Treatability Testing for Weathered Hydrocarbons in Soils: Bioremediation,Soil Washing,Chemical Oxidation,and Thermal Desorption

Soils previously treated with landfarming to reduce petroleum hydrocarbon concentrations are often left with a less biodegradable residual fraction that can present challenges for additional treatment. Four possible polishing technologies were tested on the bench scale for weathered hydrocarbons present in fine-grain soils obtained from a previously landfarmed area at an active oil refinery. The technologies included additional bioremediation (both biostimulation and bioaugmentation tested), soil washing, chemical oxidation, and low-temperature thermal desorption. Multiple parameters were tested separately for each technology to identify possible factors that were relevant across technologies. Extractable hydrocarbons comprised only approximately 35% of the organic carbon in the soils, and this component was considerably less affected by biological, surfactant, and oxidant treatment than organic materials that are not quantified by the TEH analysis. Treatment testing of thermal desorption indicated removal of large quantities of extractable hydrocarbons despite the presence of high organic matter. The additional demand to the system would likely result in considerably large timeframes (biological treatment), reagent quantities (soil washing and oxidation), or energy input (thermal desorption) for treatment of target hydrocarbons on a full scale.     

生物技术在放射性污染土壤修复中的研究进展

综述了植物提取和植物稳定等植物修复技术和微生物修复技术等生物技术在放射性重金属污染土壤修复中的研究进展,并对其研究中存在的问题及今后的应用前景进行了讨论。     

On-Site Treatment of Contaminated Soils: An Approach to Bioremediation of Weathered Petroleum Compounds

A bench-scale investigation was conducted prior to on-site bioremediation of 52,000 cubic yards of contaminated soil containing weathered, structurally complex petroleum compounds from an inactive oil refinery. Addition of bulking agents was required to improve soil physical properties. A supplemental study was also conducted to evaluate the effectiveness of bio-enhancement products. Loss of n-alkanes was rapid in soil mixtures containing a high nitrogen sludge compost, but very slow in mixtures containing wood products as bulking agents. By completion of the study at day 110, the isoprenoids pristane and phytane had nearly disappeared from mixtures containing sludge compost. Clearly, pristane and phytane are inadequate biomarkers when conditions favor an advanced stage of biodegradation. Nearly half the complex branched and cyclic alkanes in the unresolved complex mixture also degraded. After 70 days, depletion of dibenzo-thiophenes and phenan-threnes was 75 and 90%, respectively. The most stable PAHs within each group were the highly methylated homologues. Because of their complex structures, both steranes and hopanes were stable in all soil mixtures. Data were normalized to hopanes as a conserved internal standard or biomarker. Use of hopane-normalized data successfully eliminated much of the data variability and permitted a more accurate assessment of biodegradation. A relatively slow decline in total hydrocarbons occurred later in the study. This slowing tendency of microbial utilization is caused not only by substrate depletion, but also because remaining hydrocarbons are structurally more complex and persistent. Because of this, it is important to avoid using kinetic data from early stages of bioremediation to predict later hydrocarbon losses, such as the time required to attain a cleanup standard. In the supplemental study, an oleophilic fertilizer product accelerated hydrocarbon degradation when compared with a conventional fertilizer. This product will be tested in combination with organic bulking agents under field conditions to determine its cost effectiveness.     

Oxidation of bovine serum albumin initiated by the Fenton reaction--effect of EDTA, tert-butylhydroperoxide and tetrahydrofuran

Oxidation of bovine serum albumin (BSA) was investigated using different oxidants: The water-soluble azo-initiator 2,2'azo-bis-(2-amidinopropane) hydrochloride (AAPH), a combination of FeCl₃ and ascorbate or the Fenton oxidant consisting of FeCl₂, H₂O₂ and EDTA. In addition, the effects of exogenous compounds such as tert-butyl hydroperoxide (tBuOOH) or solvents such as tetrahydrofuran (THF), often used in model systems, was evaluated. The extent of protein damage was studied by measuring protein carbonyl groups and protein hydroperoxides. The interaction between Fenton oxidant and EDTA, THF or tBuOOH was further characterized using spin trapping electron spin resonance (ESR) spectroscopy. The results showed that the extent of protein oxidation depended on the oxidant used. The Fenton oxidant was the most reactive of the initiators tested. However, in the absence of EDTA, the Fenton system produced protein carbonyl groups on BSA equivalent to that obtained with the other oxidants, however, significantly more protein hydroperoxide was produced. Surprisingly, it was also found that addition of tBuOOH or THF to BSA reduced protein damage when the oxidation was initiated with the Fenton oxidant. ESR investigation showed that EDTA played a key role in the generation of free radicals. It was also revealed that in an EDTA containing system both tBuOOH and THF were able to react with radicals without inducing protein damage in effect protecting BSA from oxidative damage.     

Limitations to Natural Bioremediation of Perchlorate in a Contaminated Site

Perchlorate (ClO₄ ^?) has been detected in many drinking water supplies in the United States, including the Las Vegas Wash and Lake Mead, Nevada. These locations are highly contaminated and contribute perchlorate to Lake Mead and the Colorado River system. Essential elements for perchlorate bioremediation at these locations were examined, including the presence of perchlorate-reducing bacteria (PRB), sufficient electron donors, occurrence of competing electron acceptors, and ability of PRB to utilize a variety of electron donors. Enumeration of PRB was performed anoxically using most probable number (MPN). Values ranged from ≤20 to 230 PRB/100 ml or ≤20 to ≥ 1.6× 10⁵ PRB/g for Lake Mead water samples and Las Vegas Wash sediments, respectively. 16S rRNA sequences revealed that isolates were γ -proteobacteria, Aeromonas, Dechlorosoma, Rahnella and Shewanella. A screening of potential electron donors using BIOLOG^TM demonstrated that all isolates were capable of metabolic versatility. Measurements of total organic carbon (TOC), nitrate and dissolved oxygen (DO) indicated limited presence of electron donor at all sites, whereas the electron acceptors varied throughout the Wash and Lake Mead. The persistence of perchlorate in the sites is attributed to lack of available electron donor and/or the presence of competing electron acceptors. A location has been identified where perchlorate biodegradation could be implemented thereby halting the transport of perchlorate to Lake Mead and the Colorado River.     

Bioremediation of Vegetable Oil and Grease from Polluted Wastewater Using a Sand Biofilm System

Pseudomonas sp. (L1), P. diminuta(L2) were among eight bacterial strains isolated from vegetable grease and oil-contaminated industrial wastewater, four of which only were found to have the ability to degrade oil and grease. They were identified and investigated for oil and grease degradation either individually or in combinations in previous unpublished work by the authors. Since the combination M1 (Pseudomonas sp. andP. diminuta) produced the highest degradative activity, it was used in the present study in a biofilm sand filter system for vegetable oil and grease removal. This system was tested either as one unit or two units in sequence where different flow rates (30, 50, 100 ml/h) were applied compared to a control unit(s). Results showed that both biofilm systems reduced oily wastewater, even in cases of high degree of pollution (fat, oil & grease (FOG), 7535 ppm; biochemical oxygen demand (BOD₅), 525 ppm; chemical oxygen demand (COD), 1660 ppm). Results also showed a removal of FOG with efficiency at 100%; BOD₅ at 95.9% and COD at 96%, at 50 ml/h flow rate using one unit of biofilm system. On using two units in sequence, a complete removal of FOG, BOD₅ and COD with efficiency 100%, at flow rate 100 ml/h was achieved. In conclusion, the previous biofilm results indicated the efficiency of such a system in treating oily polluted wastewater (vegetable oil origin) on the basis of bacterial isolates being used, the optimum flow rate, and the number of biofilm units used in sequence to obtain the highest removal capacity of such a system. This revised version was published online in July 2006 with corrections to the Cover Date.     

GC/MS-SCAN to follow the fate of crude oil components in bioreactors set to remediate contaminated soil

In this paper GC/MS-SCAN was used to identify the crude oil components that persist after bioremediation treatment of contaminated soil and the metabolites generated during this process. The soil was treated in bioreactors inoculated with an adapted bacterial population. In the first of two sets of conditions used, the water phase of the reactor was circulated continuously at a flow rate of 7 l day⁻¹, and in the other case, it was circulated for a short period once a day to give the equivalent of 0.5 l day⁻¹. Data showed that acyclic, n- and substituted alkanes C₁₂ were still present after one year of remediation, while the majority of substituted derivatives of polycyclic and aromatic hydrocarbons could not be detected by GC/MS-SCAN analysis. The number of components identified was about one-half of that initially observed. After treatment the same number of components was detected at the top and bottom of the reactor in which the water phase was circulated continuously, whereas a smaller number of metabolites were observed at the top rather than at the bottom of the reactor with discontinuous circulation. The analysis has pointed to the importance of n-alkanes, their substituted derivatives and polycyclic aromatic hydrocarbons as the most significant pollutants.     

Limitations to Natural Bioremediation of Perchlorate in a Contaminated Site

Perchlorate (ClO₄^-) has been detected in many drinking water supplies in the United States, including the Las Vegas Wash and Lake Mead, Nevada. These locations are highly contaminated and contribute perchlorate to Lake Mead and the Colorado River system. Essential elements for perchlorate bioremediation at these locations were examined, including the presence of perchlorate-reducing bacteria (PRB), sufficient electron donors, occurrence of competing electron acceptors, and ability of PRB to utilize a variety of electron donors. Enumeration of PRB was performed anoxically using most probable number (MPN). Values ranged from ≤20 to 230 PRB/100 ml or ≤20 to ≥ 1.6× 10⁵ PRB/g for Lake Mead water samples and Las Vegas Wash sediments, respectively. 16S rRNA sequences revealed that isolates were γ -proteobacteria, Aeromonas, Dechlorosoma, Rahnella and Shewanella. A screening of potential electron donors using BIOLOG^TM demonstrated that all isolates were capable of metabolic versatility. Measurements of total organic carbon (TOC), nitrate and dissolved oxygen (DO) indicated limited presence of electron donor at all sites, whereas the electron acceptors varied throughout the Wash and Lake Mead. The persistence of perchlorate in the sites is attributed to lack of available electron donor and/or the presence of competing electron acceptors. A location has been identified where perchlorate biodegradation could be implemented thereby halting the transport of perchlorate to Lake Mead and the Colorado River.     

Bioremediation of soil polluted with fuels by sequential multiple injection of native microorganisms: Field-scale processes in Poland

Research was conducted to estimate impact of the multiple bioaugmentation on the treatment of soil contaminated by fuels - diesel oil and aircraft fuel. The bacteria used to inoculate the remediation plots were isolated from the polluted soil and proliferated in field conditions. The amount of biomass applied to the polluted soil was set to ensure the total number of bacteria in soil 10⁷-10⁸ cfu/g d.w. The multiple inoculation of soil with indigenous bacteria active in diesel oil and engine oil (plot A) degradation increased bioremediation effectiveness by 50% in comparison to the non-inoculated control soil and by 30% in comparison to the soil that was inoculated only once. The multiple inoculation of soil with indigenous microorganisms was then applied in bioremediation of the soil polluted with double high concentration of diesel oil (soil B) and in bioremediation of the soil polluted with aircraft fuel (soil C). The process efficiency was 80% and 98% removal of TPH for soil B and C, respectively.     

两种植物条件下土壤中矿物油和多环芳烃（PAHs）的生物修复研究

选择苜蓿草和水稻为供试植物,以污染物水平、有机以、专性细菌和真菌为调控因子,进行土壤中矿物油和PAHs的生物修复研究,结果表明,投肥对苜蓿草土壤中矿物油降解有促进作用,但对水稻土壤中矿物油降解无明显作用,投肥均使苜蓿草和水稻土壤中多环芒烃总量（11种列于美国EPA黑名单上的多环芳烃）降解率提高,这一降解促进效果在水稻土壤中好于苜蓿草土壤,有机肥量与苜蓿草根际土著真菌、细菌数量明显呈正相关,但仅与水稻根际土著细菌数量呈明显正相关,两种土壤中实测真菌和细菌总数均与试验投加专性真菌和细菌量无关,水稻土和苜蓿草土壤中3环多环芳烃的降解随投肥量增大而降解率提高,其在水稻土蓑中的效果好于苜蓿草土壤,投肥怪4环多环芳烃的降解并未产生有效作用。     

Muskegon Wastewater Land Treatment System: Fate and Transport of Phosphorus in Soils and Life Expectancy of the System

The build‐up of phosphorus (P) in soil is a major factor limiting the operating life of a wastewater land treatment system. In this study, effects of long‐term wastewater application on changes in chemical properties, P profiles, and P adsorption capacity were evaluated in soils of the Muskegon wastewater land treatment plant that has been treating wastewater for > 30 years. Results indicate that the major soil properties have been changed. In the 15 cm topsoil, the pH increased from ～ 5–6 in 1973 to ～ 7.4–7.8 in 2003; the soil's total organic carbon (TOC) increased by 10–71 %; and the level of exchangeable Ca in 2003 is 8–9 times higher than that in 1973. The amount of Ca/Mg absorbed in the soil affects the P adsorption capability of the soil; Ca‐ and Mg‐bound P accounts for > 70 % of the total P adsorbed in the soil. The net P accumulated in the Rubicon soil increased from ～ 700 in 1993 to ～ 1345 kg/ha soil in 2001, but the plant available P varied between ～ 100–500 kg/ha soil during the same period, indicating a large amount of the applied P has become the fixed P that is unavailable to plants. P sorption in the soil consists of a fast adsorption and a slow transformation process. The soil's maximum P sorption capacity (P_max) (based on 1‐day isotherm tests) has been increased by ～ 2–4 times since 1973; the actual P_max of the Muskegon soils could be much higher than the 1‐day P_max. Therefore, the life expectancy of the Muskegon system has been extended significantly with the application of wastewater.     

Developments in Bioremediation of Soils and Sediments Polluted with Metals and Radionuclides. 3. Influence of Chemical Speciation and Bioavailability on Contaminants Immobilization/Mobilization Bio-processes

The biotransformation of metals is an exciting, developing strategy to treat metal contamination, especially in environments that are not accessible to other remediation technologies. However, our ability to benefit from these strategies hinges on our ability to monitor these transformations in the environment. That’s why remediation of contaminated sediments and soil requires detailed in situ characterization of the speciation of the toxic substances and their transformations with respect to time and spatial distribution. The present paper gives an overview of the literature regarding research performed in the laboratory as well as in the field.     

The Occurrence of Antibiotic Resistance Genes in Taq Polymerases and a Decontamination Method Applied to the Detection of Genetically Modified Crops

Different antibiotic resistance (AR) genes, such as Bla, Tet and NPTII, contaminate commercially available Taq polymerases. The specificity of the AR gene PCR can be increased when using a restriction enzyme-based decontamination of polymerase. The elimination of Taq polymerase contamination allows the use of PCR tests to screen seeds (corn) and processed food for the presence of genetically modified organisms (GMO) based on the detection of AR genes. Without a decontamination procedure for AR genes, PCR screening tests should be interpreted with caution. Revisions requested 1 November 2005; Revisions received 28 November 2005     

用钴卟啉修饰电极催化测定多巴胺等神经递质

将5, 10, 15, 20－四－（3－甲氧基－4－羟基苯基）卟啉钴（CoTMHPP）修饰在玻碳电极表面,制备成对多巴胶等神经递质有高灵敏度响应的CoTMHPP修饰电极．电极具有灵敏度高、响应快、稳定性好等特点．电极响应时间小于10s,儿茶酚类化合物的检测浓度为10^-6mol／L．     

Enhancing the Removal of Sorbed Crude Oil from Soil Through Multiple Oxidation Steps in Stepwise Fenton Processes

The stepwise Fenton oxidation process, in which hydrogen peroxide (H₂O₂) is added in a step-by-step manner instead of at the beginning, can achieve better sorbed crude oil removal effects. The results showed that if a high ratio of sorbed total petroleum hydrocarbon (TPH) was present in soil samples S1 (100%, initial TPH: 10,009 mg/kg) and S2 (94.2%, initial TPH: 4850 mg/kg), the TPH was oxidized in each step. In addition, the total TPH removal efficiency was 49.6% compared with the 27.9% achieved in conventional Fenton oxidation in which all H₂O₂ was added at the beginning. Nevertheless, when the ratio of sorbed TPH in the soil sample S3 was low (45.3%, initial TPH: 2850 mg/kg), the TPH removal efficiency was 18.9%, which was slightly higher than 18.2% achieved in the conventional Fenton process because if the sorbed TPH concentration was low, the sorbed TPH was mainly removed in the first step. The second and the third step resulted in long-chain alkanes entering the aqueous phase rather than removing them from the soil, which posed environmental risk. Therefore, it is clear that stepwise Fenton oxidation could improve sorbed TPH removal efficiency when the sorbed TPH concentration in the soil is high.     

Seasonal Dynamics of Atmospheric Methane Oxidation in Gray Forest Soils

Seasonal fluctuations in the methane fluxes in the soil–atmosphere system were determined for gray forest soils of Central Russia. Consumption of atmospheric methane was found to exceed methane emission in gray forest soils under forest and in the agrocenosis. The average annual rates of atmospheric methane consumption by the soil under forest and in the agrocenosis were 0.026 and 0.008 mg C-CH₄/(m² h), respectively. The annual rate of atmospheric methane oxidation in the gray forest soils of Moscow oblast was estimated to be 0.68 kton. Seasonal fluctuations in the methane oxidation activity were due to changes in the hydrothermal conditions and in the reserves of readily decomposable organic matter and mineral nitrogen, as well as to changes in the activity of methane oxidizers.     

Chlorinated and brominated phosphatidylcholines are generated under the influence of the Fenton reagent at low pH-a MALDI-TOF MS study

Lipid (phospholipid) oxidation is an increasingly important research topic due to the significant physiological relevance. The Fenton reaction, i.e. the transition metal catalyzed decomposition of H₂O₂ is frequently used to generate hydroxyl radicals (HO). Lipids with unsaturated fatty acyl residues are primarily converted by HO radicals into peroxides.In contrast, chloro- and bromohydrins as well as dihalogenides are formed by the addition of HOCl or HOBr to the olefinic groups of the fatty acyl residues of lipids or under the influence of the enzyme myeloperoxidase (MPO) from Cl⁻ and H₂O₂. We will show here by using MALDI-TOF MS for product analysis that halogenated products may also be generated in the presence of the Fenton reagent, if either FeCl₂ or FeBr₂ is used. In the presence of FeSO₄, however, peroxides are exclusively generated. It will also be shown that the generation of halogen-containing products is a competing reaction with the cleavage of the double bond under generation of the corresponding aldehyde or carboxylic acid that is favored at prolonged incubation times and at elevated pH.     

Bioavailability of 2, 4, 6-Trinitrotoluene (TNT) to Earthworms in Three Different Types of Soils in China

To study the effects of aging time (the length of time when contaminants are sequestered in soil) and soil properties on TNT bioavailability in soil, earthworms (Eisenia fetida) were exposed to three types of soils (fluvo-aquic soil, loessal soil, and black soil) contaminated by TNT for 7, 14, 21, 28, 35, and 42 days. The Earthworm-Soil Accumulation Factor (ESAF) of TNT and soil properties were analyzed. The ESAFs in black soil were significantly lower than those in fluvo-aquic soil and loessal soil (P < 0.05). In loessal soils, the ESAF increased with aging time, while that in black soils decreased. The ESAF of TNT had a significantly negative correlation with soil organic matter content, clay contents, and cation exchange capacity, which were the main factors affecting the TNT bioavailability in soils (P < 0.01). There was more quartz and feldspar in black soil, as well as more particles and micropores on the surface, which resulted in the easy adsorption and lower bioavailability of TNT. In conclusion, TNT bioavailability in soils is affected by aging time, soil physical and chemical properties, and mineral and surface properties, which must be considered when biotreatment for TNT in soils is applied.     

Coupling of Microbial Processes of Methane and Ammonium Oxidation in Soils

The effect of ammonium ions on the activity of methane oxidation in soils was studied. The degree of inhibition of the methanotrophic activity in the presence of ammonium in the soil solution was quantitatively assessed as dependent on ammonium concentration and the properties of different types of soils of the European part of Russia.