石油污染土壤的生物修复技术

1　前　言在石油生产、贮运、炼制加工及使用过程中 ,由于事故 ,不正常操作及检修等原因 ,都会有石油烃类的溢出和排放。例如 ,油田开发过程中的井喷事故 ;输油管线和贮油罐的泄漏事故 ;油槽车和油轮的泄漏事故 ;油井清蜡和油田地面设备检修 ;炼油和石油化工生产装置检修等。石油烃类大量溢出 ,应当尽可能予以回收 ,但有的情况下回收很困难 ,即使尽力回收 ,仍会残留一部分 ,对环境 (土壤、地面和地下水 )造成污染。其进入土壤后 ,会破坏土壤结构 ,分散土粒 ,使土壤的透水性降低。其富含的反应基能与无机氮、磷结合并限制硝化作用和脱磷酸作…     

Profiling of plants at petroleum contaminated site for phytoremediation

The paucity of information in the literature on the characteristics of plants that could be used for phytoremediation of petroleum hydrocarbons (PHC)-contaminated sites was the principal reason for this study. The aim of the study was to identify indigenous plants growing in PHC-impacted soil in Umuahia in eastern-Nigeria that have the ability to phytoremediate soils contaminated with hydrocarbons under tropical monsoon climate conditions. A total of 28 native plant species from different families growing in and around hydrocarbon-impacted soil in the vicinity of vandalized pipelines carrying petroleum products were collected and studied for their ability to grow in a hydrocarbon-impacted soil and remove the PHC from the impacted soil. Some of the plants demonstrated the ability to grow in soil with high levels of the total petroleum hydrocarbons (TPH), which shows that they may be tolerant to hydrocarbons in soil and could potentially phytoremediate a hydrocarbon-contaminated soil. Chromolaena odorata, Aspilia africana, Chloris barbata, Pasparlum vaginatum, Bryophyllum pinnatum, Paspalum scrobiculatum, Cosmos bipinnatus, Eragrostis atrovirens, Cyperus rotundus, and Uvaria chamae showed tendencies to phytoremediate contaminated soil. By using bioaccumulation coefficient (BAC) as a measure of phytoremediation, results showed that C. odorata, A. africana, and U. chamae demonstrated the highest potentials to phytodegrade hydrocarbons in soil.     

Enhancing Degradation of Total Petroleum Hydrocarbons and Uptake of Heavy Metals in a Wetland Microcosm Planted with Phragmites Communis by Humic Acids Addition

The effects of humic acid (HA) on heavy-metal uptake by plants and degradation of total petroleum hydrocarbons (TPHs) in a wetland microcosm planted with Phragmites communis were evaluated by comparing waterlogged soils and water-drained upland soils. Experiments were conducted on soils artificially contaminated with heavy metals (Pb, Cu, Cd, Ni) and diesel fuel. HA showed a positive influence on biomass increase for all conditions, but more for belowground than aboveground biomass, and lower in contaminated than uncontaminated soil. The bioavailability and leachability factor (BLF) for all heavy metals except Ni increased with HA addition in both the control and the P. communis planted microcosms, suggesting that more heavy metals could be potentially phytoavailable for plant uptake. Microbial activities were not affected by both heavy metals and TPH contamination, and HA effects on stimulating microbial activities were much greater in the contaminated soil than under uncontaminated conditions. HA addition enhanced the degradation of TPH and n-alkane in waterlogged conditions. The results show that HA can increase the remedial performance in P. communis dominated wetlands simultaneously contaminated with heavy metals and petroleum hydrocarbons and thus prevent contamination of groundwater or other adjacent ecosystems.     

Background levels of polycyclic aromatic hydrocarbons (PAH) and selected metals in new England urban soils

Polycyclic aromatic hydrocarbons (PAH) are byproducts of combustion and are ubiquitous in the urban environment They are also present in industrial chemical wastes, such as coal tar, petroleum refinery sludges, waste oils and fuels, and wood‐treating residues. Thus, PAHs are chemicals of concern at many waste sites. Risk assessment methods will yield risk‐based cleanup levels for PAHs that range from 0.1 to 0.7 mg/kg. Given their universal presence in the urban environment, it is important to compare risk‐based cleanup levels with typical urban background levels before utilizing unrealistically low cleanup targets. However, little data exist on PAH levels in urban, nonindustrial soils. In this study, 60 samples of surficial soils from urban locations in three New England cities were analyzed for PAH compounds. In addition, all samples were analyzed for total petroleum hydrocarbons (TPH) and seven metals. The upper 95% confidence interval on the mean was 3 mg/kg for benzo(a)pyrene toxic equivalents, 12 mg/kg for total potentially carcinogenic PAH, and 25 mg/kg for total PAH. The upper 95% confidence interval was 373 mg/kg for TPH, which exceeds the target level of 100 mg/kg used by many state regulatory agencies. Metal concentrations were similar to published background levels for all metals except lead. The upper 95% confidence interval for lead was 737 mg/kg in Boston, 463 mg/kg in Providence, and 378 mg/kg in Springfield.     

不同类型原油污染土壤生物修复技术研究

对不同类型原油污染土壤在实用规模的预制床上采用堆制技术进行生物修复 .通过投加肥料、菌剂、控制水分和pH ,可使微生物获得较好的生态环境 .当稀油、高凝油、特稠油和稠油污染的土壤中原油总量为 2 5 .8～ 77.2 g·kg-1土时 ,经过近 2个月的运行 ,石油总量的去除率可达 38.37%～ 5 6 .74 % .石油中芳烃、沥青和胶质混合物是制约石油快速降解的主要因素 .在处理过程中筛选出石油降解的优势菌株 ,其中有 6株真菌、6株细菌和 1株放线菌 .研究结果为石油污染土壤异位生物修复技术实用化提供了理论依据 .     

Bioremediation of Oil-contaminated Soil Using Chicken Manure

In less developed countries, the prevalence of soil contaminated with used lubricating oil is high and the situation worsens with the economic advancement. The contamination has been shown to adversely affect the environment and human health. To mitigate, bioremediation could be adopted to tackle the problem of hydrocarbon-contaminated soil. Thus, this experimental research carried out the bioremediation using chicken manure in soils contaminated with 5%, 10% and 20% w/w used lubricating oil for a 42-day composting period. To compare, this research also experimented with the 5%, 10% and 20% oil-contaminated soils untreated with chicken manure. The results showed that the highest total petroleum hydrocarbons (TPHs) reduction efficiency of >60% was achieved in the 5% oil-contaminated compost remediated with chicken manure. The highest biodegradation rate of lubricating oil of 0.023–0.0025 day^?1 as measured by the first-order kinetics could also be achieved under the 5% oil contamination condition with the application of chicken manure. The findings highlight the prospect of chicken manure as a proper nutrient for enhanced remediation of hydrocarbon-contaminated soils, particularly of low contamination concentrations.     

胜利油田采油区土壤石油污染状况及其微生物群落结构

基于不同开采年代新油井(2011—)和老油井(1966—2003年)周边土壤的调查取样,研究了采油区土壤石油污染状况,利用PCR-DGGE和克隆测序技术,探讨了新、老油井周边土壤微生物的群落结构.结果表明:油井周边土壤均受到不同程度的石油污染,其石油烃含量大多高于土壤石油污染临界值(500 mg·kg^-1),且老油井周边土壤污染水平更高.污染土壤石油烃含量与土壤有机碳、全氮和速效钾含量呈显著正相关.老油井周边土壤微生物群落多样性指数随污染水平的增大而减小,新油井则呈相反的趋势.DGGE图谱优势条带测序结果表明,油井周边土壤均存在明显的优势菌,大多为石油烃相关菌和烃类降解菌,如微杆菌属、链霉菌属、迪茨氏菌属、黄杆菌属及α、γ变形菌等.
     

In-Situ Remediation of Lead–Zinc Polymetallic Mine Contaminated Soils by MnFe2O4 Microparticles

In-situ remediation is a practical approach to remediate soils contaminated with heavy metals. The MnFe₂O₄ microparticles (MM) were prepared for the in-situ remediation of contaminated soils from a lead–zinc polymetallic mine in Inner Mongolia province, China. The effects of MM dosage, pH on remediation efficiency, were determined with static vibration leaching experiment, and the release risk of heavy metals of treated soil was studied by column leaching experiment. The results showed that the leached Cu, Pb, Zn, and As concentration decreased drastically with increasing MM dosage, when the dosage was lower than 10 g/kg. Moreover, the decrease of pH caused increase of leached concentration of Cu, Pb, Zn, but slight decrease of leached As concentration. For the amended soil, concentrations of leached heavy metals were lower than Grade III limit of Chinese Environmental Quality Standards for Ground and Surface water (GB3838-2002) under simulated acid rain leaching condition. In comparison with non-amended soils, the total amount of Cu, Pb, Zn, and As release from amended soils was reduced by 93.6%, 69.2%, 57.0%, and 99.7%, respectively. The MM is a kind of promising amendment for heavy metals contaminated soil.     

污染土壤淋洗修复技术研究进展

土壤淋洗修复技术是一种行之有效的污染土壤治理技术,适合于快速修复受高浓度重金属和有机物污染土壤与沉积物。本文综述了土壤淋洗修复技术的特点、技术流程、土壤淋洗剂的研究与应用进展,指出异位土壤淋洗修复技术因修复效果稳定,易于实现系统控制和废弃物减量化等优点而具有更广阔的应用前景,天然螯合剂和生物表面活性剂等环境友好型淋洗剂正逐渐取代人工螯合剂和化学表面活性剂成为土壤淋洗剂研究的主流方向,而现代超分子化学的引入和发展有可能对复合污染土壤的高效淋洗修复研究产生新的影响。     

磷酸盐修复重金属污染土壤的研究进展

从研究方法、反应机理以及风险评价等方面综述了磷酸盐修复重金属污染土壤的研究进展,分析和讨论了其中存在的问题和不足,提出了今后加强研究的重点。目前磷酸盐修复重金属污染土壤时,使用的主要研究方法有化学形态提取法、化学平衡形态模型法和光谱及显微镜技术,各个方法都有其优缺点,应该结合使用并探索新方法。磷酸盐稳定重金属的作用机理主要有3个:磷酸盐诱导重金属吸附、磷酸盐和重金属生成沉淀或矿物和磷酸盐表面吸附重金属,但磷酸盐与重金属反应的机理十分复杂,人们尚不完全清楚,因此难以有效区分和评价诱导吸附机理和沉淀机理或其它固定机理,相应地对磷酸盐修复重金属的长期稳定性难以预测。磷酸盐修复重金属污染土壤时由于其较高的施用量可能会造成磷的积聚从而引发一些环境风险,如磷淋失造成水体富营养化,营养失衡造成作物必需的中量和微量元素缺乏以及土壤酸化等。所以应该谨慎选择磷肥种类和用量,最好是水溶性磷肥和难溶性磷肥配合、磷肥与石灰物质等配合施用。今后应着重研究磷酸盐与重金属相互作用的机理区分和评价;关注磷酸盐修复重金属污染土壤时存在的潜在风险,特别是加强植物长期不断吸收磷或其它环境条件变化致使土壤磷素持续减少过程中稳定的重金属溶解性和移动性的研究,磷酸盐修复重金属污染土壤的长期田间实践等。     

Microwave-Assisted Process (MAPTM) for the Extraction of Contaminants from Soil

Laboratory-scale tests were performed to evaluate the use of Environment Canada's patented Microwave-Assisted Process (MAP_TM) for the extraction of petroleum hydrocarbons from contaminated soil. The purpose of these tests was to determine the potential for using the process for large-scale processing of contaminated soil. Tests were performed using three soil types: a certified sediment and certified soil, both contaminated with polycyclic aromatic hydrocarbons (PAHs), and spiked peat soil contaminated with long-chain petroleum hydrocarbons. The test methods used were based on existing MAP techniques that have been proven for the sample preparation of contaminated soils for analytical purposes. The parameters evaluated concentrated on those that are amenable to a continuous large-scale process running at atmospheric pressures. This meant using solvents that are inexpensive and readily available in large volumes, low solvent to material ratios, and optimized energy inputs. In general, it was found that microwaves could be used to enhance the solvent extraction of the contaminants from the soil and that the properties of the soil greatly affected the extent to which the contaminants were removed.     

石油污染土壤的生物修复与土壤酶活性关系

研究了不同油浓度污染土壤经过两个为期125d的生物修复后的土壤中过氧化氢酶、多酚氧化酶和脂肪酶的酶活变化,分析了土壤中3种酶活性的变化特征与规律。结果表明,随着油浓度的增加,土壤中过氧化氢酶和多酚氧化酶的活性下降,脂肪酶活性增加;经过生物修复后,土壤中的过氧化氢酶和多酚氧化酶的活性在第二周期要比第一周期提高,而脂肪酶活性下降;这3种土壤酶活性变化受污染物浓度影响不显著,但不同浓度油污染土壤的修复对过氧化氢酶的影响要大于对多酚氧化酶和脂肪酶的影响。     

Analysis of Diesel Fuel Contamination in Soils by Near-Infrared Reflectance Spectrometry and Solid Phase Microextraction-Gas Chromatography

A feasibility study was undertaken to determine whether the rapid, nondestructive analytical technology, near-infrared reflectance spectrometry (NIRS) could be used to predict total petroleum hydrocarbon (TPH) in contaminated soil. Hydrocarbon concentrations were determined on samples of diesel-contaminated soils by the solid phase microextraction-gas chromatography (SPME-GC) method. The same samples were then scanned for near-infrared reflectance spectrometry over the wavelength range 1100 to 2498 nm. Calibrations were developed between the NIR spectral data and the reference SPME-GC chemical data using stepwise multiple linear regression. Linear regression relationships between NIR-predicted TPH concentrations and reference data had r² of 0.68 and 0.72. These results indicate that the combination of NIRS and SPME-GC shows promise as a method for rapid estimation of TPH in soil. A major hurdle in the evaluation of methodology for hydrocarbons residues in soil is the challenge posed by the weathering of such residues.     

Investigation of the influence of oil on soil adherence to skin

Dermal contact with contaminated soils may be a significant route of human exposure to toxic substances under some circumstances. Soil adherence to skin is an important determinant of such exposures, but factors influencing soil adherence are generally not well characterized. Petroleum hydrocarbons are often found in contaminated soils at relatively high concentrations. Results of an investigation of the influence of motor oil on soil adherence to skin are reported here. Studies were conducted at three oil concentrations (0, 1, and 10% by weight) under wet and dry conditions in three different soil types. Only two of six soil/moisture combinations showed consistently increasing adherence with increasing oil content. Overall, an increase was found in wet, but not dry soils. The results indicate that high concentrations of petroleum contaminants can increase the dermal adherence of soil, but that the magnitude of the effect is likely to be modest.     

Organic emissions from petroleum‐contaminated soil fixed in concrete

This study investigated a solidification treatment process for soils that are contaminated with hydrocarbons at levels of 0.5 and 3.0% by weight of benzene. The contaminated soils were bound in a concrete matrix and the migration of organics from the concrete to air was evaluated. If the hydrocarbon emissions are sufficiently attenuated, the concrete containing such contaminated soil can be used for exterior construction applications.

The experimental specimens consisted of concrete mixtures in which 40% of the sand was replaced with the contaminated soil. The mixtures’ ratio of cement, aggregate, sand, and water is 1:1.5:1.5:0.5 by weight. The study included specimens with and without class C fly ash replacing 10% of the cement. In addition, two unfixed control specimens were prepared for each contamination level. The concrete‐soil mixtures were placed in sealed jars and air was passed through the head space of the jars and then through carbon adsorption tubes for measurement of contaminant flux from the surface of the specimens. Measurements were made during and after concrete curing. The results were fitted to a Fickian diffusion model to estimate effective diffusivity in the concrete‐soil specimens.

The test results showed that the effective diffusivity of the contaminant within the concrete was reduced by three to five orders of magnitude over the molecular diffusivities in unfixed contaminated soil used as control. It was observed that the presence of fly ash in the concrete affects the hydrocarbon release and causes an additional decrease in effective diffusivity of about one order of magnitude. Contaminant emissions during the curing phase were found to exceed rates predicted by the Fickian model. This is apparently due to the water used in the concrete. Total emissions, however, never exceeded values emitted from the unfixed controls. This study indicates that fixation of low hydrocarbon levels within concrete is a technically viable and safe technology for recycling petroleum‐contaminated soil.     

石油污染对土壤微生物群落多样性的影响

土壤中的微生物主要有细菌、放线菌、真菌三大类群,微生物在石油污染的土壤中发挥着维持生态平衡和生物降解的功能。文中以四川省遂宁市射洪县某废弃油井周围不同程度石油污染土壤为供试土壤,首先对各组供试土壤的基本理化性质进行测定分析;然后采用平板菌落计数法测定了供试土壤中三大类微生物数量的变化,结果表明:相比未被污染的对照土壤,石油污染的土壤中细菌、放线菌、真菌数量均减少,并且土壤中可培养微生物的数量与土壤含水量呈正相关;再采用454焦磷酸测序技术对土壤中的细菌群落多样性及变化进行16S rRNA基因分析。在所有供试的4个土壤样品中,共鉴定出不少于23 982个有效读取序列和6 123种微生物,相比于未被污染的对照土壤,石油污染土壤中细菌的种类更加丰富,主要优势门类为酸杆菌门、放线菌门、拟杆菌门、绿弯菌门、浮霉菌门和变形菌门。但不同土壤样品中优势菌群的群落结构有所差异,石油污染的土壤中,酸杆菌门、放线菌门和变形菌门的数量最多,未被石油污染的土壤中,放线菌门、拟杆菌门和变形菌门的数量最多。     

Association of microbial community composition and activity with lead,chromium, and hydrocarbon contamination

Microbial community composition and activity were characterized in soil contaminated with lead (Pb), chromium (Cr), and hydrocarbons. Contaminant levels were very heterogeneous and ranged from 50 to 16,700 mg of total petroleum hydrocarbons (TPH) kg of soil(-1), 3 to 3,300 mg of total Cr kg of soil(-1), and 1 to 17,100 mg of Pb kg of soil(-1). Microbial community compositions were estimated from the patterns of phospholipid fatty acids (PLFA); these were considerably different among the 14 soil samples. Statistical analyses suggested that the variation in PLFA was more correlated with soil hydrocarbons than with the levels of Cr and Pb. The metal sensitivity of the microbial community was determined by extracting bacteria from soil and measuring [(3)H]leucine incorporation as a function of metal concentration. Six soil samples collected in the spring of 1999 had IC(50) values (the heavy metal concentrations giving 50% reduction of microbial activity) of approximately 2.5 mM for CrO(4)2- and 0.01 mM for Pb2+. Much higher levels of Pb were required to inhibit [14C]glucose mineralization directly in soils. In microcosm experiments with these samples, microbial biomass and the ratio of microbial biomass to soil organic C were not correlated with the concentrations of hydrocarbons and heavy metals. However, microbial C respiration in samples with a higher level of hydrocarbons differed from the other soils no matter whether complex organic C (alfalfa) was added or not. The ratios of microbial C respiration to microbial biomass differed significantly among the soil samples (P < 0.05) and were relatively high in soils contaminated with hydrocarbons or heavy metals. Our results suggest that the soil microbial community was predominantly affected by hydrocarbons.     

Distribution of extractable heavy metals in different soil fractions

Abstract

Due to the difficulties of precisely characterizing environmentally contaminated soil, the effects of heavy metals on plants are studied using uncontaminated soil spiked with known quantities of heavy metals. One problem in using spiked soils is how accurately the distribution of metals mimics stabilized natural soils. We studied the distribution of cadmium, chromium, copper, lead, nickel, and zinc in soil fractions after application in soluble form. The soil samples included a control (an uncontaminated Typic Argiudoll) and two samples spiked with either a moderate or high heavy metal concentration). After application of the salts the soils were subjected to wet/dry cycles over the course of three months. The soils were fractionated using a sequential chemical extraction procedure employing: (1) CaCl₂,(2) NaOH, (3) Na₂EDTA and (4) HNO₃, HCl, and HF. Soil physical separation was carried out by ultrasonic dispersion. The heavy metal levels were determined using ICP-AES. Each heavy metal displayed a unique behavior when added to soil in the form of soluble salts. Cadmium and zinc remained in the soluble fraction, indicating that no equilibrium was attained, while nickel primarily appeared in the insoluble fraction. Chromium, copper and lead were distributed among various soil chemical fractions. The highest levels of all metals appeared in the clay fraction except lead which was mainly present in the silt fraction.     

Screening of herbaceous plants for peat-enhanced rehabilitation of contaminated soil with oily sludge

A batch pot experiment using nine herbaceous species were conducted for peat enhanced rehabilitation of contaminated soil with oily sludge in the initial contents of 0%, 1.3%, 7.4%, and 12.2%, respectively. The results showed that petroleum hydrocarbons removal, plant growth indices and enzyme activities varied depending on plant species and oil contents. Cotton, ryegrass and tall fescue were effective in the rehabilitation of oily sludge contaminated soils. The total petroleum hydrocarbon (TPH) removal ranged from 30.0% to 40.0% after 170 days of treatment. Plant biomass was shown to be the preferred indicator for screening phytoremediation plant because it was closely correlated with TPH removal and enzyme activities. Peat-enhanced plant rehabilitation could be a good strategy for the treatment of oily sludge contaminated saline soils.