Cleanup standards for petroleum hydrocarbons. Part 1. Review of methods and recent developments

Many states across the U.S. use the total petroleum hydrocarbon (TPH) measurement as a regulatory tool for setting cleanup standards for underground storage tank sites and other petroleum‐related sites requiring cleanup. In Part I of this article, alternative techniques for developing site‐specific cleanup standards for petroleum hydrocarbons are reviewed, including the use of chemical fingerprinting, constituent analysis, and risk assessment methods that address hydrocarbons found in the environment. New developments in standard setting for petroleum hydrocarbons are described, including risk‐based standards for hydrocarbon mixtures and ecological risk‐based approaches. In Part 2 of this article, the cost‐effectiveness and accuracy of the most commonly used of these approaches will be evaluated by comparing a generic TPH cleanup standards approach with site‐specific cleanup standards approaches for two actual sites in Washington State, a neighborhood gas station and a former bulk fuel storage facility.     

Variation in Petroleum Hydrocarbon Chain Lengths with Depth at a Former Crude Oil and Natural Gas ProductionFacility

An investigation was performed at a former crude oil and natural gas production facility to evaluate whether releases from the product flowlines, gathering lines or water injection lines had impacted soil beneath the site. Thirty-six trenches were initially excavated and sampled beneath the former piping runs to a maximum depth of 6?m. After the trenching investigation, nine soil boreholes were advanced and sampled to a depth of approximately 18?m to further delineate the lateral and vertical extent of impacted soil. Soil samples collected from the trenches and boreholes were analyzed for total petroleum hydrocarbons (TPH) in accordance with ASTM Method 2887. The results of the investigation indicated that TPH impacted soil was present within several areas of the 40-ha site. The petroleum hydrocarbons generally had chain lengths ranging from C₆ to C₃₅, characteristic of light crude oil. The impacted soil also contained condensate, the volatile portion of crude oil. Condensate consists of short-chain hydrocarbons (C₁ to C₁₂) and is characterized by low levels of aromatic volatile organic compounds (VOCs). The condensate typically was more prevalent at depths below 4.5?m than the less volatile, longer chain length hydrocarbons. Statistical analysis of TPH data collected during subsequent excavation activities showed that the mean percentage of condensate was significantly greater at depths below 4.5?m than in shallower samples. In contrast, the mean percentage of TPH compounds in the diesel range (C₁₄ to C₂₃) was significantly greater in samples collected at depths above 4.5?m. The difference in the mean percentage of heavier hydrocarbons (C₂₄ to C₄₄+) with depth was not statistically significant.     

Cleanup standards for petroleum hydrocarbons. part 2. Case study comparisons of site‐specific cleanup standards with generic TPH standards

Many states across the U.S. use the total petroleum hydrocarbon (TPH) measurement as a regulatory tool for setting cleanup standards for underground storage tank sites and other petroleum‐related sites requiring cleanup. In Part 1 of this article (Michelsen and Petito Boyce, J. Soil Contam., 2(2): 109–124), alternative techniques and new methods for developing site‐specific cleanup standards for petroleum hydrocarbons were reviewed, including the use of chemical fingerprinting, constituent analysis, and human health and ecological risk assessment methods. In Part 2 of this article, the cost effectiveness and accuracy of these approaches are evaluated by comparing a generic TPH cleanup standards approach with site‐specific cleanup standards approaches for two actual sites in Washington State, a neighborhood gas station and a former bulk fuel storage facility. Based on these case studies, as well as consideration of other available approaches discussed in Part 1 of this article, recommendations are provided for selecting the most appropriate method of developing cleanup standards at a petroleum‐contaminated site.     

Bacterial succession in a petroleum land treatment unit

Bacterial community dynamics were investigated in a land treatment unit (LTU) established at a site contaminated with highly weathered petroleum hydrocarbons in the C(10) to C(32) range. The treatment plot, 3,000 cubic yards of soil, was supplemented with nutrients and monitored weekly for total petroleum hydrocarbons (TPH), soil water content, nutrient levels, and aerobic heterotrophic bacterial counts. Weekly soil samples were analyzed with 16S rRNA gene terminal restriction fragment (TRF) analysis to monitor bacterial community structure and dynamics during bioremediation. TPH degradation was rapid during the first 3 weeks and slowed for the remainder of the 24-week project. A sharp increase in plate counts was reported during the first 3 weeks, indicating an increase in biomass associated with petroleum degradation. Principal components analysis of TRF patterns revealed a series of sample clusters describing bacterial succession during the study. The largest shifts in bacterial community structure began as the TPH degradation rate slowed and the bacterial cell counts decreased. For the purpose of analyzing bacterial dynamics, phylotypes were generated by associating TRFs from three enzyme digests with 16S rRNA gene clones. Two phylotypes associated with Flavobacterium and Pseudomonas were dominant in TRF patterns from samples during rapid TPH degradation. After the TPH degradation rate slowed, four other phylotypes gained dominance in the community while Flavobacterium and Pseudomonas phylotypes decreased in abundance. These data suggest that specific phylotypes of bacteria were associated with the different phases of petroleum degradation in the LTU.     

Influences of chronic contamination of oil field exploitation on soil nematode communities at the Yellow River Delta of China

Oil production related activities have led to many environmental problems. Around 80% of the total output of crude oil is generated from terrestrial oilfields in the world. However, the impact of oil exploitation procedures on soil animal communities has not been fully understood. This study investigated the responses of soil nematode communities to the oil exploitation activities in the Yellow River Delta of China. By setting 10 oilfield sites and 5 relatively uncontaminated sites (controls), we found that the content of soil total petroleum hydrocarbons (TPH) was significantly higher at oilfield sites than at controls. With a longer oil exploitation history, the content of soil TPH increased. Soil nematode community structure at oilfield sites was largely different from that at controls. Soil nematodes were significantly less abundant but more diverse at oilfield sites than at controls. The proportions of fungal feeders were significantly lower at oilfield sites than at controls, attaining only half of those at controls. The nematode trophic diversity and genus number negatively correlated with the duration of petroleum exploitation history. This study elucidated the difference in soil nematode communities caused by oilfield exploitation and indicated that the nematode diversity was most obviously influenced by the soil TPH content and the oil exploitation history.     

Remarkable impact of PAHs and TPHs on the richness and diversity of bacterial species in surface soils exposed to long-term hydrocarbon pollution

Nowadays, because of substantial use of petroleum-derived fuels the number and extension of hydrocarbon polluted terrestrial ecosystems is in growth worldwide. In remediation of aforementioned sites bioremediation still tends to be an innovative, environmentally attractive technology. Although huge amount of information is available concerning the hydrocarbon degradation potential of cultivable hydrocarbonoclastic bacteria little is known about the in situ long-term effects of petroleum derived compounds on the structure of soil microbiota. Therefore, in this study our aim was to determine the long-term impact of total petroleum hydrocarbons (TPHs), volatile petroleum hydrocarbons (VPHs), total alkyl benzenes (TABs) as well as of polycyclic aromatic hydrocarbons (PAHs) on the structure of bacterial communities of four different contaminated soil samples. Our results indicated that a very high amount of TPH affected positively the diversity of hydrocarbonoclastic bacteria. This finding was supported by the occurrence of representatives of the α-, β-, γ-Proteobacteria, Actinobacteria, Flavobacteriia and Bacilli classes. High concentration of VPHs and TABs contributed to the predominance of actinobacterial isolates. In PAH impacted samples the concentration of PAHs negatively correlated with the diversity of bacterial species. Heavily PAH polluted soil samples were mainly inhabited by the representatives of the β-, γ-Proteobacteria (overwhelming dominance of Pseudomonas sp.) and Actinobacteria.     

辽河油田土壤石油污染及其微生物群落特征

本研究采取辽河油田曙光采油厂、欢喜岭采油厂和锦州采油厂井场周边土壤,并以未污染稻田土壤作为对照,分析了各采样点的土壤理化性质、石油烃浓度组成及土壤微生物群落结构。结果表明: 1) 3个采油厂井场周边土壤均受到严重的石油烃污染,但其石油烃浓度及组成存在一定的差异,曙光和欢喜岭采油厂土壤石油烃平均浓度是锦州采油厂的2倍以上;曙光采油厂土壤中胶质沥青质含量最高,而欢喜岭和锦州采油厂土壤中烷烃含量最高,比例均在40%以上。2)与稻田土壤相比,锦州采油厂土壤微生物操作分类单元(OTU)、Chao1指数和Shannon指数升高,而其在曙光和欢喜岭采油厂土壤中降低;各采油厂土壤样品中存在相同的优势菌门及菌属,但丰度存在较大差异。锦州采油厂土壤中分枝杆菌属、假单胞菌属的丰度高,曙光采油厂土壤中鞘氨醇单胞菌属、类诺卡氏菌属、马赛菌属的丰度高,而欢喜岭采油厂土壤中溶杆菌属、硫杆菌属、假节杆菌属的丰度高。3)相关分析表明,鞘氨醇单胞菌属、类诺卡氏菌属、硫杆菌属、马赛菌属、假节杆菌属与总石油烃、总有机碳和胶质沥青质含量呈显著正相关,分枝杆菌属、溶杆菌属、假单胞菌属与总氮和总磷呈显著正相关。本研究系统分析了不同采油厂土壤中石油烃、土壤理化性质和微生物群落特征,揭示了辽河油田污染土壤中特定的优势菌属和群落结构,为辽河油田石油烃污染土壤修复功能微生物筛选及修复过程菌群构建提供理论依据,也为其他油田高效降解菌筛选提供了方法借鉴。     

Influences of chronic contamination of oil field exploitation on soil nematode communities at the Yellow River Delta of China

Oil production related activities have led to many environmental problems. Around 80% of the total output of crude oil is generated from terrestrial oilfields in the world. However, the impact of oil exploitation procedures on soil animal communities has not been fully understood. This study investigated the responses of soil nematode communities to the oil exploitation activities in the Yellow River Delta of China. By setting 10 oilfield sites and 5 relatively uncontaminated sites (controls), we found that the content of soil total petroleum hydrocarbons (TPH) was significantly higher at oilfield sites than at controls. With a longer oil exploitation history, the content of soil TPH increased. Soil nematode community structure at oilfield sites was largely different from that at controls. Soil nematodes were significantly less abundant but more diverse at oilfield sites than at controls. The proportions of fungal feeders were significantly lower at oilfield sites than at controls, attaining only half of those at controls. The nematode trophic diversity and genus number negatively correlated with the duration of petroleum exploitation history. This study elucidated the difference in soil nematode communities caused by oilfield exploitation and indicated that the nematode diversity was most obviously influenced by the soil TPH content and the oil exploitation history.     

Bacterial Succession in a Petroleum Land Treatment Unit

Bacterial community dynamics were investigated in a land treatment unit (LTU) established at a site contaminated with highly weathered petroleum hydrocarbons in the C₁₀ to C₃₂ range. The treatment plot, 3,000 cubic yards of soil, was supplemented with nutrients and monitored weekly for total petroleum hydrocarbons (TPH), soil water content, nutrient levels, and aerobic heterotrophic bacterial counts. Weekly soil samples were analyzed with 16S rRNA gene terminal restriction fragment (TRF) analysis to monitor bacterial community structure and dynamics during bioremediation. TPH degradation was rapid during the first 3 weeks and slowed for the remainder of the 24-week project. A sharp increase in plate counts was reported during the first 3 weeks, indicating an increase in biomass associated with petroleum degradation. Principal components analysis of TRF patterns revealed a series of sample clusters describing bacterial succession during the study. The largest shifts in bacterial community structure began as the TPH degradation rate slowed and the bacterial cell counts decreased. For the purpose of analyzing bacterial dynamics, phylotypes were generated by associating TRFs from three enzyme digests with 16S rRNA gene clones. Two phylotypes associated with Flavobacterium and Pseudomonas were dominant in TRF patterns from samples during rapid TPH degradation. After the TPH degradation rate slowed, four other phylotypes gained dominance in the community while Flavobacterium and Pseudomonas phylotypes decreased in abundance. These data suggest that specific phylotypes of bacteria were associated with the different phases of petroleum degradation in the LTU.     

Review of chemical,physical, and toxicologic properties of components of total petroleum hydrocarbons

Risk is a function of exposure and hazard, and both aspects must be incorporated into sound risk assessment efforts. However, risk assessment for sites contaminated with petroleum products is complicated by a general lack of information relevant to exposure to and toxicity of petroleum mixtures (especially total petroleum hydrocarbons, or TPH). Specifically, there is often inadequate information about the components of the TPH present at the site and the physical and chemical properties and toxicities of these components. Such information is crucial to developing a strong conceptual model of exposure to and risk from petroleum hydrocarbons at contaminated sites. This article presents information that can be incorporated into risk assessments for sites contaminated with petroleum hydrocarbons.     

Distribution of Petroleum and Aromatic Hydrocarbons at a Former Crude Oil and Natural Gas Production Facility

Site characterization and remediation activities were performed at a former crude oil and natural gas production facility prior to redevelopment of the site. Field activities included delineation, excavation and segregation of approximately 1,250,000 m³ of soil impacted by total petroleum hydrocarbons (TPH) and the aromatic volatile organic compounds (VOCs) benzene, toluene, ethylbenzene, and xylenes (hereafter, collectively referred to as BTEX). Petroleum hydrocarbon chain length information was used to determine whether remediation was required in impacted areas, because the site-specific cleanup values for TPH compounds, established by the California State Regional Water Quality Control Board (RWQCB), were based on hydrocarbon chain length. Site-specific cleanup levels were also established by the RWQCB for BTEX. Subsurface investigation activities performed at the site indicated that the mean percentage of condensate and TPH compounds in the gasoline range was significantly greater at depths ranging from 4.6 to 18 m than in shallower samples. There was no significant difference in the mean concentration of BTEX compounds and mean percentage of diesel range and heavier hydrocarbons with depth. The occurrence of BTEX, diesel range, and heavier hydrocarbons at depth may result from preferential pathways for downward migration of contaminants, including blown out wells, abandoned wellbores, and the presence of faults. Vapor phase diffusion may also be a major transport mechanism controlling movement of BTEX compounds beneath the site.     

Impact of surrogate selection on risk assessment for total petroleum hydrocarbons

Environmental contamination involving total petroleum hydrocarbons (TPH) is being investigated and remediated at underground storage tanks, tank farms, pipelines, and refineries across the country. Human health and environmental risk play a significant role in decision making at these sites. However, risk assessment for sites contaminated with petroleum products typically is complicated by inadequate information about the composition of TPH present at the site and the physical and chemical properties and toxicity of the components. To address these data gaps, risk assessors can select surrogate compounds to represent the movement of TPH in the environment at the site and toxicity of TPH present at the site. This article illustrates the potential impact of choice of surrogates on risk estimates, which in turn affect remediation costs.     

Compositional changes during landfarming of weathered michigan crude oil‐contaminated soii

Laboratory landfarming experiments were conducted to study the bioremediation potential of weathered Michigan crude oil‐contaminated soils. It was found that landfarming was successful in removing up to 90% of the total petroleum hydrocarbons (TPH) in the soil within 22 weeks of treatment. Boiling point analyses of untreated and treated soils indicate a significant removal of TPH compounds independent of molecular weight or carbon number. Up to 85% of heavy petroleum hydrocarbons with carbon numbers above 44 were biode‐graded. In addition, approximately 93% of saturated and 79% of aromatic compounds of the TPH were biodegraded during the 22 week treatment period. The use of polyethylene sheeting as a landfarm cover does not appear to adversely affect biodegradation kinetics under laboratory conditions. Finally, equilibrium leachate concentrations for BTEX and regulated (in Michigan) polynuclear aromatics (PNAs) were below the respective detection limits for each compound. It can be concluded that landfarming of these weathered soils will be highly successful in removing petroleum hydrocarbons while not adversely impacting either ground‐water or surface water quality.     

Characterisation of the effect of a simulated hydrocarbon spill on diazotrophs in mangrove sediment mesocosm

An analysis of the effect of an oil spill on mangrove sediments was carried out by contamination of mesocosms derived from two different mangroves, one with a history of contamination and one pristine. The association between N₂ fixers and hydrocarbon degradation was assessed using quantitative PCR (qPCR) for the genes rrs and nifH, nifH clone library sequencing and total petroleum hydrocarbon (TPH) quantification using gas chromatography. TPH showed that the microbial communities of both mangroves were able to degrade the hydrocarbons added; however, whereas the majority of oil added to the mesocosm derived from the polluted mangrove was degraded in the 75 days of the experiment, there was only partially degradation in the mesocosm derived from the pristine mangrove. qPCR showed that the addition of oil led to an increase in rrs gene copy numbers in both mesocosms, having almost no effect on the nifH copy numbers in the pristine mangrove. Sequencing of nifH clones indicated that the changes promoted by the oil in the polluted mangrove were greater than those observed in the pristine mesocosm. The main effect observed in the polluted mesocosm was the selection of a single phylotype which is probably adapted to the presence of petroleum. These results, together with previous reports, give hints about the relationship between N₂ fixation and hydrocarbon degradation in natural ecosystems.     

Prepared Bed Land Treatment of Soils Containing Diesel and Crude Oil Hydrocarbons

An ex situ, field-scale, prepared bed land treatment unit (LTU) was used to bio-remediate soils containing petroleum hydrocarbons. Two soils were treated in side-by-side units to compare performance: (1) a clayey silt containing crude oil hydrocarbons from releases 30 to 40 years ago and (2) a silty sand containing diesel fuel hydrocarbons from a leak about three years prior to the bioremediation. The effectiveness of the bioremediation in the LTU was evaluated over a period of 18 months. The results indicated that: (1) prepared bed bioremediation reduced the hydrocarbon concentration, mobility, and relative toxicity in the soil with the diesel fuel, and (2) chemical bioavailability appeared to limit bioremediation of the soil containing the crude oil hydrocarbons. Although the soils containing the crude oil hydrocarbons contained an average of 10,000?mg TPH/kg dry soil, these soils had limited hydrocarbon availability, nontoxic conditions, and low potential for chemical migration. For the soils containing the diesel fuel, active prepared bed bioremediation of about 15 weeks was adequate to reach an environmentally acceptable endpoint. At that time, there was little further TPH loss, no Microtox^TM toxicity, and limited hydrocarbon mobility.     

Hydrocarbon Leaching, Microbial Population, and Plant Growth in Soil Amended with Petroleum

Two samples of oily waste organics (OWO) from petroleum wells were added to heath soils from Tierra del Fuego, Argentina, and the effects on hydrocarbon leaching, microbial population, and plant growth were studied. These mixtures and a control soil were subjected to four deionized water leachates. For each leachate, total petroleum hydrocarbons (TPH), aliphatic hydrocarbons (ALH), aromatic hydrocarbons (ARH) with three or fewer rings, ARH with more than three rings, and oil and grease (O&G) were measured. After leaching, six Dactylis glomerata L. plants were grown in each soil column. Plant growth and the total number of aerobic and nitrifier microorganisms were measured in soil. The 10% OWO sample increased the TPH in the leachate, but the 1% sample did not. The ALH, ARH, and O&G of each leachate followed patterns similar to that for TPH. Plant growth diminished and the total number of aerobic and nitrifier microorganisms decreased with increasing OWO, especially when the OWO was from a fresh residue rather than an aged residue. The greater inhibitive effect of fresh residue on plant growth was attributed to a higher concentration of light hydrocarbons, which are more toxic than heavy hydrocarbons. For soil with 1% OWO added, the TPH and other organics did not differ from the control soil. This result, combined with the 10-year average annual rainfall and the water table elevation at the site, suggests that the risk of contaminating the water table is relatively low. Thus, a 1% addition of OWO in soil would be appropriate to use in landfarming of OWO.     

Biostimulation and bioaugmentation for on-site treatment of weathered diesel fuel in Arctic soil

Bioremediation of weathered diesel fuel in Arctic soil at low temperature was studied both on-site in small-scale biopiles and in laboratory microcosms. The field study site was on Ellesmere Island (82°30'N, 62°20'W). Biostimulation was by fertilization with phosphorous and nitrogen. Bioaugmentation was with an enrichment culture originating from the field site. In biopiles, total petroleum hydrocarbons (TPH) were reduced from 2.9 to 0.5 mg/g of dry soil over a period of 65 days. In microcosms at 7 °C, TPH were reduced from 2.4 to 0.5 mg/g of dry soil over a period of 90 days. Inoculation had no effect on hydrocarbon removal in biopiles or in microcosms. Maximum TPH removal rates in the biopiles were approximately 90 μg of TPH g^–1 of soil day^–1, occurring during the first 14 days when ambient temperature ranged from 0 to 10 °C. The fate of three phylotypes present in the inoculum was monitored using most-probable-number PCR, targeting 16S rRNA genes. Populations of all three phylotypes increased more than 100-fold during incubation of both uninoculated and inoculated biopiles. The inoculum increased the initial populations of the phylotypes but did not significantly affect their final populations. Thus, biostimulation on site enriched populations that were also selected in laboratory enrichment cultures. Electronic Publication     

The impact of petroleum hydrocarbons (diesel) on periphyton in an impacted tropical estuary based on in situ microcosms

The distribution of petroleum hydrocarbons and their effects on the periphytic algal biomass using in situ microcosms were investigated in Ponggol estuary located on the northeastern coast of Singapore. Dissolved or dispersed petroleum hydrocarbon (DDPH) concentrations in the surface and bottom waters and absorbed or adsorbed petroleum hydrocarbon (AAPH) concentrations in sediments were monitored from July 1999 to June 2000. Results showed concentrations ranging from 4.42 to 248.94 μg l⁻¹, from 0.35 to 1099.65 μg l⁻¹, and from 20.55 to 541.01 mg kg⁻¹ for DDPH in surface and bottom waters and AAPH in sediments, respectively. Accidental spillages of fuel from dredgers operating in the estuary, fuel and engine oil from recreational boats, shipping operations in the adjacent strait, and runoff monsoon drains in the vicinity were some of the possible sources of petroleum hydrocarbons in the estuary. An assessment of environmentally realistic concentrations of petroleum hydrocarbons on periphytic algal biomass using in situ microcosms revealed signs of acute toxicity. A reduction in periphytic algal biomass (with respect to controls) of 68-93% was observed for various treatments exposed to diesel.     

On‐site bioremediation treatment system design and on‐site analytical screening of hydrocarbon‐contaminated dredge sediments

In early 1991, a petroleum refining facility located on the Blair Waterway in Commencement Bay near Tacoma, Washington, wished to deepen its berthing facility. Sediments had accumulated in the berthing area adjacent to the facility's petroleum handling dock to the extent that tanker ships could go aground during low tides. A preliminary sediment characterization program had indicated that elevated polynuclear aromatic hydrocarbons such as anthracene and phenanthrene, and total petroleum hydrocarbons exceeded Puget Sound Dredge Disposal Analysis maximum level guidelines for unconfined, open‐water disposal. Enviros designated an on‐shore sediment treatment facility to receive the dredged sediments. Design criteria and construction details of a treatment area capable of accommodating 8000 yd³ of sediments are presented. Onsite, real‐time sediment analysis for total petroleum hydrocarbon (TPH) concentrations was conducted by an onsite mobile laboratory. Laboratory techniques to expedite sediment analysis for TPH using infrared spectrophotometry are described.     

Effects of low temperature and freeze-thaw cycles on hydrocarbon biodegradation in Arctic tundra soil.

Degradation of petroleum hydrocarbons was monitored in microcosms with diesel fuel-contaminated Arctic tundra soil incubated for 48 days at low temperatures (-5, 0, and 7 degrees C). An additional treatment was incubation for alternating 24-h periods at 7 and -5 degrees C. Hydrocarbons were biodegraded at or above 0 degrees C, and freeze-thaw cycles may have actually stimulated hydrocarbon biodegradation. Total petroleum hydrocarbon (TPH) removal over 48 days in the 7, 0, and 7 and -5 degrees C treatments, respectively, was 450, 300, and 600 microg/g of soil. No TPH removal was observed at -5 degrees C. Total carbon dioxide production suggested that TPH removal was due to biological mineralization. Bacterial metabolic activity, indicated by RNA/DNA ratios, was higher in the middle of the experiment (day 21) than at the start, in agreement with measured hydrocarbon removal and carbon dioxide production activities. The total numbers of culturable heterotrophs and of hydrocarbon degraders did not change significantly over the 48 days of incubation in any of the treatments. At the end of the experiment, bacterial community structure, evaluated by ribosomal intergenic spacer length analysis, was very similar in all of the treatments but the alternating 7 and -5 degrees C treatment.