多环芳烃类污染土壤强化生物修复技术研究及应用

针对多环芳烃类(PAHs)污染土壤,采用富集培养的方法分离筛选得到高效PAHs降解菌,并作为外源添加至高效复合微生物降解菌剂中运行过程中控制土壤含水率、微生物菌剂、营养物质的投加比例以及人工翻抛频率,开展强化生物修复试验。土壤中PAHs的降解主要出现在前3个月,之后进入生物降解拖尾阶段,土壤中各PAHs的浓度下降缓慢。其中,堆体土壤中低环PAHs、中环PAHs和高环PAHs的最高去除率分别为66.50%、71.78%和56.99%,16种PAHs的平均去除率为64.06%。分别从生物可利用性、微生物激活营养剂、提高供氧效率和微生物菌剂4个因素进行强化生物修复研究。运行结果显示:高密度投加PAHs高效降解菌,并提供适量的营养物质,同时添加生物表面活性剂进行强化,最终污染土壤中总PAHs降解率可以达到85.07%,且16种PAHs均得到显著降解。     

生物堆修复多环芳烃类污染土壤研究进展及工业化应用初试

土壤的多环芳烃污染日益受到社会关注,经济有效的生物修复技术逐渐成为研究热点,生物堆即其中新兴的技术之一。本文先结合国内外运用生物堆技术修复多环芳烃污染土壤的案例,从生物堆技术简介、修复过程影响因子、修复过程机理简析等三个方面进行综合阐述。在此基础上于某工业污染场地现场建立处理能力为500m3的生物堆进行为期6个月的工业化应用初试。运行结束后,各采样点最终浓度均低于风险评估中所确定的修复目标值,土壤中2环至6环的PAHs降解率依次分别为78%,55%,45%,43%和22%。最后对该技术在"土十条"出台后的研究应用进行展望。     

固相微萃取和固相萃取评价多环芳烃降解过程中的生物有效性变化

为了揭示多环芳烃(PAHs)降解过程中的生物有效性变化规律,应用PAHs降解菌剂对PAHs污染焦化厂土壤进行微生物修复,采用固相微萃取及固相萃取方法提取评价PAHs的生物有效性,分析降解率和生物有效性变化的差异及相关关系.结果表明,该焦化厂土壤中PAHs总量以低环PAH为主,微生物菌剂对土壤总PAHs降解率为68.3%;微生物作用后,孔隙水中PAHs的降低以3、4环为主,孔隙水中PAHs变化率普遍低于土壤中的降解率;Tenax-TA提取降解前后土壤中的PAHs,降解后3、4环PAHs的快速解吸组分降低,5、6环的快速解吸组分变化不大;土壤中PAHs降解量分别与PAHs孔隙水浓度和Tenax-TA快速提取量存在相关关系.以上结果表明可用PAHs孔隙水浓度以及Tenax-TA快速提取量预测微生物对土壤PAHs的降解,这为焦化厂土壤PAHs污染的修复提供了理论依据.     

春冬季节对堆肥修复多环芳烃（PAHs）污染土壤的影响

采用强制通风堆肥法修复多环芳烃PAHs(16种)污染土壤,比较了春季和冬季时堆肥法对PAHs污染土壤的修复效果.结果表明,冬季时受污染土壤中PAHs降解率高于春季,1号堆料[m(土壤)∶ m(猪粪)∶ m(锯末)=1∶ 1∶ 1(干重)]和2号堆料[m(土壤)∶ m(猪粪)∶ m(锯末)=1∶3∶1(干重)]的总PAHs降解率>70%,但1号堆料的总PAHs降解率(74.61%)高于2号堆料,低、中和高环三类PAHs的降解率分别为66.46%、 79.12%和75.88%;堆肥过程结束后,受污染土壤(干重)中大部分PAHs残留量均≤1000 μg/kg,但苯并[b]荧蒽在春季试验的残留量较高,它在1号和2号堆料的残留量分别为25000 μg/kg和20000 μg/kg,而它在冬季2个堆体的残留量均低于5000 μg/kg;堆肥修复污染土壤过程中总PAHs降解的一级反应动力学拟合结果表明,冬季拟合程度高于春季,R2>0.6,半衰期约为13 d.     

通风及营养元素对多环芳烃污染土壤修复影响

文章在无外源接种体的条件下,评估了强制通风(通风量为1.51 L/min)与营养元素对土壤中多环芳烃(PAHs)降解的交互作用。结果表明:仅靠合适的营养液配方和长时间通风可以刺激污染土壤中的土著微生物生长,并影响微生物菌群的形成。通风同时添加营养液有利于好氧菌生长、加快PAHs的降解;与通风相比,添加营养元素是影响PAHs降解的主要因素。通风和添加营养元素对3环PAHs降解影响不显著,但可促进4环、5环和6环PAHs污染物降解。60 d内,仅通风、仅添加营养元素、同时通风和添加营养元素处理的PAHs分别降解了52%、59%、67%。     

生物表面活性剂-微生物强化紫花苜蓿修复多环芳烃污染土壤

在温室盆栽条件下,通过单独或联合添加生物表面活性剂鼠李糖脂(RH)和接种多环芳烃专性降解菌(DB),研究了利用生物表面活性剂-微生物强化紫花苜蓿(Medicago sativa L.)修复多环芳烃(PAHs)长期污染土壤的效果.结果表明,添加鼠李糖脂和接种PAHs专性降解菌能促进紫花苜蓿的生长和土壤中PAHs的降解.培养90d后,RH、DB处理的PAHs的降解率分别为30.0%和49.6%,均高于对照处理(CK)(21.7%).RH+DB处理PAHs的降解率最高达53.9%,说明鼠李糖脂和PAHs专性降解菌协同作用显著.另外,随着PAHs苯环数的增加,其平均降解率逐渐降低,但是接种PAHs专性降解菌能够提高4环和5环PAHs的降解率.同时也发现土壤中脱氢酶活性和PAHs降解菌数量越高的处理,土壤PAHs的降解率也越高.所以添加鼠李糖脂和接种PAHs专性降解菌能够有效促进土壤多环芳烃降解.     

芹菜对土壤中多环芳径修复作用的初步研究

利用盆栽实验研究了水芹对某实际多环芳烃(PAHs)污染场地土壤的修复作用。通过75 d的温室培养试验,对污染土壤和植物根、茎中PAHs的含量进行测定。结果显示种植水芹的土壤中PAHs的去除量要显著高于对照土壤,并且水芹促进微生物降解是其去除土壤PAHs的主要途径,占到了PAHs去除总量的99%以上。水芹较易吸收2~4环PAHs,而易促进3~6环PAHs的微生物降解。芘在水溶液中的增溶实验表明,脂溶性根系物质利用其表面活性能够提高对PAHs生物可利用性,从而促进土壤中微生物对PAHs的降解。     

土壤中PAHs的污染现状及修复对策

概述了我国土壤受多环芳烃(PAHs)污染的水平及多环芳烃(PAHs)的分布特点:①我国土壤已普遍受到多环芳烃(PAHs)的污染,但大多是中低污染水平;②北京、上海、大连、天津等地土壤受多环芳烃(PAHs)污染较为严重,属严重污染水平,存在较大的生态风险;③在同一个研究区,农村、郊区、城区土壤中多环芳烃(PAHs)的污染逐渐加重,而且不同土壤利用下多环芳烃(PAHs)的污染也存在差异。总结了受多环芳烃(PAHs)污染土壤的修复对策:植物修复;微生物修复;植物-微生物联合修复。植物-微生物联合修复的效率较高。     

表面活性剂增效微生物修复PAHs污染土壤的研究进展

生物降解是去除土壤环境中多环芳烃（PAHs）的重要途径,通过使用表面活性剂增效修复可显著提高PAHs降解速度和程度。本文系统评述了表面活性剂增效修复PAHs污染土壤的研究现状和存在的问题。     

难降解多环芳烃污染土壤的机械力化学修复

利用机械力化学法修复多环芳烃污染土壤,以四环芳烃芘为代表污染物,研究了球磨时间和球磨转速对土壤中芘去除率的影响。当球磨时间为6 h,球磨速度为500 r/min时,土壤中芘去除率为93.78%。利用SiO₂作为模拟土壤,通过对球磨前后模拟土壤的GC-MS、红外光谱和拉曼光谱分析,探索芘的降解途径和机理。机械力化学修复过程中,芘的苯环被破坏,部分中间产物为环数较少的多环芳烃(PAHs)、碳链较短的烷烃,还有部分被碳化成石墨和不定形碳。利用机械力化学法对实际污染土壤进行修复,修复后土壤中芘和荧蒽浓度分别为21.45,35.68 mg/kg。机械力化学法修复多环芳烃污染土壤具有可行性和广泛的应用前景。     

Removal of high concentrations of polycyclic aromatic hydrocarbons from contaminated soil by biodiesel

Solubilizing experiments were carried out to evaluate the ability of biodiesel to remove polycyclic aromatic hydrocarbons (PAHs) from highly contaminated manufactured gas plant (MGP) and PAHs spiked soils with hydroxypropyl-β-cyclodextrin (HPCD) and tween 80 as comparisons. Biodiesel displayed the highest solubilities of phenanthrene (420.7 mg·L⁻¹), pyrene (541.0 mg·L⁻¹), and benzo(a)pyrene (436.3 mg·L⁻¹). These corresponded to several fold increases relative to 10% HPCD and tween 80. Biodiesel showed a good efficiency for PAH removal from the spiked and MGP soils for both low molecular weight and high molecular weight PAHs at high concentrations. Biodiesel was the best agent for PAH removal from the spiked soils as compared with HPCD and tween 80; as over 77.9% of individual PAH were removed by biodiesel. Tween 80 also showed comparable capability with biodiesel for PAH solubilization at a concentration of 10% for the spiked soils. Biodiesel solubilized a wider range of PAHs as compared to HPCD and tween 80 for the MPG soils. At PAH concentrations of 229.6 and 996.9 mg·kg⁻¹, biodiesel showed obvious advantage over the 10% HPCD and tween 80, because it removed higher than 80% of total PAH. In this study, a significant difference between PAH removals from the spiked and field MGP soils was observed; PAH removals from the MGP soil by HPCD and tween 80 were much lower than those from the spiked soil. These results demonstrate that the potential for utilizing biodiesel for remediation of highly PAH-contaminated soil has been established.     

Removal of polycyclic aromatic hydrocarbons from different soil fractions by persulfate oxidation

Removal of polycyclic aromatic hydrocarbons (PAHs) from different soil fractions of contaminated soil was investigated by using activated persulfate oxidation remediation in our research. The results showed that the light fraction, which accounted for only 10% of the soil, contained 30% of the PAHs at a concentration of 4352?mg/kg. The heavy fraction contained more high-molecular-weight PAHs, and the total PAH concentration was 625?mg/kg. After being oxidized, the removal rate of PAHs was 39% in the light fraction and nearly 90% in the heavy fraction. Among the different fractions of the heavy fraction, humic acid contained the highest concentration of PAHs, and consequently, the highest removal efficiency of PAHs was also in humic acid. Compared with the light fraction, the heavy fraction has more aromatic compounds and those compounds were broken down during the oxidation process, which may be the removal mechanism involved in the oxidation of high-ring PAHs. Similarly, the enhancement of C = C bonds after oxidation can also explain the poor removal of high-ring PAHs in the light fraction. These results imply that different fractions of soil vary in composition and structure, leading to differences in the distribution and oxidation efficiencies of PAHs.     

表面活性剂强化好氧生物修复PAHs污染土壤效果研究

通过实验测试不同浓度梯度表面活性剂对PAHs的增溶效果,筛选出一种能够提升PAHs脱附于液相的表面活性剂,利用其与好氧生物促进剂的协同作用,强化土壤中PAHs的脱附及生物降解过程,并应用于中低浓度PAHs污染土壤的中试实验。通过对比营养物质投加量、氧气供给方式、含水率控制、人工翻抛频次等条件确定最佳的现场实施方式,其中氧气供给方式采用缓释氧药剂和人工翻抛2种曝气方式。结果显示:缓释氧+生物促进剂,辅以定期补水的养护操作,是最为有效的处理方式,总PAHs降解率可达91.24%,苯并(a)芘降解率可达89.86%,此技术路线不需要人工曝气,可大幅节省实施成本。该成果为国内中低浓度PAHs污染土壤提供了一种更加经济高效的解决方案。     

耐冷腐殖酸吸附态PAHs降解菌筛选及其降解特性

为了寻找自然环境中高效PAHs降解菌,并应用于北方寒冷地区PAHs污染土壤修复,从沈抚灌渠冻融土壤中筛选出一株以腐殖酸(HA)吸附态PAHs为碳源和能源且生长良好的耐冷菌株,结合其生理生化特征和16S rDNA序列比对,鉴定此菌株为假单胞菌(Pseudomonas sp.SDR4),并研究了其对冻融土壤中HA吸附态PAHs的降解性能.结果表明:Pseudomonas sp.SDR4对冻融土壤中Phe、Pyr和Ba P均具有一定的降解能力,42 d降解率分别为73.88%、64.88%和49.39%.加入HA能够提高其对Phe、Pyr和Ba P的降解率,42 d降解率分别提高15.9%、13.8%和8.6%;在降解初期加入HA可显著提高Phe、Pyr和Ba P的降解速率,第1周,降解速率分别提高37.8%、28.4%和39.1%,但在后期促进效果减弱.若要在寒冷地区选择Pseudomonas sp.SDR4作为固定化菌株,可添加HA提高其修复效果.本研究为北方寒冷地区PAHs污染土壤修复提供了新的固定化菌种.     

优化SO4-·高级氧化技术修复PAHs复合污染土壤

采用硫酸根自由基高级氧化技术（SR-AOPs）修复南京某炼钢厂附近PAHs复合土壤,通过调整过硫酸钠（Na2S2O8）和亚铁离子（Fe²⁺）比例,结合添加不同种类和浓度的螯合剂和表面活性剂,获得修复的最佳条件,并比较分析不同类型PAHs的降解特征.结果表明：Na₂S₂O₈和Fe²⁺的配比显著影响土壤PAHs的降解效果,当Na₂S₂O₈用量为5mmol/g,Fe²⁺用量为0.5mmol/g,二者比例为10：1时,培养24h,PAHs总去除率最高,为29.32%;在此基础上添加螯合剂柠檬酸0.5mmol/g时,PAHs总去除率可提高至49.9%;继续添加0.27mg/g表面活性剂IGEPAL CA-720,PAHs总去除率最大,为80.8%.分析不同条件下SR-AOPs对PAHs的降解效果,得到总体上SR-AOPs对四环PAHs去除效果最好.添加柠檬酸和IGEPAL CA-720可以进一步强化对土壤中3环、6环PAHs的去除.柠檬酸和IGEPAL CA-720的添加可以更有效去除污染土壤中PAHs,尤其是针对高环PAHs.     

Effect of organic wastes on the plant-microbe remediation for removal of aged PAHs in soils

The effectiveness of in-situ bioremediation of polycyclic aromatic hydrocarbons (PAHs) may be inhibited by low nutrients and organic carbon. To evaluate the effect of organic wastes on the PAHs removal efficiency of a plant-microbe remediation system, contaminated agricultural soils were amended with different dosages of sewage sludge (SS) and cattle manure (CM) in the presence of alfalfa (Medicago sativa L.) and PAHs-degraders (Bacillus sp. and Flavobacterium sp.). The results indicated that the alfalfa mean biomasses varied from 0.56 to 2.23 g/pot in root dry weight and from 1.80 to 4.88 g/pot in shoot dry weight. Low dose amendments, with rates of SS at 0.1% and CM at 1%, had prominent effects on plant growth and soil PAHs degradation. After 60-day incubation, compared with about 5.6% in the control, 25.8% PAHs removal was observed for treatments in the presence of alfalfa and PAHs-degraders; furthermore, when amended with different dosages of SS and CM, the removed PAHs from soils increased by 35.5%-44.9% and 25.5%-42.3%, respectively. In particular, the degradation of high-molecular-weight PAHs was up to 42.4%. Dehydrogenase activities (DH) ranged between 0.41 and 1.83 μupg triphenylformazan/(g dry soil. hr) and the numbers of PAHs-degrading microbes (PDM) ranged from 1.14× 10⁶ to 16.6× 10⁶ most-probable-number/g dry soil. Further investigation of the underlying microbial mechanism revealed that both DH and PDM were stimulated by the addition of organic wastes and significantly correlated with the removal ratio of PAHs. In conclusion, the effect of organic waste application on soil PAHs removal to a great extent is dependent on the interactional effect of nutrients and dissolved organic matter in organic waste and soil microorganisms.