Successful solid-phase bioremediation of petroleum-contaminated soil

Biological processes have been used to remediate petroleum hydrocarbons, pesticides, chlorinated solvents, and halogenated aromatic hydrocarbons. Biological treatment of contaminated soils may involve solid-phase, slurry-phase, or in situ treatment techniques. This article will review the general principle of solid-phase bioremediation and discuss the application of this technique for the cleanup of total petroleum hydrocarbons on two sites. These remedial programs will reduce total petroleum hydrocarbon contamination from the mean concentration of 2,660 ppm to under the 200-ppm cleanup criteria for soil and under the 15-ppm cleanup criteria for groundwater. Over 32,000 yards of soil have been treated by solid-phase treatment to date. The in situ system operation is effectively producing biodegradation in the subsurface. The project is approximately one-third complete.     

黑麦草-不动杆菌组合体系对石油污染土壤的生物强化修复

以盆栽实验为基础,研究了植物（黑麦草,Lolium perenne L）-微生物（不动杆菌,Acinetobacter sp.）组合体系对石油污染土壤的修复效果。实验结果表明：在总石油烃含量为4 420.18 mg/kg、脱氢酶活性为230.52 μg/（g·d）、苯酚毒性当量浓度（TEQphenol）为1 633.21 mg/L的初始条件下,强化组总石油烃降解率最高为53.08%,是对照组的1.60倍;土壤的脱氢酶活性达到637.73 μg/（g·d）,是对照组的10.64倍;石油污染土壤的生物毒性大幅降低, TEQphenol最终降低至171.08 mg/L。说明该组合体系对石油污染土壤具有很好的修复作用,且微生物对土壤中有毒物质的降解起主要作用。     

内酯型槐糖脂修复石油污染土壤的影响因素

采用内酯型槐糖脂(SL50)修复石油污染土壤。通过单因子实验与正交实验,考察了槐糖脂溶液质量浓度、振荡时间、反应体系初始pH、NaCl加入量以及固液比(土壤质量与表面活性剂溶液体积之比)对污染土壤石油烃洗脱率的影响。单因子模型回归分析结果表明,参数变量均符合二次拟合模型,槐糖脂溶液质量浓度、反应体系初始pH以及NaCl加入量的二次模型拟合效果较好。正交实验结果表明,槐糖脂溶液质量浓度和反应体系初始pH是该实验的敏感性因子,最优洗脱条件为槐糖脂溶液质量浓度40 mg/L、反应体系初始pH 9、NaCl加入量6%(w)。     

有机溶剂浸取石油污染土壤中的多环芳烃

采用索氏提取法和气相色谱分析了某炼油厂周边土壤中的多环芳烃的种类及含量,考察了6种有机溶剂对土壤中多环芳烃的浸取效果,探讨了溶剂与溶质溶解度参数差异对浸取效果的影响。结果表明：土壤试样中含有蒽、荧蒽、芘、 、苯并[a]蒽、苯并[b]荧蒽、苯并[k]荧蒽和苯并[a]芘8种多环芳烃,其含量分别为4.20,22.05,10.62,4.26,5.54,0.80,0.94,4.18 mg/kg;筛选出二氯甲烷作为土壤中多环芳烃的浸取溶剂;最佳浸取条件为浸取时间10 min、浸取温度30 ℃、溶剂与土壤的液固比5:1（mL/g）、土壤含水量8%,在此条件下,总多环芳烃浸出率为83.0%,各种多环芳烃的浸出率分别为蒽97.8%、荧蒽78.2%、芘99.9%、 98.5%、苯并[a]蒽81.1%、苯并[b]荧蒽47.6%、苯并[k]荧蒽14.8%、苯并[a]芘58.7%。     

真空紫外光对含氧挥发性有机物的矿化效果

以醛类、醚类和酯类化合物作为目标污染物,考察了真空紫外光解法对含氧挥发性有机物（OVOCs）的矿化效果。实验结果表明,几种OVOCs在真空紫外光照射下都能达到90%以上的矿化率,且OVOCs的物质结构越简单,官能团的反应活性越强,越容易被矿化。直链结构比环状结构OVOCs的矿化效果更好,且分子链越短矿化速率越快;具有五元环结构的OVOCs比具有六元环结构的反应速率更快;官能团的键能越弱,反应活性越强,越容易被矿化。     

Using biopolymers to remove heavy metals from soil and water

Chemical remediation of soil may involve the use of harsh chemicals that generate waste streams, which may adversely affect the soil's integrity and ability to support vegetation. This article reviews the potential use of benign reagents, such as biopolymers, to extract heavy metals. The biopolymers discussed are chitin and chitosan, modified starch, cellulose, and polymer-containing algae.     

Managing compost stability and amendment to soil to enhance soil heating during soil solarization

Soil solarization is a method of soil heating used to eradicate plant pathogens and weeds that involves passive solar heating of moist soil mulched (covered) with clear plastic tarp. Various types of organic matter may be incorporated into soil prior to solarization to increase biocidal activity of the treatment process. Microbial activity associated with the decomposition of soil organic matter may increase temperatures during solarization, potentially enhancing solarization efficacy. However, the level of organic matter decomposition (stability) necessary for increasing soil temperature is not well characterized, nor is it known if various amendments render the soil phytotoxic to crops following solarization. Laboratory studies and a field trial were performed to determine heat generation in soil amended with compost during solarization. Respiration was measured in amended soil samples prior to and following solarization as a function of soil depth. Additionally, phytotoxicity was estimated through measurement of germination and early growth of lettuce seedlings in greenhouse assays. Amendment of soil with 10% (g/g) compost containing 16.9 mg CO₂/g dry weight organic carbon resulted in soil temperatures that were 2–4 °C higher than soil alone. Approximately 85% of total organic carbon within the amended soil was exhausted during 22 days of solarization. There was no significant difference in residual respiration with soil depth down to 17.4 cm. Although freshly amended soil proved highly inhibitory to lettuce seed germination and seedling growth, phytotoxicity was not detected in solarized amended soil after 22 days of field solarization.     

An IR study to investigate the structural relationship of lignin-like matter and lignosulphonates obtained from animal-vegetable wastes

Lignin-like matter (I) from rice hull residues and humin-like matter and (II) from rice hull-fecal matter compost yield, upon sulphonation by SO(3), the lignosulphonates III and IV, respectively. The solid state IR spectra of I and II are analysed and interpreted based on the functional groups content values obtained for III and IV by solution NMR spectroscopy. IR absorbance values at five selected wavelengths for I and II correlate well with functional groups content values for III and IV according to Beer's law. It is concluded that the sulphonated derivatives, aside from the -SO(3)H content, reflect well the chemical structure of the parent materials. No side reaction of I or II with SO(3), other than C sulphonation, is apparent. The above correlation may be useful for waste management purposes.     

Using organoclays to enhance carbon filtration

Organoclays have found increased acceptance as pre-treatment for activated carbon adsorption systems in both groundwater and wastewater cleanup. The reason is that activated carbon tends to become quickly blinded by large organic molecules of low solubility, particularly oils. However, it is also well established that activated carbon is more efficient at low concentrations of organic contaminants than at higher ones, i.e. at less than 1 ppm. With organoclays it is exactly the opposite, they are better at removing organics at higher concentrations, above 3 ppm. Therefore it is cost effective in these applications to use two or more vessels in series, the first one filled with organoclay, the remainder with activated carbon. The economics make sense, even though the organoclay is not regenerated, because of the reduction in down time every time a carbon vessel has to be changed out. Use of organoclays increases the volume treated by carbon in many applications seven to nine fold. In the case of other organic contaminants, as the aqueous solubility increases, the efficiency decreases, except in the case of methylene chloride, which it removes at far higher efficiency then carbon. This article presents the results of a series of tests, including Kd determinations, jar tests, and mini-column tests. These tests determined the adsorption capacity and efficiency of organoclay and activated carbon for the removal of benzene, toluene, xylene and naphtalene from water. These tests were followed by adding the four compounds into one container to see if the combination of organoclay, followed by carbon, would be more efficient then each sorbent alone. The tests also compared the efficiency of organoclay versus carbon for the removal of various oils from water.     

Update to the light nonaqueous phase liquid infiltration conceptual model

The 1970s oil spill model described the infiltration of oil (light nonaqueous phase liquid or LNAPL) into the subsurface, resulting in an oil pancake depressing the water table within the capillary fringe. An update to the 1970s model is needed because, according to the discussion by Lenhard et al. on the work of Lenhard and Parker and Farr et al., “A key concept of their efforts was that LNAPL-saturated ‘pancakes’ do not exist.” Lenhard and Parker and Farr et al. showed that the distribution of water, LNAPL, and air in the subsurface was a function of the LNAPL, water, and air pressures; fluid properties; and the pore-size distribution of the porous medium, and that the fluid saturations can be calculated from fluid levels in a monitoring well. The 1970s oil spill infiltration model described that spilled LNAPL migrates downward through the vadose zone under the force of gravity with some lateral spreading. The vadose zone, where all of the liquid pressures are less than atmospheric pressure, becomes a three-fluid zone consisting of variable saturations of air, water, and LNAPL, which together fully saturate the pore spaces. One important update to the 1970s model is that instead of the infiltrating LNAPL stopping at and depressing the water table, LNAPL penetrates the water table to a depth consistent with the gravitational and capillary forces experienced during LNAPL infiltration and creates a two-fluid zone below the water table where LNAPL and water pressures are greater than atmospheric pressure. After the LNAPL release stops, LNAPL infiltration and migration will cease after reaching equilibrium. The updated LNAPL infiltration conceptual model, like the 1970s model, describes the situation where the LNAPL release has stopped and LNAPL infiltration and migration have ceased after reaching equilibrium. The volume of LNAPL released is also assumed to be sufficient to pass through the vadose zone and enter the saturated zone.     

An ultracompact photo-ionization time-of-flight mass spectrometer with a novel vacuum ultraviolet light source for on-line detection of organic trace compounds and as a detector for gas chromatography

A recently developed novel intense rare-gas excimer vacuum ultraviolet (VUV) light source, the electron beam-pumped excimer lamp (EBEL), has been applied to the soft single-photon ionization (SPI) of organic molecules in a compact orthogonal acceleration time-of-flight mass spectrometer (oaTOFMS). The SPI-oaTOFMS system was applied to the on-line monitoring of tobacco smoke. With this setup, it was possible to analyze the composition of individual puffs of cigarette smoke. Furthermore, a gas chromatograph (GC) was coupled to the EBEL SPIoaTOFMS system. Soft photo-ionization represents an additional separation dimension. By combination of the gas chromatographic and the soft-ionization mass spectroscopic separation dimensions, a truly multidimensional comprehensive analytical method could be derived.     

Bioremediation of PCP-contaminated soil: Bench to full-scale implementation

Pentachlorophenol (PCP) is a widely used wood treatment agent and pesticide that is often listed among the contaminants at hazardous waste sites. Bench-scale studies were performed to develop a microbial culture and biodegradative process that could treat PCP at higher concentrations than previously reported. Several substrate formulations and culture techniques were evaluated. Ultimately a “self-feeding” (pH auxostat) continuous culture system (pH auxostat) was used to select for biodegradative activity with PCP as the carbon and energy source. After a period of 50 days, influent PCP concentrations reached 3,500 mg/liter at a dilution rate of 0.066 H^?1. Of the total theoretical chloride that could be released from PCP, 99% was detected as free chloride in the reactor effluent. PCP analysis of the effluent verified complete degradation by the microbial consortium. The reactor was converted to a constant PCP feed. At steady state conditions, the dilution rate was 0.05 H^?1 with an influent PCP concentration of 2,560 mg/liter and a biomass yield of 018 mg (dry weight) per mg of PCP. Mineralization studies performed with the microbial consortium using [U-14C1]-PCP indicated that 36.5% of the label was released as 14C-carbon dioxide.     

Systematically selecting an alternative to remediate soil contaminating groundwater

Contaminated soil is a continuing source of ground water contamination at some hazardous waste sites. Even if that soil does not pose a threat to human health or the environment, soil remediation may benefit ground-water cleanup in terms of time, money, or protectiveness. A method has been developed to provide a systematic manner to select a soil cleanup alternative. Using commercially available Windows-based software, the method consists of the development of a decision tree whose chance nodes are the restoration time frame probability distributions. Uncertainty associated with site data is quantitatively evaluated using Monte Carlo analysis to develop the probability distributions. The decision tree selects the alternative with the lowest cost. Data from an actual remedial investigation/feasibility study demonstrate the ease and practicality of the selection method.     

Alternatives to incineration in remediation of soil and sediments assessed

Contamination of soil and sediment by pollutants represents a major environmental challenge. Remediation of soil during the original Superfund years consisted primarily of dig and haul, capping, or containment. The 1986 amendments to CERCLA—SARA—provided the incentive for treatment and permanent remedies during site remediation. Thermal treatment, which routinely achieves the low cleanup criteria required by RCRA land-ban regulations, became one of the major technologies used for cleanup under the concept of ARAR. As the remediation industry matured and recognized specific market niches in soil remediation, a number of new technologies emerged. Thermal desorption, bioremediation, soil vapor extraction, soil washing, and soil extraction are being used on sites at which the technology offers advantages over incineration. In addition, a continuing stream of emerging technologies is being presented that requires careful evaluation relative to existing cleanup methods. Each of these technologies offers a range of options for achieving appropriate cleanup criteria, application to different soil matrices, cost, time of remediation, and public acceptability. Balancing cleanup criteria defined by regulation or risk assessment with technology cost and capability affords the opportunity to solve these problems with appropriate balance of cost and protection of human health and the environment.     

Best management practices to prevent cross-media transfers during soil cleanup

Cleanup activities often focus on the initial and final concentration levels of contaminants. What happens in-between, during implementation of treatment technologies, has raised major concerns by several environmental groups. To address this issue, the U.S. Environmental Protection Agency (EPA) has undertaken the task of developing a guidance that would identify the potential for cross-media transfer during implementation of various soil treatment technologies and recommend best management practices (BMPs) to prevent or control these cross-media transfers. The soil treatment technologies have been grouped into seven major categories in this effort. This article provides some details of the seven soil treatment technology groups and the general BMPs recommended in the draft BMP guidance document. One case history of existing control practices is also presented in this article and compared with the recommended BMPs.     

Contributions of common sources of polycyclic aromatic hydrocarbons to soil contamination

Asphalt products, particularly sealants, are prepared using petroleum products that contain a com‐plex mixture of aliphatic and aromatic hydrocarbons, including polycyclic aromatic hydrocarbons (PAHs). Clearly, these products are ubiquitous in urban environments, which raises an issue regard‐ing the potential for PAHs to be transported from parking lots to underlying or adjacent soil, surface‐water bodies, or groundwater. Based on a literature review, there are limited studies focus‐ing on this issue; however, the studies that have been published have fascinating conclusions. The literature shows, as expected, that asphalt‐based products contain PAHs. The highest PAH concen‐trations are present in asphalt sealants, particularly those manufactured using coal tar. Furthermore, due to the low solubility and high partition coefficients of PAHs, the potential for PAHs to leach from asphalt surfaces is negligible, which has been confirmed by leachability studies. Thus, there is little risk that PAHs will be present in stormwater runoff or leach into groundwater from asphalt‐paved areas in a dissolved form. However, asphalt pavement and sealants produce particulate matter that can contain concentrations of PAHs in the sub‐percent range (100s to 1,000s mg/kg total PAHs) that is transported in stormwater runoff. Some studies show that this can cause soil and sediment con‐tamination with total PAH concentrations in the range of 1 to 10 mg/kg. From a remediation per‐spective, many site cleanups are conducted to remediate the presence of PAHs to cleanup goals below 1 mg/kg or, in some cases, 0.1 mg/kg or lower. From a total risk perspective, remediating sites to low PAH cleanup goals may be unwarranted in light of the risk of transportable PAHs produced from paved parking surfaces. In other words, is it reasonable to conduct a cleanup to remediate low PAH concentrations and then redevelop the area with asphalt pavement and sealant, which may pose a greater PAH‐related risk? © 2006 Wiley Periodicals, Inc.     

Using community relations to reduce costs during remediation projects

Almost everyone who has been involved in a site remediation project has seen schedules slip and costs escalate due to political pressure from the public or the press. While focusing on remediation technologies and containment techniques to control costs, many organizations have neglected a major cost driver—public opinion. This article examines community relations from the perspective of an organization trying to control costs during a site remediation project. It details the strong correlation between the cost of a site cleanup and the level of public dissatisfaction and provides an organization with specific strategies on how to use proven communications techniques to lower costs. Examination of several case studies is provided, including a study involving a site in which community representatives actively worked to reduce project costs. It is clear that any responsible cleanup must be protective of public health and the environment. But it is becoming increasingly apparent that wise allocation of available resources has a profound effect on the program's ability to ensure public and environmental safety. In many cases, it has been proven that some costly cleanups—for example, involving excavation—sometimes actually increase risk by creating an exposure pathway where none existed before. In turn, such cleanups waste resources that are needed elsewhere. The challenge in dealing with this complicated issue is to help stakeholders understand the true ramifications of the choices that are faced at each site. If these stakeholders feel uninformed, powerless, or excluded from the process, it is likely that they will be unable to enter a productive discussion. The community relations programs outlined in documents such as a Superfund guidance can be helpful in familiarizing the community with site-related issues and with gathering public input. These activities act as a baseline for the programs discussed in this article. However, existing programs are not focused on providing a strategic advantage in reaching cleanup solutions and balancing health and environmental considerations with economic considerations.     

Analysis of soil vapor extraction laboratory data to obtain equilibrium constants

A method of analyzing soil vapor extraction (SVE) laboratory data using a sample of contaminated soil is presented to allow the calculation of equilibrium constants for an assumed gas/soil equilibrium expression. The constants can be determined for any compound measured in the exit gas. A Freundlich equilibrium expression was shown to represent the equilibrium in a soil contaminated with trichloroethylene (TCE) and several aromatic solvents.     

Case study: Using soil washing/leaching for the removal of heavy metal at the twin cities army ammunition plant

COGNIS TERRAMET® soil leaching and Bescorp soil washing systems have been successfully combined to remediate an ammunition test burn area at the Twin Cities Army Ammunition Plant (TCAAP), New Brighton, Minnesota. This cleanup is the first in the country to successfully combine these two technologies, and it offers a permanent solution to heavy metal remediation. Over 20,000 tons of soil were treated in the project. The cleaned soil remained on-site, and the heavy metal contaminants were removed, recovered, and recycled. Eight heavy metals were removed from the contaminated soil achieving the very stringent cleanup criteria of <175 ppm for residual lead and achieving background concentrations for seven other project metals (antimony, cadmium, chromium, copper, mercury, nickel, and silver). Initial contaminant levels were measured as high as 86,000 ppm lead and 100,000 ppm copper, with average concentrations over 1,600 ppm each. In addition, both live and spent ordnance were removed in the soil treatment plant to meet the cleanup criteria. By combining soil washing and leaching, COGNIS and Bescorp were able to assemble a process which effectively treats all the soil fractions so that all soil material can be returned on-site, no wastewater is generated, and the heavy metals are recovered and recycled. No hazardous waste requiring landfill disposal was generated during the entire remedial operation.