植物修复重金属污染土壤的强化措施

植物修复技术作为一种新兴的绿色环保技术,有着高效、经济和生态协调等特点而成为当前研究的热点领域,而且由于其修复的彻底性和环境友好性而在治理污染土壤实地过程得到广泛应用.概述了当前植物修复研究的基本类型和修复机理,并着重从生物技术、农艺措施和物理化学等强化手段上阐述了利用超富集植物修复污染土壤,以进一步提高超富集植物的修复效率,为大规模治理重金属污染土壤和商业化应用提供技术途径和科学依据.     

石油污染土壤的植物与微生物修复技术

石油污染土壤的生物修复技术具有成本低、简便高效、对环境影响小等优点,正逐步成为石油污染治理研究的热点领域,具有广阔的发展前景.介绍了我国的石油污染概况及生物修复技术在石油污染治理中的应用,重点对石油污染土壤的微生物修复、植物修复、植物一微生物联合修复技术的研究进展及各自的优点、局限性进行了综述,并提出了石油污染土壤生物修复技术研究的重点领域.     

Phytoremediation of pyrene contaminated soils amended with compost and planted with ryegrass and alfalfa

Ryegrass (Lolium perenne) and alfalfa (Medicago sativa) were planted in pots to remediate pyrene contaminated quartz sand (as a control group), alluvial and red soils amended with and without compost. The pyrene degradation percentages in quartz sand, alluvial soil, and red soil amended with compost (5%, w/w) and planted with ryegrass and alfalfa for 90 d growth were 98-99% and 97-99%, respectively, while those of pyrene in the corresponding treatments amended without compost but planted with ryegrass and alfalfa were 91-96% and 58-89%, respectively. Further, those of pyrene in the respective treatments amended with and without compost but unplanted were 54-77% and 51-63%, respectively. Pyrene contents in both roots and aboveground parts of ryegrass and alfalfa after 90 d growth in quartz sand and the two soils amended with or without compost were trace amounts. Statistical analyses for the parameters of ryegrass planted in red and alluvial soils including the concentrations of total water-soluble volatile low molecular weight organic acids, microbial population, pyrene degradation percentage, and spiked pyrene concentration show significant correlations at 5% and mostly 1% probability levels, by the analysis of variance. It was thus suggested that the interactions among the consortia of plant root exudates, microorganisms, and amended compost in rhizosphere soils could facilitate bioavailability of pyrene and subsequently enhance its dissipation.     

碳纳米管顶空固相微萃取-气相色谱法测定土壤中有机氯农药

采用碳纳米管顶空固相微萃取-气相色谱法测定了土壤中有机氯农药,探讨了萃取时间、萃取温度、搅拌速度、离子强度、有机溶剂和土壤加水量对萃取效率的影响.该方法的线性范围为0.5～50.0 ng/g,r0.991 5,检出限为0.03～0.33 ng/g.样品的加标回收率为91.4%～120.0%,相对标准偏差不大于12.7%.     

Agricultural soil as a potential source of input of organochlorine pesticides into a nearby pond

A study was conducted in the southeastern region of Buenos Aires province, Argentina, to assess an agricultural soil as a potential source of organochlorine (OC) pesticides for the aquatic biota of a nearby pond. We analyzed gamma-HCH (lindane), still in use, and the following banned compounds: DDT, DDE, DDD heptachlor, heptachlor epoxide, aldrin, dieldrin and endrin in soil, bulrush, grass shrimp and fish using gas chromatography with electron capture detection (GC-ECD). Among the OC pesticides, lindane was most dominant in the soil (32.6 ng/g dry wt in the upper and 173.9 ng/g dry wt in the lower horizon) and bulrush (1.9 pg/g lipid). Macrophyte also accumulated high levels of heptachlor epoxide (1.5 pg/g lipid). Heptachlor, although present in the soil, was below the detection limit in all aquatic biota studied. Its primary degradation product, heptachlor epoxide, was found in both soil and biota samples. DDT was found at low levels in the surface soil (6.8 ng/g dry wt), but at higher concentrations in fish (3.6 pg/g lipid), although levels were still below permissible levels for human consumption. Since most of the compounds were found in both soil and aquatic biota, our study suggests that agricultural soil could be an important source for OC pesticides in the nearby pond.     

The potential inhalation hazard posed by dioxin contaminated soil.

Mathematical models and field data were used to estimate the airborne concentrations of 2,3,7,8 tetrachlorodibenzo-p-dioxin (TCDD) vapor and particulates which could originate from soil containing 100 ppb TCDD. The model of Jury et al. (1983) and the box approach were used to predict the concentration of TCDD vapor from soil. The daily soil temperature was assumed to vary between 20 degrees C and 40 degrees C for six months of the year to account for diurnal warming and cooling of the soil. The depth of contamination was 50 mm. The model predicted average vapor flux rate for TCDD from soil for this temperature profile was 1.5 x 10(-14) mg/sec-cm2. The upper-bound estimates of the TCDD vapor concentration on-site at 40 degrees C and 20 degrees C were 2.5 pg/m3 and 1.8 pg/m3, respectively. Using a recently proposed unit risk value (URV) of 2.9 x 10(-6) (pg/m3)-1 [slope factor = 1.0 x 10(-14) (mg/kg-day)-1], the maximum plausible cancer risk is about 1 x 10(-5). If one accepts the EPA URV of 3.3 x 10(-5) (pg/m3)-1 (slope factor = 1.2 x 10(-13) (mg/kg-day)-1), then the risk is no greater than 1 x 10(4). A maximum TCDD vapor concentration of 0.21 pg/m3 was predicted 100 meters downwind (for summer days). The on-site concentration of TCDD in suspended particulate was estimated to be 1.4 pg/m3 (based on a TSP level of 0.07 mg/m3 from site soil). For persons exposed to vapors and particulates about 100 meters off-site, the exposure was about 10-fold less.(ABSTRACT TRUNCATED AT 250 WORDS)     

Activated carbon amendment to sequester PAHs in contaminated soil: a lysimeter field trial

Activated carbon (AC) amendment is an innovative method for the in situ remediation of contaminated soils. A field-scale AC amendment of either 2% powder or granular AC (PAC and GAC) to a PAH contaminated soil was carried out in Norway. The PAH concentration in drainage water from the field plot was measured with a direct solvent extraction and by deploying polyoxymethylene (POM) passive samplers. In addition, POM samplers were dug directly in the AC amended and unamended soil in order to monitor the reduction in free aqueous PAH concentrations in the soil pore water. The total PAH concentration in the drainage water, measured by direct solvent extraction of the water, was reduced by 14% for the PAC amendment and by 59% for GAC, 12 months after amendment. Measurements carried out with POM showed a reduction of 93% for PAC and 56% for GAC. The free aqueous PAH concentration in soil pore water was reduced 93% and 76%, 17 and 28 months after PAC amendment, compared to 84% and 69% for GAC. PAC, in contrast to GAC, was more effective for reducing freely dissolved concentrations than total dissolved ones. This could tentatively be explained by leaching of microscopic AC particles from PAC. Secondary chemical effects of the AC amendment were monitored by considering concentration changes in dissolved organic carbon (DOC) and nutrients. DOC was bound by AC, while the concentrations of nutrients (NO(3), NO(2), NH(4), PO(4), P-total, K, Ca and Mg) were variable and likely affected by external environmental factors.     

Fate of pyrene in contaminated soil amended with alternate electron acceptors

Creosote-contaminated soil samples from the Libby Ground Water Contamination Superfund Site in Libby, MT, were amended with the potential alternate electron acceptors (AEA) nitrate (KNO3), manganese oxide (MnO2), and amorphous iron oxyhydroxide (FeOOH) and incubated at low oxygen tensions (0-6% O2). The fate of 14C-pyrene was evaluated with respect to the different soil amendments. The fate of 14C from the radiolabeled pyrene with regard to mineralization and bound residue formation within soil humic fractions was not significantly different from controls for the iron and manganese amended soils. Nitrate amendments appeared to stimulate 14C-pyrene mineralization at a level of 170 mg NO3-N kg(-1), and inhibit mineralization at 340 mg NO3-N kg(-1). The stimulatory effect did not appear to be the result of nitrate serving as an electron acceptor. Although AEA amendments did not significantly affect the rate or extent of 14C-pyrene mineralization, results of oxygen-deprived incubations (purged with N2) indicate that AEA may be utilized by the microbial community in the unsaturated contaminated soil system.     

Application of a novel cold activated carbon fiber-solid phase microextraction for analysis of organochlorine pesticides in soil

A novel and simple analytical procedure using cold activated carbon fiber-solid phase microextraction (CACF-SPME) was applied to determine organochlorine pesticides (OCs) in soil samples. The pesticides in this study consist of alpha -, beta -, gamma -, and delta -hexachlorocyclohexane (HCH). By heating the sample while cooling the fiber, the developed method not only provides better performance in terms of sensitivity, linearity and recovery but also offers shorter adsorption procedure than that of traditional headspace-solid phase microextraction (HS-SPME). The experimental conditions such as the amount of water, adsorption time and adsorption temperature were optimized. Matrix effects were investigated with different types of soils. We concluded that using the standard addition method was required for quantification purposes. The limits of detection obtained using the proposed method range from 0.01 to 0.05 ng/g, and the recoveries for CACF-SPME are in the range of 80.01% to 89.68% with relative standard deviation (RSDs) better than 8.60%. The proposed method was further applied to determine OCs in real agricultural soil. The results are in good agreement with those obtained using traditional ultrasonic extraction. The research demonstrates the suitability of the CACF-SPME for the analysis of OCs in soil.     

Application of a novel cold activated carbon fiber-solid phase microextraction for analysis of organochlorine pesticides in soil

A novel and simple analytical procedure using cold activated carbon fiber-solid phase microextraction (CACF-SPME) was applied to determine organochlorine pesticides (OCs) in soil samples. The pesticides in this study consist of α -, β -, γ -, and δ -hexachlorocyclohexane (HCH). By heating the sample while cooling the fiber, the developed method not only provides better performance in terms of sensitivity, linearity and recovery but also offers shorter adsorption procedure than that of traditional headspace-solid phase microextraction (HS-SPME). The experimental conditions such as the amount of water, adsorption time and adsorption temperature were optimized. Matrix effects were investigated with different types of soils. We concluded that using the standard addition method was required for quantification purposes. The limits of detection obtained using the proposed method range from 0.01 to 0.05 ng/g, and the recoveries for CACF-SPME are in the range of 80.01% to 89.68% with relative standard deviation (RSDs) better than 8.60%. The proposed method was further applied to determine OCs in real agricultural soil. The results are in good agreement with those obtained using traditional ultrasonic extraction. The research demonstrates the suitability of the CACF-SPME for the analysis of OCs in soil.     

Effects of amended compost on mobility and uptake of arsenic by rye grass in contaminated soil

Arsenic poses a major environmental and human health problem because of its carcinogenic nature and effect on the ecosystem. Therefore, a cost effective and socially acceptable technique is needed for its remediation. The effect of different combinations of compost amended with zeolite and/or iron oxide (up to 20% w/w) was tested on a contaminated soil with high arsenic levels (34470 mg kg(-1)). The bioavailability of arsenic was determined in terms of uptake by rye grass (Lolium perenne L.) under greenhouse experimental conditions. The results indicated that the arsenic concentrations in the rye grass was reduced to 2 mg kg(-1) dry weight by using 15% compost with 5% iron oxide and 15% compost with 5% zeolite. Less than 0.01% of the total arsenic content in the soil was being taken up by the plants. Both treatments were effective in establishing significantly higher plant growth on the contaminated soil compared to other treatments. The results from sequential extraction tests indicated that in all the compost-amended soils, there was a reduction in the soluble fraction (10-37%). Arsenic in soil was examined using Scanning Electron Microscopy coupled with Energy Dispersive X-ray spectroscopy. The results indicated that arsenic was distributed mostly within the matrix of iron and oxygen in treated samples. Amongst various treatment mixtures tested, high percent of compost (15%) with zeolite (5%) and/or iron oxide (5%) is effective in reducing arsenic uptake by plants and establish re-vegetation on the contaminated soil.     

大豆、龙葵单作和间作对芘污染土壤的修复

土壤多环芳烃(PAHs)污染控制是当前土壤污染防治与保护的热点问题.采用室内盆栽实验,选择PAHs中具有代表性的四环化合物芘(Pyrene)作为研究对象,研究了大豆、龙葵单作和间作对不同浓度芘污染土壤的修复效果.结果表明:低浓度的芘(10 mg/kg)在一定程度上促进了大豆的生长,而高浓度的芘(250 mg/kg)则对大豆的生长有抑制作用;龙葵的生长没有受到芘污染(10~250 mg/kg)的影响;间作对大豆、龙葵的生长均有不同程度的促进作用.污染物芘在大豆和龙葵(成熟期)中的分布情况是:地下部分>地上部分;间作并未对大豆、龙葵中的芘含量造成显著影响.同一污染水平下,不同种植模式的修复效果为:大豆-龙葵间作> 大豆单作 >龙葵单作> 无植物对照.因此,大豆-龙葵间作是一种既能有效修复芘污染土壤,又能充分利用污染土地资源的修复模式.     

Sequestration of organochlorine pesticides in soils of distinct organic carbon content

In the present study, five soil samples with organic carbon contents ranging from 0.23% to 7.1% and aged with technical dichlorodiphenyltrichloroethane (DDT) and hexachlorocyclohexane (HCH) for 15 months were incubated in a sealed chamber to investigate the dynamic changes of the OCP residues. The residues in the soils decreased over the incubation period and finally reached a plateau. Regression analysis showed that degradable fractions of OCPs were negatively correlated with soil organic carbon (SOC) except for α-HCH, while no correlation was found between degradation rate and SOC, which demonstrated that SOC content determines the OCP sequestration fraction in soil. Analysis of the ratio of DDT and its primary metabolites showed that, since it depends on differential sequestration among them, magnitude of (p,p′-DDE + p,p′-DDD)/p,p′-DDT is not a reliable criterion for the identification of new DDT sources.     

不同洗脱剂对有机氯农药污染场地土壤修复效果比较

为了筛选出能有效修复有机氯农药污染土壤的洗脱剂,选取了16种洗脱剂对2种复合有机氯农药(六六六(HCHs)和滴滴涕(DDTs)、氯丹和灭蚁灵)污染场地土壤进行超声洗脱修复。结果表明,对于HCHs和DDTs复合污染土壤,乙酸乙酯和丙酮对HCHs的洗脱率最高,分别为87.6%和87%,其余有机溶剂对其洗脱率也在70%以上。乙酸乙酯和丙酮对于DDT仍为最优,分别为86.9%与78.4%,其余有机试剂对DDT的洗脱率在60%以上。相对于有机溶剂,表面活性剂对HCHs和DDTs复合污染土壤的洗脱效果不好,总洗脱率均低于4%。同样,对于氯丹和灭蚁灵复合污染土壤,有机溶剂的洗脱效果也明显优于表面活性剂。有机溶剂对灭蚁灵的洗脱率,除了正丙醇较低(63.5%)外,其余均在80%左右。对氯丹的洗脱率,除石油醚(59.6%)、正己烷(49.3%)和正丙醇(42%),其余均在70%以上。相同摩尔浓度的表面活性剂中,吐温80对氯丹的洗脱率为54%,环糊精为20%,鼠李糖脂和曲拉通100为13%左右,其余则小于5%,吐温80对灭蚁灵的洗脱率为29.6%,曲拉通100的为12.4%,鼠李糖脂为5.7%,其余则更低。因此,高效低毒的有机试剂,如乙酸乙酯、丙酮和乙醇等可作为有机氯农药污染土壤修复的首选。     

微米Cu／Fe对污染土壤洗脱液中有机氯农药的降解

以表面活性剂TritonX-100（TX-100）为洗脱剂,某有机氯农药（organochlorinepesticides,OCPs）污染场地土壤为对象,七氯、氯丹和灭蚁灵为目标污染物,研究微米Cu／Fe双金属对污染土壤洗脱液中OCPs的降解效果。考察了洗脱液中OCPs初始浓度、洗脱液pH值、微米零价铁加入量和cu负载量对Cu／Fe去除OCPs效果的影响。结果表明,微米Cu／Fe可以有效的去除土壤洗脱液中目标污染物。当微米零价铁加入量为1．0g（25g／L）,cu负载量为1．0％,洗脱液pH值为6．89时,Cu／Fe对2号土壤洗脱液中七氯、γ-氯丹、α-氯丹和灭蚁灵的去除效果最好,去除率分别为100．0％、99．3％、80．8％和71．1％。洗脱液中OCPs初始浓度越低,微米零价铁加入量越大,Cu／Fe对OCPs去除率越高;偏酸性条件有利于Cu／Fe对γ-氯丹和灭蚁灵的去除,而α-氯丹在中性条件下去除效果最好;1号土壤和2号土壤洗脱液的最佳铜负载量分别为2．O％和1．0％。     

Dynamics of PCB removal and detoxification in historically contaminated soils amended with activated carbon

Activated carbon (AC) can help overcome toxicity of pollutants to microbes and facilitate soil bioremediation. We used this approach to treat a Histosol and an Alluvial soil historically contaminated with PCB (4190 and 1585 mg kg⁻¹, respectively; primarily tri-, tetra- and pentachlorinated congeners). Results confirmed PCB persistence; reductions in PCB extractable from control and AC-amended soils were mostly due to a decrease in tri- and to some extent tetrachlorinated congeners as well as formation of a bound fraction. Mechanisms of PCB binding by soil and AC were different. In addition to microbial degradation of less chlorinated congeners, we postulate AC catalyzed dechlorination of higher chlorinated congeners. A large decrease in bioavailable PCB in AC-amended soils was demonstrated by greater clover germination and biomass. Phytotoxicity was low in treated soils but remained high in untreated soils for the duration of a 39-month experiment. These observations indicate the utility of AC for remediation of soils historically contaminated with PCB.     

Phytoremediation of an aged petroleum contaminated soil using endophyte infected and non-infected grasses

Phytoremediation is a promising technique for cleaning petroleum contaminated soils. In this study, the effects of two grass species (Festuca arundinacea Schreb. and Festuca pratensis Huds.), infected (E(+)) and non-infected (E(-)) by endophytic fungi (Neotyphodium coenophialum and Neotyphodium uncinatum, respectively) on the degradation of petroleum hydrocarbons in an aged petroleum contaminated soil was investigated. Plants were grown in the soil for 7 months and unplanted soil considered as control. At the end of the experiment, total and oil-degrading bacteria, dehydrogenase activity, water-soluble phenols, total petroleum hydrocarbons (TPH) and polycyclic aromatic hydrocarbons (PAHs) contents were measured in the soil. The results demonstrated that E(+) plants contained more root and shoot biomass than E(-) plants and created higher levels of water-soluble phenols and dehydrogenase activity in the soil, while there was no significant difference in bacterial counts of planted soils. Planting stimulated total and oil-degrading bacterial numbers, dehydrogenase activity and the soil content of water-soluble phenols. Regardless of endophyte infection, PAH and TPH removal in the rhizosphere of plants were 80-84 and 64-72% respectively, whereas the removals in controls were 56 and 31%, respectively. It was revealed that TPHs in retention time range of n-alkanes with C(10)-C(25) chain lengths and TPH were more degraded in the rhizosphere of E(+) plants compared to E(-) ones. Thus, grasses infected with endophytic fungi could be more efficient for removal of TPH from oil-contaminated soils.     

Chiral analysis of organochlorine pesticides in Alabama soils.

The enantiomeric composition of organochlorine (OC) pesticide residues was investigated in 32 agricultural and 3 cemetery soils from Alabama. The enantiomeric signatures were similar to those from other soils in US and Canada. The enantiomer fractions (EFs) of o,p'-DDT showed great variability, ranging from 0.41 to 0.57 while the EFs of chlordanes and chlordane metabolites were less variable and differed in general significantly from racemic. Enantioselective depletion of (+)trans-chlordane, (-)cis-chlordane, the first eluting enantiomer of MC5, and enrichment of (+)heptachlor-exo-epoxide and (+)oxychlordane was found in a large majority of the samples with detectable residues. The enantiomeric composition of alpha-hexachlorocyclohexane was racemic or close to racemic.     

Reduction in uptake by rice and soybean of aromatic arsenicals from diphenylarsinic acid contaminated soil amended with activated charcoal

Activated charcoal (AC) amendment has been suggested as a promising method to immobilize organic contaminants in soil. We performed pot experiments with rice and soybean grown in agricultural soil polluted by aromatic arsenicals (AAs). The most abundant AA in rice grains and soybean seeds was methylphenylarsinic acid (MPAA). MPAA concentration in rice grains was significantly reduced to 2% and 3% in 0.2% AC treated soil compared to untreated soil in the first year of rice cultivation. In the second year, MPAA concentration in rice grains was significantly reduced to 15% in 0.2% AC treated soil compared to untreated soil. MPAA concentration in soybean seeds was significantly reduced to 44% in 0.2% AC treated soil compared to untreated soil. AC amendment was effective in reducing AAs in rice and soybean.     

Evaluation of soil flushing potential for clean-up of desert soil contaminated by industrial wastewater

The flushing potential of a desert loess soil contaminated by the flame retardant Tetrabromobisphenol A (TBBPA), chloride (Cl(-)) and bromide (Br(-)) was studied in undisturbed laboratory column experiments (20 cm diameter, 45 cm long) and a small field plot (2 x 2 m). While the soluble inorganic ions (Cl(-) and Br(-)) were efficiently flushed from the soil profile after less than three pore volumes (PV) of water, about 50% of the initial amount of TBBPA in the soil was also flushed, despite its hydrophobic nature. TBBPA leaching was made possible due to a significant increase in the pH of the soil solution from 7.5 to 9, which increased TBBPA aqueous solubility. The remaining TBBPA mass in the soil was not mobilized from its initial location in the topsoil due to the decrease in pH at this horizon. In situ soil flushing demonstrated that this method is a feasible treatment for reducing soil contamination at this site.