表面活性剂对焦化污染土壤中多环芳烃淋洗修复研究

异位土壤淋洗是一种高效修复污染土壤技术。以孝义市某焦化厂污染土壤为研究对象,采用批处理实验,探究表面活性剂曲拉通-100(TX-100)、吐温80(TW80)、烷基糖苷(APG)作为淋洗剂对土壤中16种多环芳烃(PAHs)的淋洗效果,并以TW80为代表,考察了淋洗剂浓度、淋洗时间、pH以及淋洗方式对污染土壤中PAHs的去除效果。结果表明,TW80、TX-100和APG对土壤中16种PAHs的总去除率分别为25.67%、18.89%和16.77%。TW80作为淋洗剂,3环PAHs的去除率低于高环(3环)PAHs,主要与焦化污染土壤中以3环PAHs为主有关;高环PAHs随着环数的增加,去除率降低。焦化污染土壤中PAHs的去除在240min达到平衡;大部分PAHs去除率随TW80浓度的增加而增大;pH可不作调整;在TW80用量相同情况下,建议采用单次淋洗。     

Role of dissolved humic acids in the biodegradation of a single isomer of nonylphenol by Sphingomonas sp

This study shows the important role of humic acids in the degradation of ¹⁴C and ¹³C labeled isomer of NP by Sphingomonas sp. strain TTNP3 and the detoxification of the resulting metabolites. Due to the association of NP with humic acids, its solubility in the medium was enhanced and the extent of mineralization of nonylphenol increased from 20% to above 35%. This was accompanied by the formation of significant amounts of NP residues bound to the humic acids, which also occurred via abiotic reactions of the major NP metabolite hydroquinone with the humic acids. Gel permeation chromatography showed a non-homogenous distribution of NP residues with humic acids molecules, with preference towards molecules with high-molecular-weight. Solid state ¹³C nuclear magnetic resonance spectroscopy indicated that the nonextractable residues resulted exclusively from the metabolites. The chemical shifts of the labeled carbon indicated the possible covalent binding of hydroquinone to the humic acids via ester and possibly ether bonds, and the incorporation of degradation products of hydroquinone into the humic acids. This study provided evidences for the mediatory role of humic acids in the fate of NP as a sink for bacterial degradation intermediates of this compound.     

PAHs污染土壤的热修复可行性

以某煤制气厂污染场地中16种US EPA优先控制多环芳烃（Σ16 PAHs）为目标污染物进行了热修复批量实验和可行性实验。热修复批量实验结果表明,当热修复温度为400 ℃、加热时间为8 h时,土壤中的Σ16 PAHs去除率达99.9%。热修复可行性实验选择重污染、中污染和轻污染土壤以400 ℃作为目标温度,恒温72 h进行实验。热修复前后不同程度污染土壤的Σ16 PAHs的总去除率均可达到99.9%,但重污染土壤浓度非常高,部分苯并类物质未达到修复目标值,需进一步延长加热时间或提高加热温度保证达到修复目标值。土壤土工参数影响分析结果表明,热修复后土壤颗粒粒径呈增大趋势,土壤稳定性、抗压强度均增强。此外,土壤中可溶性盐含量增多,盐渍化程度增大。     

Remediation of soil contaminated with dioxins by subcritical water extraction

The effectiveness of subcritical water extraction (SCWE) was examined for removing dioxins from contaminated soil. Most dioxins in the soil sample were reduced at 300 degrees C or more, but decreased dioxin concentrations were also observed at 150 degrees C. After 4 h of extraction, 99.4%, 94.5% and 60% of PCDDs were removed from samples at 350, 300 and 150 degrees C, respectively. It was also determined that degradation of dioxins had occurred, since the sum of dioxins in the soil plus water extracts after the experiments had considerably decreased. This study revealed that pressurizing is not essential for the removal of dioxins. Reduction was complete within 30 min at 350 degrees C; however, it took a much longer time at lower temperatures. The results of addition experiments in which OCDDs were added to different types of soil samples have shown that dechlorination is one of the major reaction pathways. After addition of OCDD to soil samples, experiments were carried out to examine in detail the degradation pathways of PCDDs. The removal rates and congener profiles varied among soil types. Although it was previously assumed that removal rates and congener profiles depended on the chemical components in soil, nonparametric statistical analysis revealed no significant relationship between the rate of reduction and elements present in the soil. It was confirmed from isomer patterns that dechlorination of the 2,3,7,8-positions in PCDDs takes place somewhat faster than for the 1,4,6,9-positions.     

Surfactant-enhanced biodegradation of crude oil by mixed bacterial consortium in contaminated soil

This study evaluated the effects of two surfactants (i.e., Tween 80 and SDS) on biodegradation of crude oil by mixed bacterial consortium in soil-aqueous system. The mixed bacterial consortium was domesticated from the activated sludge of cooking plant through a progressive domestication process. High-throughput sequencing analysis revealed that Rhodanobacter sp. was the dominant bacteria. The higher CMC_eff value for two surfactants was observed in soil-aqueous system compared with that in aqueous system, which was likely due to their adsorption onto soil particles. Either Tween 80 or SDS can be utilized as carbon source and promote the growth of mixed bacterial consortium. Further findings evidenced that the degradation of crude oil can be enhanced by adding either Tween 80 or SDS. The performance of Tween 80 was generally superior to SDS for the crude oil degradation. The highest crude oil degradation efficiency was 42.2 and 31.0% under the conditions of 5 CMC_eff of Tween 80 and 2 CMC_eff of SDS, respectively. Furthermore, the degradation efficiency of crude oil in remediation experiment (i.e., 77%) evidenced that the integration of adding Tween 80 and inoculating mixed bacterial consortium was effective for crude oil-contaminated soil decontamination.     

Bioremediation of soil contaminated with polynuclear aromatic hydrocarbons (PAHs): a review

Polynuclear aromatic hydrocarbons (PAHs) constitute a group of priority pollutants which are present at high concentrations in the soils of many industrially contaminated sites. Criteria established for the removal or treatment or both of soils contaminated with PAHs vary widely within and between nations. The bioremediation of contaminated soils with in-situ, on-site, and bioreactor techniques is reviewed, together with the factors affecting PAH degradation. Current in-situ remediation techniques are considered ineffective for the removal of most PAHs from contaminated soil. On-site 'landforming' methods have been used successfully (and within a reasonable period of time) to degrade only those PAHs with three or fewer aromatic rings. Bioreactors have proved most effective for soil remediation, since conditions for enhanced degradation can be achieved most readily. However, bioreactors are still at the development stage, and further research is required to optimise their efficiency and economy for routine use. Degradation of the more recalcitrant high-molecular-weight PAHs is contaminated soil has not been particularly successful to date. Further research needs are identified to help develop bioremediation into a most cost-effective technology. The importance of full site assessments and treatability studies for successful application in the field is emphasised.     

工业化规模生物堆修复焦化类PAHs污染土壤的效果

现场建立处理能力为450 m3工业化规模的生物堆对焦化类PAHs污染土壤进行为期8个月的修复,运行过程中控制土壤C∶N∶P=100∶10∶1、水分10%～20%(质量百分比)、堆内氧气不低于7%(体积百分比)。结果表明:O2与CO2浓度呈负相关。系统连续运行时,微生物数量增加至107数量级,高出自然状态下土壤中微生物数量1～2个数量级。除NO3-在运行后期显著增加外,其余土壤因子均无明显变化。PAHs的降解主要出现在前6个月,之后进入"拖尾"阶段,土壤中各PAH浓度基本不再降低。运行结束后,堆体0.5 m处土壤中含2、3、4、5和6个苯环PAHs的降解率分别介于56.3%～99.5%、34.8%～71.6%、30.7%～40.6%、28.6%～39.2%和39.3%,16种PAHs的平均去除率为65.1%。1.5 m处土壤中含2、3、4、5和6个苯环PAHs的降解率分别介于50.9%～99.8%、57.7%～60.9%、55.9%～63.0%、27.3%～57.1%和52.2%,16种PAHs的平均去除率为71.4%。     

Dissolution and removal of PAHs from a contaminated soil using sunflower oil

This study reports on the feasibility of remediation of polycyclic aromatic hydrocarbon (PAH) contaminated soils using sunflower oil, an environmentally-friendly solvent. Batch experiments were performed to test the influence of oil/soil ratio on the remediation of PAH contaminated soil, and to test the mass transfer behaviors of PAHs from soil to oil. An empirical model was employed to describe the kinetics of PAH dissolution and to predict equilibrium concentrations of PAHs in oil. PAH containing oil was regenerated using active carbon. Results show that dissolution of PAHs from a Manufactured Gas Plant (MGP) soil at oil/soil ratios of one or two were almost the same. Nearly all PAHs (81-100%) could be removed by sunflower oil dissolution. Mass transfer coefficients for low molecular PAHs namely fluoranthene, phenanthrene and anthracene were one or two orders of magnitude higher than those for high molecular PAHs with 4-6 rings. Ninety milliliters of PAH containing oil could be regenerated by 10 g active carbon in a batch reactor. Such a remediation procedure indicates that sunflower oil is a promising agent for the removal of PAHs from MGP soils. However, further research is required before the method can be used for in situ remediation of contaminated sites.     

零价铁活化过硫酸钠体系降解污染土壤中的多环芳烃

采用Fe0活化Na2S2O8体系降解污染土壤中的PAHs,其代表化学物为NAP、PHE、FLA和BAP。分别研究了Na2S2O8的添加量、Na2S2O8与Fe0的物质的量比、水土比和温度对降解效果的影响,同时探讨了PAHs的降解动力学;并利用电子顺磁共振法(EPR)验证了Fe0活化Na2S2O8的自由基产生情况。结果表明,当1 mol·L-1的Na2S2O8添加量为10 mL、Na2S2O8与Fe0物质量之比为200∶1、水土比为2∶1、温度为60 ℃时反应36 h后,NAP、PHE、FLA、BAP的降解率分别为98.15%、78.41%、93.47%和97.64%。PAHs的降解符合一级反应动力学,且BAP的反应速率常数最大为0.030 5 h-1。EPR谱图表明,Fe0活化Na2S2O8降解PAHs污染的土壤是SO4-·和·OH共存的反应体系。该研究可为Fe0活化Na2S2O8体系降解PAHs污染土壤的机理提供一定的依据。     

Combined treatment of PAHs contaminated soils using the sequence extraction with surfactant-electrochemical degradation

Polycyclic aromatic hydrocarbons (PAHs) cause a high environmental impact when released into the environment. The objective of this study was to evaluate the capacity of decontamination of polluted soils with PAHs using the sequence extraction-electrochemical treatment: extraction of PAHs from the soil with surfactant followed by electrochemical degradation of the liquid collected. Several PAHs (anthracene, benzo[a]pyrene, and phenanthrene) have been used as model compounds since such PAHs are found in high concentrations in contaminated environmental samples. Due to their hydrophobic nature, soil extraction has been limited. In this work, the use of six surfactants, Brij 35, Merpol, Tergitol, Tween 20, Tween 80 and Tyloxapol, has been evaluated on the PAH extraction from a model soil such as kaolin. Furthermore, the electrochemical degradation of PAHs with the surfactant that gave the best result was investigated working with neat solutions. The electrochemical treatment of these solutions was carried out in two electrochemical cells with different working volumes, 0.4 and 1.5l, and electrode material (graphite or titanium). Near complete degradation was reached for all the experiments in both cells.     

Spatial uncoupling of biodegradation, soil respiration, and PAH concentration in a creosote contaminated soil

Hotspots and coldspots of concentration and biodegradation of polycyclic aromatic hydrocarbons (PAHs) marginally overlapped at the 0.5-100 m scale in a creosote contaminated soil in southern Sweden, suggesting that concentration and biodegradation had little spatial co-variation. Biodegradation was substantial and its spatial variability considerable and highly irregular, but it had no spatial autocorrelation. The soil concentration of PAHs explained only 20-30% of the variance of their biodegradation. Soil respiration was spatially autocorrelated. The spatial uncoupling between biodegradation and soil respiration seemed to be governed by the aging of PAHs in the soil, since biodegradation of added ¹³C phenanthrene covaried with both soil respiration and microbial biomass. The latter two were also correlated with high concentrations of phospholipid fatty acids (PLFAs) that are common in gram-negative bacteria. However, several of the hotspots of biodegradation coincided with hotspots for the distribution of a PLFA indicative of fungal biomass.     

Evolution of bacterial community during bioremediation of PAHs in a coal tar contaminated soil

The monitoring of a windrow treatment applied to soil contaminated by mostly 2-, 3- and 4-ring PAHs produced by coal tar distillation was performed by following the evolution of both PAH concentration and the bacterial community. Total and PAH-degrading bacterial community structures were followed by 16S rRNA PCR-DGGE in parallel with quantification by bacterial counts and 16 PAH measurements. Six months of biological treatment led to a strong decrease in 2-, 3- and 4-ring PAH concentrations (98, 97 and 82% respectively). This result was associated with the activity of bacterial PAH-degraders belonging mainly to the Gamma-proteobacteria, in particular, the Enterobacteria and Pseudomonas genera, which were detected over the course of the treatment. This group was considered to be a good bioindicator to determine the potential PAH biodegradation of contaminated soil. Conversely, other species, like the Beta-proteobacteria, were detected after 3months, when 2-, 3- and 4-ring PAHs were almost completely degraded. Thus, presence of the Beta-proteobacteria group could be considered a good candidate indicator to estimate the endpoint of biotreatment of this type of PAH-contaminated soil.     

Butanol extraction to predict bioavailability of PAHs in soil

The feasibility of a mild-solvent extraction procedure to predict the bioavailability of individual polycyclic aromatic hydrocarbons (PAHs) in soil was assessed. The quantities that were degraded during the course of biodegradation of phenanthrene and pyrene in soil with or without plants correlated with the amounts extracted by n-butanol, with R2 values of 0.971 and 0.994, respectively. Six consecutive groups of earthworms removed ca. 70% of the pyrene remaining after extensive biodegradation, a value similar to the quantity extracted by n-butanol. The amount of chrysene aged in sterilized soil that was extracted by n-butanol was not statistically different from the quantities assimilated by earth-worms (Eisenia fetida) introduced into the soil. Such a mild extraction procedure may be useful as a means of predicting PAH bioavailability.     

PCB congener selective biodegradation by the white rot fungus Pleurotus ostreatus in contaminated soil

Six strains of white rot fungi were tested for their biodegradation ability of low chlorinated polychlorinated biphenyl (PCB) commercial mixture (Delor 103) in real soil system. Phanerochaete chrysosporium and Trametes versicolor did not show any ability to degrade PCBs in soil. On the contrary, four strains of Pleurotus ostreatus were able to remove about 40% of Delor 103 in two months. All P. ostreatus strains decomposed PCBs selectively with the preference for congeners with chlorine atoms in ortho > meta > para position. Degradation efficiency decreased with increasing number of chlorination.     

Dynamics of nitrogen in a PAHs contaminated soil amended with biosolid or vermicompost in the presence of earthworms

Nitrogen mineralization in PAHs contaminated soil in presence of Eisenia fetida amended with biosolid or vermicompost was investigated. Sterilized and unsterilized soil was contaminated with PAHs, added with E. fetida and biosolid or vermicompost and incubated aerobically for 70 days, while dynamics of inorganic N were monitored. Addition of E. fetida to sterilized soil increased concentration of NH(4)(+) 100> mg N kg(-1), while concentrations in unsterilized remained <60 mg N kg(-1) except for soil amended with biosolid plus PAHs where it increased to >80 mg kg(-1). Addition of PAHs had no significant effect on concentration of NH(4)(+) compared to the unamended soil, except in the soil added with biosolid. Addition of E. fetida to sterilized soil increased concentration of NO(2)(-) 15> mg N kg(-1) while concentrations in unsterilized soil remained <7.5 mg N kg(-1) except for soil amended with biosolid where it increased to >20 mg kg(-1). Addition of PAHs had no significant effect on concentration of NO(2)(-) compared to the unamended soil. Addition of biosolid and vermicompost increased concentration of NO(3)(-), while addition of E. fetida decreased concentration of NO(3)(-) in biosolid amended soil. It was found that NH(4)(+) and NO(2)(-) oxidizers were present in the gut of E. fetida, but their activity was not sufficient enough to inhibit a temporarily increase in concentrations of NH(4)(+) and NO(2)(-). Contamination with PAHs induced immobilization of N in biosolid or vermicompost amended soil, as did feeding of E. fetida on biosolid or vermicompost.     

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.     

A remediation strategy based on active phytoremediation followed by natural attenuation in a soil contaminated by pyrite waste

Phytoremediation of metal-polluted soils can be promoted by the proper use of soil amendments and agricultural practices. A 4-year phytoremediation programme was applied to a site affected by the toxic spill of pyrite residue at Aznalcóllar (Spain) in 1998, contaminated with heavy metals (Zn, Cu, Pb, Cd) and arsenic. This consisted of active phytoremediation, using organic amendments (cow manure and compost) and lime and growing two successive crops of Brassica juncea (L.) Czern., followed by natural attenuation without further intervention. Changes in soil pH, extractable metal and As concentrations, organic carbon content and microbial biomass was evaluated. The initial oxidation of metal sulphides from pyrite residues released soluble metals and reduced soil pH to extremely acidic values (mean 4.1, range 2.0-7.0). The addition of lime (up to 64 t ha(-1)) increased soil pH to adequate values for plant growth, resulting in a significant decrease in DTPA-extractable metal concentrations in all plots. The natural attenuation phase showed also a decrease in extractable metals. Organic treatments increased the soil total organic carbon, which led to higher values of microbial biomass (11.6, 15.2 and 14.9 g kg(-1) TOC and 123, 170 and 275 microg g(-1) biomass-C in control, compost and manure plots, respectively). Active phytoremediation followed by natural attenuation, was effective for remediation of this pyrite-polluted soil.     

高锰酸钾修复PAHs污染土壤过程中Mn迁移转化规律

为探究高锰酸钾氧化修复技术应用过程中Mn元素迁移转化规律及其潜在的环境风险,通过室内模拟实验,采用某焦化厂PAHs污染土壤作为研究材料,探究了高锰酸钾修复技术中不同药剂投加量对PAHs去除、高锰酸钾消耗量、土壤中Mn质量分数、Mn赋存形态分布及有效态Mn质量分数等的影响。结果表明,高锰酸钾氧化处理可有效去除土壤中PAHs;当高锰酸钾投加量为0.20 mmol·g⁻¹、反应时间为1 d时,PAHs去除率最高,可达89.61%。氧化处理过程中,高锰酸钾消耗量和土壤Mn质量分数均与高锰酸钾的投加量有关,随投加量增加而升高。其中,土壤Mn的质量分数与高锰酸钾消耗量呈显著正相关关系。高锰酸钾氧化处理后土壤中Mn主要以铁锰氧化物结合态存在,所占比例为77.04%~92.17%。土壤经0.05 mmol·g⁻¹高锰酸钾氧化处理后,土壤有效态Mn的质量分数比对照组增加了0.94倍;而在高锰酸钾投加量为0.10~0.40 mmol·g⁻¹的处理条件下,土壤有效态Mn的质量分数下降了77.65%~99.09%。药剂投加量是影响高锰酸钾氧化修复PAHs污染土壤过程中Mn环境行为的关键因子。本研究结果可为高锰酸钾氧化修复技术应用工艺优化提供参考。     

The effects of LMWOAs on biodegradation of multi-component PAHs in aqueous solution using dual-wavelength fluorimetry

Biodegradation of dissolved fluorene (Flu), phenanthrene (Ph) and pyrene (Py), three polycyclic aromatic hydrocarbons (PAHs), singly or as a mixture of the three, by two bacterial strains, MEBIC 5140 (Mycobacterium flavescens) and MEBIC 5141 (Mycobacterium scrofulaceum), as well as the effects of low molecular weight organic acids (LMWOAs), e.g. malic acid, citric acid and butyric acid on biodegradation of the three PAHs in mineral salts medium aqueous solution were investigated using a newly established dual-wavelength fluorimetric method. The results showed that biodegradation processes can be monitored simultaneously, quickly and simply by dual-wavelength fluorimetry. Both co-metabolism and inhibitory effects were found during the biodegradation of the three PAHs by MEBIC 5140 and MEBIC 5141. Positive effects of butyric acid and negative effects of citric acid on biodegradation of the three PAHs in a mixture were observed.     

热强化气相抽提法修复半挥发性石油烃污染土壤的影响因素

热强化气相抽提技术（T-SVE）在修复半挥发性石油烃污染土壤方面极具应用潜力。本文基于实验室模拟T-SVE装置,研究了加热温度及土壤含水量、有机质对4种半挥发性石油烃（正十三烷、正十四烷、正十五烷和正十六烷）去除效率的影响,并对石油烃去除动力学进行了拟合。结果表明,温度决定性地影响了石油烃污染土壤的修复效率,污染土壤残留率与加热温度基本呈反比。石油烃去除过程符合Elovich和Freundlich热脱附动力学方程。加热温度为140 ℃时,土壤含水量（5%~30%）的增加降低了石油烃去除效率;当温度上升到180 ℃,石油烃去除率在土壤含水量5%~20%时也表现出降低趋势,但在土壤含水量为30%时反而达到最高值。土壤有机质含量增加明显降低了石油烃去除率,尤其对于辛醇-水分配系数值高的石油烃;当加热温度从140 ℃升高到220 ℃,土壤有机质对石油烃污染去除的限制明显降低。实验获得结果可为T-SVE技术修复石油烃污染的工程设计提供参考。