Significance of organic chemical adsorption in soil and groundwater remediation

Adsorption of organic chemicals onto soils is affected by a number of factors related to the soil properties, chemical type, and environment. Organic chemical adsorption has significant impact on soil and groundwater cleanup criteria and on the time required for remediation using in situ vapor extraction, bioventing, and biosparging methods. Phase equilibrium relationships will permit specifying the contaminant concentration levels in soil that would prevent groundwater contamination beyond the limits prescribed by provincial regulations. Computer programs that neglect the adsorption effects will significantly underestimate the time required for soil remediation by vapor extraction.     

Evaluation of Soil Vapor Extraction and Bioventing for a Petroleum-Contaminated Shallow Aquifer in Korea

The feasibility of soil vapor extraction and bioventing technologies was examined for a petroleum hydrocarbon-contaminated site. The test site was highly contaminated with toluene, ethylbenzene, and xylene, due to leakage from petroleum storage tanks. Three respiration tests demonstrated that the test site conditions were appropriate for application of air-based remediation technologies. The oxygen consumption rates ranged from 4.32 to 7.68 %-O₂/day and biodegradation rates ranged from 2.72 to 4.84?mg/kg-day in respiration tests. In a 120-day soil vapor extraction pilot test, high initial mass removals (with tailing effects) were observed. As expected for the soil vapor extraction, the volatilization rate was much higher than the biodegradation rate. In a bioventing trial, the biodegradation effect was predominant, but a tailing effect was not observed. From this study, the suggested sequence of remediation is to construct an integrated system of soil vapor extraction and bioventing and initially operate the soil vapor extraction system until the volatilization rate becomes smaller than the biodegradation rate. After that, the system needs to be changed over to a bioventing mode. Field demonstration supports the feasibility of the proposed integrated system.     

Environmental Risk Controllability and Management of VOCs during Remediation of Contaminated Sites

The environmental risk controllability assessment system and its method of controlling volatile organic compounds (VOCs) during remediation of contaminated sites are established in this article based on soil vapor extraction (SVE) technology. According to the properties of VOCs and the technical and operational characteristics of the site remediation process, the environmental risk controllability index system includes environmental risk identification, risk source analysis, and risk assessment. Environmental risk management during site remediation was focused on technical control methods and engineering control technologies. Specifically, acceptance based on risk management was suitable for low-risk levels such as RRI3 and RRI4. Furthermore, control methods for high-level risk (RRI1 or RRI2) could be developed along with transformation and control, combined with the necessary emergency risk plan.     

Methodology for using contaminated soil leachability testing to determine soil cleanup levels at contaminated petroleum underground storage tank (UST) sites

The costs of environmental remediation at leaking petroleum underground storage tank (UST) sites are influenced significantly by soil cleanup levels. The use of conservative generic soil cleanup levels may be inappropriate at some sites contaminated by leaking petroleum USTs. At many contaminated sites, a primary objective of site remediation is long‐term protection of water resources (e.g., groundwater) from pollution. Leaching of pollutants from residual soil contamination to groundwater is a primary consideration in establishing site‐specific soil cleanup levels at fuel‐contaminated sites. The use of laboratory soil leachability testing methods may be useful in objectively evaluating the leaching potential of contaminants from residual soil contamination and estimating potential groundwater impacts. Developing soil cleanup levels that are protective of water resources must include a technically sound integration of site‐specific soil leachability data and contaminant attenuation factors. Evaluation of the leaching potentials of soil contaminants may also provide essential supplementary information for other site characterization methods that may be used to evaluate risks to human health. Contaminant leachability testing of soils may provide a cost‐effective and technically based method for determining soil cleanup levels that are protective of groundwater resources at contaminated petroleum UST sites.     

Post-remediation use of macrophytes as composting materials for sustainable management of a sanitary landfill

To increase the remediation ability and life expectancy of a leachate channel in a sanitary landfill, the plants used for remediation were composted as a post-remediation management technique. Phragmites australis or Typha angustifolia used for phytoremediation in a landfill leachate channel was harvested and used as a co-composting material with sewage sludge. The macrophyte compost was applied to the slope of a landfill on which plants were introduced for revegetation and to plants grown in pots to test for acute effects of the compost. The compost of the macrophytes successfully increased soil moisture and nutrient contents both on the landfill slope and in the soil of the pot experiment. Additionally, the rates of photosynthesis and the nutrient contents increased for plants grown in macrophyte compost. Thus, the revegetation or restoration management of the landfill would improve with the macrophyte compost used as a soil conditioner. The harvest of the macrophytes has the additional benefit of improving the remediation function of the leachate channel. Therefore, to sustainably manage both the leachate channel and the landfill, the composting of post-remediation macrophytes is an environmentally friendly and economically affordable method.     

Heavy Metal Contamination in the Brownfield Soils of Cleveland

The results esults of a survey of heavy metal contamination at Cleveland area brownfields and public spaces are presented. Soils were analyzed using a 24?h, 1N HCl extraction procedure. The study was conducted to seek brownfield soils that manifest properties of “old” sequestered contamination and to develop a better understanding of the nature and extent of heavy metal burdens at brownfield sites in the Greater Cleveland area. The results indicated that Cleveland brownfields commonly yield soil burdens well above remediation triggers for residential soils and often yield values above industrial remediation triggers. It was also discovered that public areas in the vicinity of brownfields commonly have heavy metal contamination significantly above background levels and occasionally above residential remediation triggers. These results indicate that brownfields redevelopment initiatives should proceed with caution. The appropriate remediation goals or restrictions must be imposed to control urban exposure to heavy metal contamination.     

Liming to remediate Ni contaminated soils with diverse properties and a wide range of Ni concentration

Historic emissions from a Ni refinery at Port Colborne, Ontario, caused Ni contamination of regional soils and raised concerns about potential Ni phytotoxicity. Previous tests revealed that if these soils were made alkaline and fertilized with Mn and other common nutrients as needed to maintain fertility of such alkaline soils, full remediation (prevention of Ni phytotoxicity) would be obtained. This experiment was conducted to test this method of remediation on diverse soils from Port Colborne, and to evaluate chemical extraction tests which would be predictive of plant uptake and potential for Ni phytotoxicity in Ni-contaminated soils. Ten soils with varied levels of Ni contamination and varied soil properties were amended with limestone or nitric acid to raise or lower pH so that a wide pH range could be examined for the soils. For lower Ni organic and mineral soils near the Ontario remediation limit (200 mg/kg), neither crop suffered Ni phytotoxicity at any pH tested. Only when more highly contaminated soils were strongly acidic did Ni phytotoxicity occur. Phytotoxic soils were fully remediated by making soils alkaline even for these Ni-sensitive crop species. Only the most contaminated organic soil remained slightly toxic – but this soil was remarkably contaminated (over 1.1% of Ni). The Sr nitrate extraction method was much more effective in predicting plant Ni concentrations than the DTPA method. This test provides an inexpensive soil extraction result highly predictive of potential for Ni phytotoxicity across soils.     

Composite Sampling Approaches for Bacillus anthracis Surrogate Extracted from Soil

Any release of anthrax spores in the U.S. would require action to decontaminate the site and restore its use and operations as rapidly as possible. The remediation activity would require environmental sampling, both initially to determine the extent of contamination (hazard mapping) and post-decon to determine that the site is free of contamination (clearance sampling). Whether the spore contamination is within a building or outdoors, collecting and analyzing what could be thousands of samples can become the factor that limits the pace of restoring operations. To address this sampling and analysis bottleneck and decrease the time needed to recover from an anthrax contamination event, this study investigates the use of composite sampling. Pooling or compositing of samples is an established technique to reduce the number of analyses required, and its use for anthrax spore sampling has recently been investigated. However, use of composite sampling in an anthrax spore remediation event will require well-documented and accepted methods. In particular, previous composite sampling studies have focused on sampling from hard surfaces; data on soil sampling are required to extend the procedure to outdoor use. Further, we must consider whether combining liquid samples, thus increasing the volume, lowers the sensitivity of detection and produces false negatives. In this study, methods to composite bacterial spore samples from soil are demonstrated. B. subtilis spore suspensions were used as a surrogate for anthrax spores. Two soils (Arizona Test Dust and sterilized potting soil) were contaminated and spore recovery with composites was shown to match individual sample performance. Results show that dilution can be overcome by concentrating bacterial spores using standard filtration methods. This study shows that composite sampling can be a viable method of pooling samples to reduce the number of analysis that must be performed during anthrax spore remediation.     

Uncertainty-based dynamic multimedia human health risk assessment for polycyclic aromatic hydrocarbons (PAHs) in a land oil exploitation area

With the increasing development of the petrochemical industry and the growing demand for oil, polycyclic aromatic hydrocarbons (PAHs) pollutions in the environment, especially in petroleum exploitation areas, are caused by the discharge of waste from the petroleum extraction process into an environmental system. This study aims to develop a new health risk assessment approach based on interval dynamic multimedia fugacity (IDMF) model and uncertainty analysis that could analyze the human exposure risk level for PAH contamination. The developed IDM health risk assessment (IDMHRA) approach is applied to assess previous, current, and future risks at a case study site in Daqing, Heilongjiang, China, from 1985 to 2020 for model validation. The human health risk assessment results show that 11 PAHs (NAP, ANT, FLA, PYR, BaA, CHR, BbF, BkF, BaP, IPY, and DBA) in the study site require further remediation efforts in terms of their unacceptable non-carcinogenic and carcinogenic risk. The results of risk source analysis reveal that soil media is the main risk pathway as compared with other exposure pathways. It can be seen that remediation process for soil contamination in the study site is urgently demanded. The assessment results demonstrate that the developed IDMHRA approach provides an effective tool for decision-makers and environmental managers to make remediation decisions in contaminated sites.     

Nitrogen Cycling and Nitric Oxide Emissions in Oil-Impacted Prairie Soils

A remote site in the Tallgrass Prairie Preserve of Oklahoma (The Nature Conservancy) was contaminated with crude oil from a pipeline break and is being bioremediated using landfarming techniques. Landfarming is designed to stimulate microbial-based catabolism of petroleum through combined dilution/mixing and fertilization-based effects. To evaluate nitrogen-based effects during remediation, the site was sectioned and treated with urea, ammonium sulfate, or ammonium nitrate. Samples were obtained from prairie soil without chemical nitrogen addition and with or without hydrocarbon contamination. Nitrogen cycling dynamics were followed by measuring ammonium, nitrite, nitrate, and volatile nitric oxide (NO_x) levels. Nitrifying and denitrifying bacterial numbers were estimated and compared to soil oxygen, carbon dioxide, and methane levels as well as to overall total petroleum hydrocarbon (TPH) reduction. For a prairie ecosystem of this type, a high level of fertilization, particularly with nitrogen, can have ecological effects almost as profound as the petroleum contamination itself. Fertilization of the oil-contaminated soil with the reduced and/or oxidized forms of nitrogen quickly resulted in elevated steady-state levels of both ammonium and nitrate, and exceptionally high levels of NO_x released from soil. Although nitrogen fertilization increased microbial nitrogen metabolism and nitrogen cycling, it had minimal effects on the overall remediation efficiency.     

A decision framework for selecting remediation technologies at hydrocarbon‐contaminated sites

A variety of remediation technologies are available to address hydrocarbon contamination, including free product recovery, soil venting, air sparging, groundwater recovery and treatment, and in situ bioremediation. These technologies address hydrocarbon contamination distributed between free, adsorbed, and dissolved phases in both the vadose and saturated zones. Selection of appropriate technologies is dependent on a number of factors, including contaminants, site‐specific characteristics, clean‐up goals, technology feasibility, cost, and regulatory and time requirements. This article describes a decision framework for selecting appropriate remediation technologies at hydrocarbon‐contaminated sites in a structured and tiered manner. Decision modules include (1) site characterization and product recovery; (2) vadosezone treatment: soil venting, bioremediation, and excavation; (3) saturated zone treatment: sparging, bioremediation, groundwater recovery, and excavation; and (4) groundwater treatment: carbon, air stripping, advanced oxidation, and bioreactors. Selection criteria for treatment technologies that address vadose‐ and saturated‐zone soils, as well as recovered groundwater, are described. The decision framework provides a systematic process to formulate solutions to complex problems and documents the rationale for selecting remediation systems designed to achieve closure at hydrocarbon‐contaminated sites.     

Phytoremediation of arsenic and lead in contaminated soil using Chinese brake ferns (Pteris vittata) and Indian mustard (Brassica juncea)

Field and greenhouse experiments were performed to assess the performance of phytoremediation of arsenic and lead from contaminated soil at an EPA Superfund site (Barber Orchard). Chinese Brake ferns (Pteris vittata) were used to extract arsenic. On average, fern shoot arsenic concentrations were as high as 20 times the soil arsenic concentrations under field conditions. It was estimated that 8 years would be required to reduce the acid-extractable portion of soil arsenic to safe levels (40 mg/kg). The effect of soil pH on arsenic extraction was also investigated. Results indicate that increasing soil pH may improve arsenic removal. Indian mustard plants (Brassica juncea) were used under greenhouse conditions to phytoextract soil lead. EDTA was applied to soil and was found to improve lead extraction. When the EDTA concentration was 10 mmol EDTA/kg soil in soil containing 338 mg Pb/kg soil, mustard plants extracted approximately 32 mg of lead. In conclusion, phytoremediation would be a suitable alternative to conventional remediation techniques, especially for soils that do not require immediate remediation.     

Social acceptability of phytoremediation: The role of risk and values

A former gas production site that was converted to a public park was chosen as the research location for the present study. Some of the contaminants at the site have been remediated; however, much of the soil is still contaminated with polycyclic aromatic hydrocarbons (PAHs). PAHs are toxic pollutants that have been shown to have numerous negative health effects. The primary form of remediation at the site has been capping, which is usually considered a temporary remediation strategy since it does not remove contaminants from the site but simply covers them, and this requires repeated re-capping efforts. Endophyte-assisted phytoremediation using willow shrubs is an alternative remediation strategy that could improve soil quality and permanently reduce contaminant levels in the soil. The goal of the present study was to explore the social acceptability of utilizing phytoremediation strategies. Surveys were used to explore public perceptions of the park and of using phytoremediation to clean up existing contamination. Results indicated a high level of social acceptability of phytoremediation at the park. Additionally, ecocentrism was shown to be a significant predictor of phytoremediation acceptability. Risk and anthropocentrism were not significant predictors of acceptability. Results suggest that messages intended to encourage the use and acceptability of phytoremediation should focus on the environmental benefits of phytoremediation.     

Estimating the availability of polycyclic aromatic hydrocarbons for bioremediation of creosote contaminated soils

Bioremediation of soil contaminated by organic compounds can remove the contaminants to a large extent, but residual contamination levels may remain which are not or only slowly biodegraded. Residual levels often exceed existing clean-up guidelines and thereby limit the use of bioremediation in site clean-up. A method for estimating the expected residual levels would be a useful tool in the assessment of the feasability of bioremediation. In this study, three soil types from a creosote-contaminated field site, which had been subjected to 6 months of bioremediation in laboratory column studies, were used to characterize the residual contamination levels and assess their availability for biodegradation. The soils covered a wide range of organic carbon levels and particle size distributions. Results from the biodegradation studies were compared with desorption rate measurements and selective extractability using butanol. Residual levels of polycyclic aromatic hydrocarbons after bioremediation were found to be strongly dependent on soil type. The presence of both soil organic matter and asphaltic compounds in the soil was found to be associated with higher residual levels. Good agreement was found between the biodegradable fraction and the rapidly desorbable fraction in two of the three soils studied. Butanol extraction was found to be a useful method for roughly estimating the biodegradable fraction in the soil samples. The results indicate that both desorption and selective extraction measurements could aid the assessment of the feasability for bioremediation and identifying acceptable end-points. Received: 15 September 1999 / Received revision: 7 February 2000 / Accepted: 13 February 2000     

Assessing the applicability of phytoremediation of soils with mixed organic and heavy metal contaminants

Soil pollution is a major environmental problem and many contaminated sites are tainted with a mixture of organic and heavy metal contaminants. Compared to other remedial strategies, phytoremediation is a low cost, environmentally-friendly, sustainable means of remediating the contamination. This review first provides an overview of phytoremediation studies where the soil is contaminated with just one type of pollutant (heavy metals or organics) and then critically evaluates the applicability of phytotechnologies for the remediation of contaminated sites where the soil is polluted by a mixture of organic and heavy metal contaminants. In most of the earlier research studies, mixed contamination was held to be detrimental to plant growth, yet there were instances where plant growth was more successful in soil with mixed contamination than in the soil with only individual contaminants. New effective phytoremediation strategies can be designed for remediation of co-contaminated sites using: (a) plants species especially adapted to grow in the contaminated site (hyperacumulators, local plants, transgenic plants); (b) endophytic bacteria to enhance the degradation in the rizhosphere; (c) soil amendments to increase the contaminants bioavailability [chelating agents and (bio)surfactants]; (d) soil fertilization to enhance the plant growth and microbial activity in the soil; and (e) coupling phytoremediation with other remediation technologies such as electrokinetic remediation or enhanced biodegradation in the rhizosphere.     

A fugacity model for soil vapor extraction

A relatively simple fugacity‐based model is developed for predicting the effectiveness of soil vapor extraction (SVE), an in situ soil remediation technique used for removing volatile organic chemicals from unsaturated soils. The model accounts for the natural processes of volatilization, degradation, and leaching, as well as gas‐phase advection due to SVE. Model predictions are compared with published data for a field‐scale SVE operation. An exponentially declining sweep efficiency for SVE is introduced to improve the fit between simulated and measured soil extraction gas concentrations. The model permits the magnitudes of the various processes affecting the fate and transport of 1,1,1‐trichloroethane (TCA) and perchloroethylene (PCE) in soils to be evaluated. Without SVE, the dominant removal process is biodegradation, but the rate of degradation is low, requiring more than 9 years for soil gas concentrations from a spill of about 13 kg of TCA to be reduced to a concentration of 0. 001 μg/l. The removal time may be reduced to only about 2 years if SVE is used. Moreover, substantially less chemical leaches into the underlying groundwater, greatly reducing the potential extent of ground water contamination.     

The development of chemical‐specific,risk‐based soil cleanup guidelines results in timely and cost‐effective remediation

Millions of dollars of limited state cleanup funds are spent each year in New Hampshire to identify, sample, excavate, and treat thousands of tons of contaminated soil. Cost analyses of numerous sites indicated that soil remediation costs alone reach upwards of $300,000.00 per site. The New Hampshire Department of Environmental Services “Interim Policy for Management of Soils Contaminated from Spills/Releases of Virgin Petroleum Products”; (DES, 1989, 1991) set conservative remediation goals based on total petroleum hydrocarbons in 1989 using the Leaching Potential Analysis method (California Luft Manual, 1989). A current review of available literature and several case histories indicated that chemical‐specific soil cleanup levels may be more appropriate for establishing remedial goals. New chemical‐specific soil cleanup guidelines using a risk‐based approach have been developed. These new guidelines are conservatively based using two principal considerations: (1) an assumed soil exposure scenario that estimated the human health risks associated with potential long‐term exposure to site soils via ingestion, inhalation and dermal contact and (2) the estimated fate and transport of chemicals of concern in the soil unsaturated zone. The first consideration assumed a total cancer risk that did not exceed 1 × 10^‐6. The second consideration employed the use of the SEasonal SOIL Compartment (SESOIL) model which simultaneously models water transport, sediment transport, and pollutant fate (US EPA, 1981). Several state soil standards from Oregon, Wisconsin, Massachusetts, and other states were extensively reviewed in order to develop a level of confidence that use of the SESOIL model was appropriate. A series of “sensitivity”; analyses was also performed in order to evaluate the response of the model to changes in various input parameters unique to New Hampshire's hydrogeologic conditions. Generic soil cleanup guidelines were developed for 24 petroleum‐based volatile and semivolatile chemicals of concern to be applied statewide. Site‐specific soil cleanup guidelines will be allowed if it can be demonstrated that insertion of site‐specific data into the model will not adversely affect groundwater quality. As a result of the above processes, timely and much more cost‐effective remediation will be achieved while still maintaining a high degree of protection of the groundwater quality and human health.     

Simplified methods for monitoring petroleum‐contaminated ground water and soil vapor

Portable meters and simplified gas Chromatographic (GC) techniques were investigated for monitoring volatile hydrocarbon (HC), CO₂, and O₂, concentrations in groundwater, exhaust gases, and soil vapor during in situ remediation using soil vapor extraction (SVE) and air sparging (AS). Results of groundwater samples analyzed in‐house using a headspace technique compared well to split samples analyzed by a certified analytical laboratory (r² = 0.94). SVE exhaust gas HC and CO₂ concentrations measured using a GT201 portable HC/O₂ meter and a RA‐411A meter (GasTech), respectively, were highly correlated with in‐house laboratory GC analyses (r² = 0.91). O₂ concentrations fell in a small range and meter analyses were not well correlated with laboratory analyses. Results of soil gas monitoring were not as well correlated as those for exhaust gases for HC, CO₂, or O₂, perhaps due to environmental conditions such as changes in relative humidity or the wider range of soil gas values. Overall, the meters were good indicators of vapor contamination, they greatly simplified estimates of total HC mass removal, and they allowed estimates of the biological contribution to contaminant removal during the remediation process.     

Aerobic Reduction of Hexavalent Chromium in Soil by Indigenous Microorganisms

Surface soil containing 25,100 mg/kg total Cr [12,400 mg/kg Cr(VI)] obtained from a Superfund site was used in laboratory microcosm studies to evaluate the potential for aerobic reduction of Cr(VI) by the indigenous soil microbial community. Hexavalent chromium in soil was reduced by as much as 33% (from 1840 to 1240 mg/L) within 21 days under enrichment conditions. Reduction of Cr(VI) in this system was biologically mediated and depended on the availability of usable energy sources. Mass balance studies suggested that the microbial populations removed Cr(VI) from the soil solutions by reduction. Indigenous microbial soil communities even with no history of Cr(VI) contamination were capable of mediating this process. However, Cr(VI) removal was not observed when microbial populations from a sewage sludge sample were added to the soil microcosms. The results suggest that Cr(VI)-reducing microbial populations are widespread in soil, and thus the potential exists for in situ remediation of environmentally significant levels of Cr( VI) contamination.     

Soil Washing Enhanced by Humic Substances and Biodegradable Chelating Agents

Industrial timber treatment sites have resulted in widespread soil contamination by Cu, Cr, and As, presenting potential long-term liability and associated risks to human health and the environment. This study evaluated the roles of natural humic substances (lignite-derived humic substances, standard and commercially available humic acids) and biodegradable chelating agents (ethylenediamine-N,N-disuccinic acid (EDDS) and glutamic-N,N-diacetic acid (GLDA)) for soil washing. Batch kinetic experiments revealed that humic substances promoted Cu extraction at pH 8, but they were significantly adsorbed on the soil at pH 4, possibly posing impediment to soil remediation. The metal extraction by EDDS and GLDA was comparable to that of EDTA (ethylenediamine-tetraacetic acid), and it was more effective at pH 4 than pH 8, probably due to acidic dissolution of metal precipitates and oxides. Metal distribution analysis indicated that the carbonate fraction of Cu and the oxide fraction of As and Cr were mainly extracted, while the exchangeable fraction of Cu increased. The residual leachability tests showed that humic substances reduced the Cu and As leachability but the reduction was insufficient. In contrast, EDDS was able to reduce the leachate concentrations of Cu and As to below 5 mg L^?1, meeting the waste acceptance criteria for landfill disposal. Nevertheless, soil washing methods and remediation strategy may need further modifications to facilitate site restoration and promote soil recycling.