parallel Factor Analysis (PARAFAC) modeling attributed DOM samples to specific contamination traits. Nuclear magnetic resonance (NMR) spectroscopy evaluated the aromatic compounds and their degradation products in samples influenced by the petroleum contamination and its biodegradation. Our orthogonal high resolution analytical approach enabled a comprehensive molecular level understanding of the DOM with respect to in situ petroleum hydrocarbon biodegradation and microbial sulfate reduction. The role of natural DOM as potential cosubstrate and detoxification reactant may improve future bioremediation strategies.

Thermal DNAPL Source Zone Treatment Impact on a CVOC Plume

AbstractThe tetrachloroethene (PCE) source zone at a site in Endicott, New York had caused a dissolved PCE plume. This plume was commingled with a petroleum hydrocarbon plume from an upgradient source of fuel oil. The plume required a system for hydraulic containment, using extraction wells located about 360 m downgradient of the source. The source area was remediated using in situ thermal desorption (ISTD). Approximately 1406 kilograms (kg) of PCE was removed in addition to 4082 kg of commingled petroleum‐related compounds. The ISTD treatment reduced the PCE mass discharge into the plume from an estimated 57 kg/year to 0.07 kg/year, essentially removing the source term. In the 5 years following the completion of the thermal treatment in early 2010, the PCE plume has collapsed, and the concentration of degradation products in the PCE‐series plume area has declined by two to three orders of magnitude. Anaerobic dechlorination is the suspected dominant mechanism, assisted by the presence of a fuel oil smear zone and a petroleum hydrocarbon plume from a separate source area upgradient of the PCE source. Based on the post‐thermal treatment groundwater monitoring data, the hydraulic containment system was reduced in 2014 and discontinued in early 2015.

Chemical Oxidation Performance in High Temperature, Saline Groundwater Impacted With Hydrocarbons

A series of laboratory microcosm experiments and a field pilot test were performed to evaluate the potential for in situ chemical oxidation (ISCO) of aromatic hydrocarbons and methyl tertiary butyl ether (MTBE), a common oxygenate additive in gasoline, in saline, high temperature (more than 30 °C) groundwater. Groundwater samples from a site in Saudi Arabia were amended in the laboratory portion of the study with the chemical oxidants, sodium persulfate (Na2S2O8) and sodium percarbonate (Na2(CO3)2), to evaluate the changes in select hydrocarbon and MTBE concentrations with time. Almost complete degradation of the aromatic hydrocarbons, naphthalene and trimethylbenzenes (TMBs), was found in the groundwater sample amended with persulfate, whereas the percarbonate‐amended sample showed little to no degradation of the target hydrocarbon compounds in the laboratory. Isotopic analyses of the persulfate‐amended samples suggested that C‐isotope fractionation for xylenes occurred after approximately 30 percent reduction in concentration with a decline of about 1 percent in the δ13C values of xylenes. Based on the laboratory results, pilot‐scale testing at the Saudi Arabian field site was carried out to evaluate the effectiveness of chemical oxidation using nonactivated persulfate on a high temperature, saline petroleum hydrocarbon plume. Approximately 1,750 kg of Na2S2O8 was delivered to the subsurface using a series of injection wells over three injection events. Results obtained from the pilot test indicated that all the target compounds decreased with removal percentages varying between 86 percent for naphthalene and more than 99 percent for the MTBE and TMBs. The benzene, toluene, ethylbenzene, and xylene compounds decreased to 98 percent on average. Examination of the microbial population upgradient and downgradient of the ISCO reactive zone suggested that a bacteria population was present following the ISCO injections with sulfate‐reducing bacteria (SRB) being the dominant bacteria present. Measurements of inorganic parameters during injection and postinjection indicated that the pH of the groundwater remained neutral following injections, whereas the oxidation–reduction potential remained anaerobic throughout the injection zone with time. Nitrate concentrations decreased within the injection zone, suggesting that the nitrate may have been consumed by denitrification reactions, whereas sulfate concentrations increased as expected within the reactive zone, suggesting that the persulfate produced sulfate. Overall, the injection of the oxidant persulfate was shown to be an effective approach to treat dissolved aromatic and associated hydrocarbons within the groundwater. In addition, the generation of sulfate as a byproduct was an added benefit, as the sulfate could be utilized by SRBs present within the subsurface to further biodegrade any remaining hydrocarbons. ©2015 Wiley Periodicals, Inc.

Evaluation of Seasonal Factors on Petroleum Hydrocarbon Vapor Biodegradation and Intrusion Potential in a Cold Climate

AbstractA detailed seasonal study of soil vapor intrusion at a cold climate site with average yearly temperature of 1.9 °C was conducted at a house with a crawlspace that overlay a shallow dissolved‐phase petroleum hydrocarbon (gasoline) plume in North Battleford, Saskatchewan, Canada. This research was conducted primarily to assess if winter conditions, including snow/frost cover, and cold soil temperatures, influence aerobic biodegradation of petroleum vapors in soil and the potential for vapor intrusion. Continuous time‐series data for oxygen, pressure differentials, soil temperature, soil moisture, and weather conditions were collected from a high‐resolution monitoring network. Seasonal monitoring of groundwater, soil vapor, crawlspace air, and indoor air was also undertaken. Petroleum hydrocarbon vapor attenuation and biodegradation rates were not significantly reduced during low temperature winter months and there was no evidence for a significant capping effect of snow or frost cover that would limit oxygen ingress from the atmosphere. In the residual light nonaqueous phase liquid (LNAPL) source area adjacent to the house, evidence for biodegradation included rapid attenuation of hydrocarbon vapor concentrations over a vertical interval of approximately 0.9 m, and a corresponding decrease in oxygen to less than 1.5% v/v. In comparison, hydrocarbon vapor concentrations above the dissolved plume and below the house were much lower and decreased sharply within a few tens of centimeters above the groundwater source. Corresponding oxygen concentrations in soil gas were at least 10% v/v. A reactive transport model (MIN3P‐DUSTY) was initially calibrated to data from vertical profiles at the site to obtain biodegradation rates, and then used to simulate the observed soil vapor distribution. The calibrated model indicated that soil vapor transport was dominated by diffusion and aerobic biodegradation, and that crawlspace pressures and soil gas advection had little influence on soil vapor concentrations.

Evaluation of Intrinsic Bioremediation of Methyl Tert-butyl Ether (MTBE) Contaminated Groundwater

This paper reported the use of real-time polymerase chain reaction (PCR), denaturing gradient gel electrophoresis (DGGE), and the culture-based method in the intrinsic bioremediation study at a petroleum contaminated site. The study showed that phenol hydroxylase gene was detected in groundwater contaminated with benzene, toluene, ethylbenzene, xylene isomers (BTEX) and methyl tert-butyl ether (MTBE). This indicated that intrinsic bioremediation occurred at the site. DGGE analyses revealed that the petroleum-hydrocarbon plume caused the variation in microbial communities. MTBE degraders including Pseudomonas sp. NKNU01, Bacillus sp. NKNU01, Klebsiella sp. NKNU01, Enterobacter sp. NKNU01, and Enterobacter sp. NKNU02 were isolated from the contaminated groundwater using the cultured-based method. Among these five strains, Enterobacter sp. NKNU02 is the most effective stain at degrading MTBE without the addition of pentane. The MTBE biodegradation experiment indicated that the isolated bacteria were affected by propane. Biodegradation of MTBE was decreased but not totally inhibited in the mixtures of BTEX. Enterobacter sp. NKNU02 degraded about 60% of MTBE in the bioreactor study. Tert-butyl alcohol (TBA), acetic acid, 2-propanol, and propenoic acid were detected using gas chromatography/mass spectrometry during MTBE degraded by the rest cells of Enterobacter sp. NKNU02. The effectiveness of bioremediation of MTBE was assessed for potential field-scale application.

Aerobic Biodegradation of Hydrocarbons in High Temperature and Saline Groundwater

A series of laboratory microcosm experiments and a field pilot test were performed to evaluate the potential for aerobic biodegradation of aromatic hydrocarbons and methyl tert‐butyl ether (MtBE; a common oxygenate additive in gasoline) in saline, high temperature (>30° C) groundwater. Aquifer, sediment, and groundwater samples from two sites, one in Canada and another in Saudi Arabia, were incubated for 106 days to evaluate the changes in select hydrocarbon and MtBE concentrations and microbial community structure. Almost complete biodegradation of the aromatic hydrocarbons was found in the Saudi Arabian microcosm samples whereas the Canadian microcosm samples showed no significant biodegradation during the laboratory testing. MtBE degradation was not observed in either set of microcosms. Denaturing gradient gel electrophoresis analyses showed that, while the Canadian microorganisms were the most diverse, they showed little response during incubation. The microbial communities for the Saudi Arabian sample contained significant numbers of microorganisms capable of hydrocarbon degradation which increased during incubation.Based on the laboratory results, pilot‐scale testing at the Saudi Arabian field site was carried out to evaluate the effectiveness of enhanced aerobic biodegradation on a high temperature, saline petroleum hydrocarbon plume. Dissolved oxygen was delivered to the subsurface using a series of oxygen diffusion emitters installed perpendicular to groundwater flow, which created a reactive zone. Results obtained from the seven‐month field trial indicated that all the target compounds decreased with removal percentages varying between 33 percent for the trimethylbenzenes to greater than 80 percent for the BTEX compounds. MtBE decreased 40 percent on average whereas naphthalene was reduced 85 percent on average. Examination of the microbial population upgradient and downgradient of the emitter reactive zone suggested that the bacteria population went from an anaerobic, sulfate‐reducing dominated population to one dominated by a heterotrophic aerobic bacteria dominant population.These studies illustrate that field aerobic biodegradation may exceed expectations derived from simple laboratory microcosm experiments. Also, high salinity and elevated groundwater temperature do not appear to inhibit in situ aerobic biorestoration. © 2014 Wiley Periodicals, Inc.

Application of natural attenuation for the control of petroleum hydrocarbon plume: Mechanisms and effectiveness evaluation

Summary The objective of this study was to evaluate the effectiveness and mechanisms of natural attenuation (NA) on the remediation of petroleum-hydrocarbon contaminated groundwater caused by gasoline and diesel fuel leakage. During the effectiveness investigation, site groundwater samples were collected and analyzed for the variations in geochemical indicators, microbial diversity, dominant bacteria, biodegradation rates, biodegradation capacity, and the trend of contaminant degradation. Results show that the total BTEX (benzene, toluene, ethylbenzene, and xylenes) concentrations dropped from 9.5 mg/L at the source zone to 0.06 mg/L at a 120-m downgradient line. The calculated BTEX biodegradation capacity (20 mg/L) was much higher than the BTEX concentrations (9.5 mg/L) within the most contaminated area. This indicates that the spilled BTEX could be completely biodegraded through different intrinsic microbial processes using available electron acceptors. Results from polymerase chain reaction (PCR), denaturing gradient gel electrophoresis (DGGE), and nucleotide sequence analyses reveal that the petroleum-hydrocarbon plume caused the bacterial variation in microbial communities, and more than 27 different petroleum-hydrocarbon degrading bacteria were observed in site groundwater indicating that BTEX could be biodegraded by the intrinsic bacterial consortium. Results also imply that the occurrence of intrinsic biodegradation was the major cause of the limited spreading of the BETX plume and reduction of contaminant concentrations. Results from Mann–Kendall test reveal that BTEX concentrations were decreasing in all monitor wells, and the BTEX first-order NA rate was 5.4 × 10−4 1/d along the transport path. The observed NA processes within the plume included the following: (1) depletion of electron acceptors (e.g., dissolved oxygen, nitrate, sulfate), (2) production of the degradation products (e.g., ferrous iron, sulfide, methane, CO2), (3) decreased BTEX concentrations along the groundwater flow direction, (4) a decreased trend of BTEX concentrations in monitor wells, (5) increased alkalinity, (6) increased microbial populations, (7) deceased pH in the spill source area, and (8) preferential removal of certain BTEX components along the transport path. Results indicate that NA can effectively contain the plume, and intrinsic biodegradation mechanisms were the major causes for contaminant removal. Results will be useful in applying NA as an alternative option for the management of petroleum-hydrocarbon contaminated sites.

Bacterial community evidence for anaerobic degradation of petroleum hydrocarbons in cold climate groundwater

Abstract There is currently limited scientific data to assess whether groundwater bacterial communities in fractured rock environments can degrade petroleum hydrocarbon plumes in cold regions. The former Colomac Mine is located in the Canadian Shield in the Northwest Territories (mean annual air temperature of − 5 °C) and is currently listed on the Federal Contaminated Sites inventory. Groundwater in fractured rock beneath the former fuel tank-farm at the mine site is contaminated by petroleum hydrocarbons. The objectives of this study were to investigate the bacterial community structure in the groundwater associated with hydrocarbon contamination, and to probe for potential anaerobic microbial processes involved in intrinsic bioremediation. Groundwater monitoring wells previously installed at the site were used to collect samples for chemical, isotopic and microbial analyses. Denaturing gradient gel electrophoresis (DGGE) analysis identified a relatively high bacterial diversity in the least contaminated locations, but as the hydrocarbon contamination increased, bacterial diversity decreased. Sequence analysis of the 16S rRNA gene demonstrated that the bacteria belonged to a wide range of genera, such as Pseudomonas, Thiobacillus, and Geobacter, all of which have been associated with the anaerobic degradation of hydrocarbons. Two putative nitrate-reducing genes were detected in samples with high nitrate reducing activity. Both chemical and microbiological results indicated the presence of microbial anaerobic processes by using nitrate, manganese(IV), ferric iron and sulfate as electron acceptors and suggest that these anaerobic processes play an important role in the biodegradation of dissolved petroleum hydrocarbons in the groundwater at the Colomac site. Our results also revealed that more than one biogeochemical process linked to hydrocarbon degradation could be present in a single borehole and these processes could vary spatially at this site.

Application of persulfate-releasing barrier to remediate MTBE and benzene contaminated groundwater

The objective of this study was to assess the potential of using an in situ oxidation barrier system to remediate gasoline-contaminated groundwater. The passive remedial system included a persulfate-releasing barrier containing persulfate-releasing materials to release persulfate for contaminant oxidation. Bench experiments were performed to determine the components and persulfate-releasing rate of the persulfate-releasing materials. Column experiments were conducted to evaluate the effectiveness of the designed persulfate-releasing materials on the control of petroleum-hydrocarbon plume. In this study, methyl tert-butyl ether (MTBE) and benzene were used as the target compounds. The optimal persulfate releasing rate was obtained when the mass ratio of persulfate/cement/sand/water was 1/1/0.16/0.5, and the rate varied from 31 to 8 mg persulfate per day per g of material. Significant amounts of MTBE and benzene were removed through the oxidation process due to the release of persulfate, and the produced tert-butyl formate (TBF) and tert-butyl alcohol (TBA), byproducts of MTBE, were further oxidized in the system. Results suggest that the oxidation rate would be affected by the oxidant reduction potential and concentrations of ferrous iron and persulfate.

Application of real-time PCR, DGGE fingerprinting, and culture-based method to evaluate the effectiveness of intrinsic bioremediation on the control of petroleum-hydrocarbon plume

Real-time polymerase chain reaction (PCR), denaturing gradient gel electrophoresis (DGGE), and the culture-based method were applied in the intrinsic bioremediation study at a petroleum-hydrocarbon contaminated site. The genes of phenol hydroxylase (PHE), ring-hydroxylating toluene monooxygenase (RMO), naphthalene dioxygenase (NAH), toluene monooxygenase (TOL), toluene dioxygenase (TOD), and biphenyl dioxygenase (BPH4) were quantified by real-time PCR. Results show that PHE gene was detected in groundwater contaminated with benzene, toluene, ethylbenzene, xylene isomers (BTEX) and methyl tert-butyl ether (MTBE), and this indicates that intrinsic bioremediation occurred at this contaminated site. Results from DGGE analyses reveal that the petroleum-hydrocarbon plume caused the variation in microbial communities. In this study, MTBE degraders including Pseudomonas sp. NKNU01, Bacillus sp. NKNU01, Klebsiella sp. NKNU01, Enterobacter sp. NKNU01, and Enterobacter sp. NKNU02 were isolated from the contaminated groundwater using the cultured-based method. Results from MTBE biodegradation experiment show that the isolated bacteria were affected by propane. This indicates that propane may influence the metabolic pathway of MTBE by these bacteria. Knowledge and comprehension obtained from this study will be helpful in evaluating the occurrence and effectiveness of intrinsic bioremediation on the remediation of petroleum-hydrocarbon contaminated groundwater.

Enhanced biodegradation by hydraulic heterogeneities in petroleum hydrocarbon plumes

In case of dissolved electron donors and acceptors, natural attenuation of organic contaminant plumes in aquifers is governed by hydrodynamic mixing and microbial activity. Main objectives of this work were (i) to determine whether aerobic and anaerobic biodegradation in porous sediments is controlled by transverse dispersion, (ii) to elucidate the effect of sediment heterogeneity on mixing and biodegradation, and (iii) to search for degradation-limiting factors. Comparative experiments were conducted in two-dimensional sediment microcosms. Aerobic toluene and later ethylbenzene degradation by Pseudomonas putida strain F1 was initially followed in a plume developing from oxic to anoxic conditions and later under steady-state mixing-controlled conditions. Competitive anaerobic degradation was then initiated by introduction of the denitrifying strain Aromatoleum aromaticum EbN1. In homogeneous sand, aerobic toluene degradation was clearly controlled by dispersive mixing. Similarly, under denitrifying conditions, microbial activity was located at the plume's fringes. Sediment heterogeneity caused flow focusing and improved the mixing of reactants. Independent from the electron accepting process, net biodegradation was always higher in the heterogeneous setting with a calculated efficiency plus of 23–100% as compared to the homogeneous setup. Flow and reactive transport model simulations were performed in order to interpret and evaluate the experimental results.

Modelling the fate of styrene in a mixed petroleum hydrocarbon plume

Severe petroleum hydrocarbon contamination (styrene and the BTEX compounds: benzene, toluene, ethylbenzene and the isomers of xylene) from leaking sewers was detected in a Quaternary aquifer below a chemical plant in the Padana Plain, Italy. From 1994, active pump and treat remediation has been employed. The site is bordered by canals which, in combination with variable pumping rates and groundwater flow directions, control groundwater levels. In this study we sought to determine the fate of styrene at the site within a mixed styrene/BTEX plume where the hydraulic boundaries induced strong seasonal variations in flows. In order to determine the fate of styrene, detailed field investigations provided intensive depth profile information. This information was then incorporated into a staged flow and reactive transport modelling. Three sets of measurements were obtained from sampling multilevel samplers (MLSs) under different hydraulic conditions at the site. These included measurements of BTEX, styrene, all major ions, pH and redox potential. A three-dimensional transient flow model was developed and calibrated to simulate an unconfined sandy aquifer with a variable flow field. Subsequently a reactive, multi-component transport model was employed to simulate the fate of dissolved BTEX and styrene along a selected flow line at the site. Each petroleum hydrocarbon compound was transported as independent species. Different, kinetically controlled degradation rates and a toxicity effect were simulated to explain the observed, selective degradation of pollutants in groundwater. Calibration of the model was accomplished by comparison with the three different sets of measurements obtained from the MLS devices. The results from various scenarios show that the detailed simulation of geochemical changes can be very useful to improve the site's conceptual model.

Seasonal Recharge and Replenishment of Sulfate Associated with Biodegradation of a Hydrocarbon Plume

AbstractThe downward flux of sulfate in a weathered clayey aquitard to a hydrocarbon plume in ground water was investigated at a gas well site in Alberta, Canada. The dissolved hydrocarbon plume includes monoaromatic BTEX compounds and extends less than 20 m downgradient from a natural gas condensate source in silt‐ and clay‐rich deposits. The vadose zone at the site has high concentrations of water soluble sulfate, which is apparently derived from pyrite oxidation. Seasonal infiltration of snowmelt water, most notably during the “wet” spring of 2003 and also in 2004, was focused in an excavation and recharged the water table. This recharge replenished the contaminated zone with sulfate that was flushed downward from the vadose zone. Recharge in 2003 resulted in episodic increases in sulfate concentrations in the ground water condensate plume of up to 1000 mg/L. After episodic increases in sulfate concentrations within the core of the contaminant plume associated with recharge, concentrations then decreased to less than 1 mg/L, accompanied by isotopic enrichment of the residual sulfate in 34S. The monitoring data provide strong field evidence that bacterial sulfate reduction is a dominant terminal electron‐accepting process in the natural attenuation of the hydrocarbon plume in the ground water. This result suggests that engineered infiltration and replenishment of sulfate to petroleum hydrocarbon plumes in ground water might enhance biodegradation of these plumes.

Microbial reduction of sulfate injected to gas condensate plumes in cold groundwater

Despite a rapid expansion over the past decade in the reliance on intrinsic bioremediation to remediate petroleum hydrocarbon plumes in groundwater, significant research gaps remain. Although it has been demonstrated that bacterial sulfate reduction can be a key electron accepting process in many petroleum plumes, little is known about the rate of this reduction process in plumes derived from crude oil and gas condensates at cold-climate sites (mean temperature < 10 °C), and in complex hydrogeological settings such as silt/clay aquitards. In this field study, sulfate was injected into groundwater contaminated by gas condensate plumes at two petroleum sites in Alberta, Canada to enhance in-situ bioremediation. In both cases the groundwater near the water table had low temperature (6–9 °C). Monitoring data had provided strong evidence that bacterial sulfate reduction was a key terminal electron accepting process (TEAP) in the natural attenuation of dissolved hydrocarbons at these sites. At each site, water with approximately 2000 mg/L sulfate and a bromide tracer was injected into a low-sulfate zone within a condensate-contaminant plume. Monitoring data collected over several months yielded conservative estimates for sulfate reduction rates based on zero-order kinetics (4–6 mg/L per day) or first-order kinetics (0.003 and 0.01 day − 1 ). These results favor the applicability of in-situ bioremediation techniques in this region, under natural conditions or with enhancement via sulfate injection.