Influence of nonionic surfactant on the solubilization and biodegradation of phenanthrene

Phenanthrene was solubilized in two different nonionic surfactants, Tween80 and Triton X-100. The bioavailability of phenanthrane to the bacteria isolated from the petroleum contaminated soils was studied based on the rotary flasks experiments. The results showed that the concentration of nonionic surfactants above the critical micelle concentration (CMC) can increase the solubility of phenanthrene in water andwere innoxious to the phenanthrene-degrading bacteria; phenanthrene solubilized in the micelles of Tween80 was bioavailable and biodegradable. The research demonstrated the potential of surfactant-enhanced bioremediation of soils contaminated by hydrophobic organic comoounds( HOCs).     

非一阴离子表面活性剂对PAHs的增溶作用及无机盐的强化效果研究

文章研究了几种非离子和阴离子表面活性剂在单一或混合条件下对多环芳烃（PAHs）萘和菲的增溶作用,并分析了无机盐对表面活性剂增溶PAHs的强化效果.结果表明,在相同浓度条件下,非离子表面活性剂对菲和萘的增溶效果均高于阴离子表面活性剂,其增溶能力大小顺序为：Tween 80 ＞TX-100＞ Tween 20＞ SDS＞SDBS.将非离子与阴离子表面活性剂混合后,对萘和菲的增溶作用大于单一阴离子表面活性剂而小于单一非离子表面活性剂,且增溶效果随着非离子表面活性剂比例的增加而增大.低浓度（0.03 mol/L）的NaCl和Na2SO4可大幅度促进表面活性剂对萘和菲的增溶效果,但随着无机盐浓度的提高,对增溶效果的促进作用不明显.     

非离子表面活性剂溶液中多环芳烃的溶解特性

采用3种典型非离子表面活性剂(Tween80、Tween20和Triton X-100),对4种典型多环芳烃萘(naphtha-lene)、菲(phenanthrene)、芴(fluorene)和芘(pyrene)进行了溶解特性研究.结果表明,非离子表面活性剂对多环芳烃具有较好的增溶效果,在浓度大于临界胶束浓度(CMC)时,多环芳烃的溶解度与表面活性剂浓度成正比例线性相关通过质量溶解率(WSR)的比较,确定3种非离子表面活性剂对多环芳烃的增溶效果为Triton X-100＞Tween80＞Tween20,与其HLB值呈负相关.在非离子表面活性剂溶液中,多环芳烃的正辛醇-水分配系数(K_ow)与其胶束-水分配系数(K_m)呈现良好的线性相关关系.     

Uptake and accumulation of phenanthrene and pyrene in spiked soils by Ryegrass(Lolium perenne L.)

Phytoremediation has long been recognized as a cost-effective method for the removal of polycyclic aromatic hydrocarbons （PAHs） from soil. A study was conducted to investigate the uptake and accumulation of PAHs in root and shoot of Lolium perenne L. Pot experiments were conducted with series of concentrations of 3.31-378.37 mg/kg for phenanthrene and those of 4.22-365.38 mg/kg for pyrene in a greenhouse. The results showed that both ryegrass roots and shoots did take up PAHs from spiked soils, and generally increased with increasing concentrations of PAH in soil. Bioconcentration factors（BCFs） of phenanthrene by shoots and roots were 0.24- 4.25 and 0.17-2.12 for the same treatment. BCFs of pyrene by shoots were 0.20-1.5, except for 4.06 in 4.32 mg/kg treatment, much lower than BCFs of pyrene by roots （0.58-2.28）. BCFs of phenanthrene and pyrene tended to decrease with increasing concentrations of phenanthrene and pyrene in soil. Direct uptake and accumulation of these compounds by Lolium perenne L. was very low compared with the other loss pathways, which meant that plant-promoted microbial biodegradation might be the main contribution to plant-enhanced removal of phenanthrene and pyrene in soil. However, the presence of Lolium perenne L. significantly enhanced the removal of phenanthrene and pyrene in spiked soil. At the end of 60 d experiment, the extractable concentrations of phenanthrene and pyrene were lower in planted soil than in non-planted soil, about 83.24%-91.98% of phenanthrene and 68.53%-84.10% of pyrene were removed from soils, respectively. The results indicated that the removal of PAHs in contaminated soils was a feasible approach by using Lolium perenne L.     

典型表面活性剂对焦化污泥中富集多环芳烃的解吸

焦化废水中的多环芳烃(Polycyclic Aromatic Hydrocarbons,PAHs)由于其亲脂性极易转移至污泥相中,此过程成为微生物降解污泥中PAHs的传质受限步骤.基于表面活性剂解吸焦化污泥中富集的PAHs以利于微生物降解的构想,采用两种典型的表面活性剂—Triton X~(-1)00和十二烷基硫酸钠(Sodium Dodecyl Sulfate,SDS)来考察其对菲、芘和苯并[a]芘的增溶作用,对比了不同浓度的菲、芘和苯并[a]芘在焦化污泥上的吸附特征,探讨了表面活性剂对焦化污泥中富集多环芳烃的解吸行为.结果发现,表面活性剂对菲、芘和苯并[a]芘的增溶能力与三者的亲脂性存在负相关的关系,它们在焦化污泥上的吸附特征可用Freundlich等温吸附模型来描述,影响吸附容量的因素包括PAHs的亲脂性和焦化污泥的理化性质;SDS与Triton X~(-1)00共同作用时对芘和苯并[a]芘的增溶更明显;以两者混合质量计的1 g表面活性剂在16 d内可以解吸1.12mg的总PAHs.上述研究可以作为焦化污泥生物修复的增溶工艺中表面活性剂需求量计算的参考依据.     

Utilizing surfactants to control the sorption, desorption, and biodegradation of phenanthrene in soil-water system

An integrative technology including the surfactant enhanced sorption and subsequentdesorption and biodegradation of phenanthrene in the soil-water system was introduced and tested. For slightly contaminated agricultural soils, cationic-nonionic mixed surfactant- enhanced sorption of organic contaminants onto soils could reduce their transfer to plants, therefore safe-guarding agricultural production. After planting, residual surfactants combined with added nonionic surfactant could also promote thedesorption and biodegradation of residual phenanthrene, thus providing a cost-effective pollution remediation technology.0ur results showed that the cationic-nonionic mixed surfactantsdodecylpyridinium bromide (DDPB) and Triton X-100 (TX100) significantly enhanced soil retention of phenanthrene. The maximum sorption coefficient Kd* of phenanthrene for contaminated soils treated by mixed surfactants was about24.5 times that of soils without surfactant (Kd ) and higher than the combined effects of DDPB and TX100 individually, which was about 16.7 and 1.5 times Kd , respectively.0n the other hand, TX100 could effectively remove phenanthrene from contaminated soils treated by mixed surfactants, improving the bioavailability of organic pollutants. Thedesorption rates of phenanthrene from these treated soils were greater than 85% with TX100 concentration above2000 mg/L and approached 100% with increasing TX100 concentration. The biodegradation rates of phenanthrene in the presence of surfactants reached over 95% in30days. The mixed surfactants promoted the biodegradation of phenanthrene to some extent in 10-22days, and had no obvious impact on phenanthrene biodegradation at the end of the experiment. Results obtained from this study provide some insight for the production of safe agricultural products and a remediation scheme for soils slightly contaminated with organic pollutants.     

表面活性剂增溶洗脱土壤中多环芳烃的效果研究

表面活性剂增效洗脱修复技术被广泛应用于土壤修复. 本文选取11种非离子型和3种离子型表面活性剂对多环芳烃(PAHs,菲、芘、苯并[a]芘)污染土壤进行洗脱研究,筛选出洗脱效果较好的表面活性剂,并深入探索表面活性剂浓度、洗脱时间、固液比等因素以及表面活性剂的复配对土壤PAHs增效洗脱的影响,旨在比选出一种高效洗脱土壤PAHs的表面活性剂并对其洗脱方法进行优化. 结果表明:①表面活性剂浓度为10 g/L、固液比为1∶20条件下,聚氧乙烯醚-10(NSF10)的去除率最高,达到78%;其次为曲拉通X-100(TX-100)和吐温80(TW-80),去除率分别为76.7%和73.4%. ②随着表面活性剂添加浓度的增加,土壤PAHs的去除率增大,当表面活性剂浓度超过5 g/L时,PAHs去除率的增幅减缓,可见,5 g/L是相对有效且经济的表面活性剂添加浓度. ③当洗脱时间为16 h时,NSF10对PAHs的洗脱达到平衡,继续延长洗脱时间,洗脱效果并未增强. ④增加NSF10用量有利于洗脱,固液比1∶40是最优固液比,此时PAHs的去除率已达到固液比为1∶100时的85.2%. ⑤非离子表面活性剂NSF10、TX-100、TW-80与阴离子表面活性剂SDS分别以体积比9∶1进行复配时均取得了优于单一活性剂的洗脱效果,NSF10与SDS体积比为7∶3时,增溶洗脱效果最为明显,比单一表面活性剂提高了18.2%. 研究显示,NSF10是一种高效的PAHs洗脱剂,添加浓度为5 g/L、洗脱时间为16 h、固液比为1∶40是其最优参数选择,其与SDS以体积比7∶3进行复配可进一步提升增溶洗脱效果.      

非离子表面活性剂Tween20对菲生物降解的影响

以菲(PHE)为典型多环芳烃(PAHs),利用PAHs优势降解菌,研究了非离子表面活性剂Tween20(TW20)对PAHs类疏水性有机物生物降解过程的影响结果表明,TW20对PHE具有较好的增溶效果;TW20具有很好的生物降解性;不同浓度的TW20存在情况下,降解菌对PHE都有很好的去除效果.TW20可以用于PAHs污染的生物修复.     

Phytoremediation for phenanthrene and pyrene contaminated soils

Phytoremediation of soil contaminated with phenanthrene and pyrene was investigated using twelve plant species. Plant uptake nd accumulation of these chemicals were evaluated. At the end of the experiment(45 d), the remaining respective concentrations of soil henanthrene and pyrene in spiked vegetated soils, with initial phenanthrene of 133.3 mg/kg and pyrene of 171.5 mg/kg, were 8.71-16.4 nd 44.9-65.0 mg/kg, generally 4.7%-49.4% and 7.1%-35.9% lower than their concentrations in the non-vegetated soils. The loss f phenanthrene and pyrene in vegetated spiked soils were 88.2%-93.0% and 62.3%-73.8% of the added amounts of these ontaminants, respectively. Although plant uptake and accumulation of these compounds were evident, and root concentrations and RCFs(root concentration factors; defined as the ratio of PAH concentrations in roots and in the soils on a dry weight basis) of these compounds ignificantly positively correlated to root lipid contents, plant uptake and accumulation only accounted for less than 0.01% and 0.23% of the nhanced loss of these chemicals in vegetated versus non-vegetated soils. In contrast, plant-promoted microbial biodegradation was the ominant mechanism of the phytoremediation for soil phenanthrene and pyrene contamination. Results from this study suggested a easibility of the establishment of phytoremediation for soil PAH contamination.     

典型土壤中多环芳烃纵向迁移过程模拟研究

选择北京潮土、清源潮棕壤、江西红壤和黑龙江黑土4种典型土壤,采用土柱淋滤模拟实验方法,以菲和芘为代表,对比考察多环芳烃在不同土壤中的纵向迁移过程,综合分析土壤基本理化性质对多环芳烃纵向迁移过程的影响。结果表明:土壤细颗粒(0～20μm)含量和土壤有机质是制约多环芳烃在土壤中纵向迁移的主要因素,容重和阳离子交换量对该环境过程影响不大。淋滤结束后土柱中多环芳烃残留量监测结果显示:北京潮土中,菲和芘的平均浓度最低,分别为8.81,9.94 mg/kg;黑龙江黑土中,两者的残留浓度最高,分别达14.62、17.02 mg/kg。最后,SPSS相关性分析结果表明,土柱中菲、芘的残留量与土壤细颗粒(0～20μm)含量的相关系数分别为0.99和0.93,与土壤有机质的相关系数分别为0.74和0.88。     

表面活性剂Tween80及DOM对土壤中菲、芘解吸的影响

采用室内序批试验研究了水溶性有机物（DOM）及表面活性剂Tween80对污染土壤中菲、芘解吸行为的影响.结果表明,DOM能够增加土壤中菲、芘的解吸率,且猪粪堆肥的DOM作用效果较好;随着体系中Tween80浓度的增加,土壤中菲、芘的解吸率也明显地增加,当Tween80浓度为150 mg·L^-1时,菲、芘的解吸率分别是对照的1.7倍（菲）和6.2倍（芘）;DOM与Tween80联合作用时受Tween80浓度的影响,低浓度时联合作用效果不明显,当Tween80为150 mg·L^-1时,菲、芘的解吸率显著增加且大于两者单独作用的结果之和.试验结果还表明,同等条件下高相对分子质量DOM组分（>25000）对土壤中菲、芘的解吸作用大于低相对分子质量DOM组分（<1 000）.     

Tween60和SDS强化白腐真菌修复DDT污染土壤

为了提高DDT污染土壤的修复效果,研究了非离子表面活性剂Tween60及阴离子表面活性剂SDS在单一和组合两种方式对人工污染黑土中白腐真菌Phlebia lindtneri GB1027降解去除DDT的强化作用.结果表明,Tween60和SDS均能不同程度地促进土壤中DDT的生物降解,尤其在两种表面活性剂浓度为1.0mg/g干土时,土壤中DDT的降解率分别达到最高的62.9%和53.9%.相同浓度下,Tween60比SDS更有利于提高DDT污染土壤的生物修复效果,去除率提高接近10%.将Tween60与SDS以不同质量比例组合处理后的DDT去除率大小为:Tween60-SDS(3:1)＞Tween60-SDS(2:1)＞Tween60-SDS(1:1),尤其在质量比为3:1和2:1时的DDT去除率甚至高于Tween60单独处理时的去除率,表明将两种类型的表面活性剂组合后对提高DDT的生物可利用性产生了协同效果.研究还发现,菌株接种量越高,土壤中DDT的降解去除率越高,当接菌量达到1.0mL/g干土时,DDT的30d去除率达到最高的70.9%.在土壤含水率为10%~50%范围内,白腐真菌对DDT的降解去除效果随着土壤含水率的升高而增加,当土壤含水率达到50%时,土壤中有约70%的DDT被降解去除.本研究结果进一步证实了利用表面活性剂强化白腐真菌修复有机污染土壤的可行性.     

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.     

混合表面活性剂对多环芳烃的增溶作用及机理

比较了研究了单一和混合表面活性剂对萘、苊、蒽、菲、芘的增溶作用及其机理。混合表面活性剂／单一表面活性对多环芳烃协同增溶／增溶作用的大小与水溶液中表面活性剂的结构、浓度、组成及有机溶质本身的性质有关。在临界胶束浓度（CMC）以上，单一表面活性剂对多环芳烃的增溶作用顺序为TritonX100＞Brij35＞TritonX305，与其亲水亲油平衡值（HLB）呈负相关；混合表面活性剂对多环芳烃能产生显著的增溶作用，其协同增溶作用顺序为SDS－TritonX305＞SDS－Brij35＞SDS－TritonX100，协同增溶作用的大小与其中的非离子表面活性剂的HLB值及多环芳烃的辛醇－水分配系数呈正相关。混合表面活性剂溶液的CMC值降低、溶质在胶束相／水相间分配系数Kmc的增大是产生协同增溶作用的主要原因。     

Numerical simulation of PAHs sorption/desorption on soil with the influence of Tween80

In this paper, the influences of inionic surfactant Tween80 on polycyclic aromatic hydrocarbons （PAHs） sorption/desorption on artificially contaminated soil were studied, and γ model was applied to simulate the influences. Results showed that, with the use of Tween 80, the sorption behaviors of PAHs on soil altered significantly. Adsorbed Tween 80 increased the sorption amount of PAHs while the dissolved Tween80 increased the apparent solubility of PAHs. These two processes exert influences on the sorption coefficient of PAHs in soil-water system, which can be depicted by apparent sorption coefficient. The partition coefficients （the soil/water partition coefficient of PAHs and surfactants obtained fxom sorption experiments） and statistical parameters used in the amended γ model were obtained in independent experiments. With these parameters, the γ model could provide a satisfactory independent prediction of PAHs release from soil to aqueous phase at two surfactant concentrations.     

土壤微生物群落对多环芳烃污染土壤生物修复过程的响应

采用聚合酶链式反应-变性梯度凝胶电泳(PCR-DGGE)方法,研究了土壤微生物群落多样性对生物表面活性剂强化的植物-微生物联合修复多环芳烃(PAHs)污染土壤的响应.结果表明,细菌群落的Shannon-Weaver指数修复前为3.17,修复后为3.24～3.45,多样性整体呈上升趋势,其中以植物-菌根真菌-降解菌处理最高,但各处理间无显著差异(P>0.05).聚类分析结果显示,植物、植物-鼠李糖脂、植物-菌根真菌和植物-菌根真菌-鼠李糖脂这4个处理的群落相似度在90%以上,植物-降解菌处理与这4个处理群落结构最近,此外,植物-降解菌-鼠李糖脂、植物-降解菌-菌根真菌-鼠李糖脂群落相似度在80%以上.通过测序比对,DGGE图谱上优势及特征性条带分别为Bacillus、Pseudomonas、Acidobacteria、Sphingmonas、Rhodopseudomonas、Firmicutes和Methylocytaceae等,可能是与PAHs降解密切相关的种属.生物表面活性剂强化的植物-微生物联合修复污染土壤过程中,在提高PAHs生物有效性基础上,改变了土壤微生物群落结构和丰度,从而可以有效提高PAHs的降解率.     

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.     

过硫酸钠对我国典型土壤中多环芳烃氧化降解效果的影响

过硫酸钠是污染土壤化学氧化修复技术中应用较为广泛的氧化剂.为研究过硫酸钠对不同土壤中PAHs（polycyclic aromatic hydrocarbons,多环芳烃）的修复效果,以我国多种典型土壤（黑土、潮土、黄土、紫色土、褐土、砖红壤）为试验样本,以萘、菲、蒽、芘、苯并[a]芘5种PAHs为目标污染物,分析活化过硫酸钠对人为老化的降解率;此外,通过对氧化前后土壤pH、w（有机碳）等土壤性质变化的比较和分析,探讨氧化修复过程对土壤性质的影响.结果表明:当活化过硫酸钠用量为0.8 mmol/g、温度为25℃时,PAHs污染土壤中萘、菲、蒽、芘、苯并[a]芘的降解率最高,分别为87.82%、79.68%、87.93%、83.40%、94.31%.随着温度的升高,PAHs降解率逐渐升高,当温度达到25℃时,PAHs的降解率（85.69%）达到最高,随后随着温度的继续升高,总PAHs的降解率没有明显增加;随着pH的升高,PAHs的降解率逐渐升高,当pH达到6~7时,PAHs降解率维持在一个较高水平;随后随着pH的继续升高,总PAHs的降解率逐渐降低.随着温度以及pH的变化,5种PAHs的降解率与总PAHs的降解率变化趋势一致. w（有机碳）越低,PAHs环数越高,PAHs降解率越高;高环（5~6环）、中环（4环）、低环（2~3环）PAHs降解率与总PAHs降解率变化趋势一致.此外,过硫酸钠氧化修复后土壤结构遭到一定程度的破坏,土壤的pH、w（有机碳）和土壤肥力会有不同程度的下降,对土壤的再次利用有较大影响.研究显示,过硫酸钠可有效氧化降解不同性质土壤中PAHs,在氧化修复PAHs污染土壤方面具有较好的应用前景.      

微生物对芘和苯并[a]芘污染土壤的修复

将枯草芽孢杆菌、白腐真菌和分离筛选菌群分别用于芘和苯并[a]芘污染土壤的修复,比较其修复性能,并对表面活性物剂Tween80和葡萄糖对修复效果的影响规律做了初步探讨.结果表明,60 d时,枯草芽孢杆菌和分离筛选菌修复芘污染的土壤,芘的残留率分别为7.58%±0.59%和8.69%±61.35%,空白残留率为48.18%...     

Effect of surfactant on phenanthrene metabolic kinetics by Citrobacter sp. SA01

To attain a better understanding of the effects of surfactants on the metabolic kinetics of hydrophobic organic compounds, the biodegradation of phenanthrene by Citrobacter sp. SA01 was investigated in a batch experiment containing Tween 80, sodium dodecyl benzene sulfonate and liquid mineral salt medium. The Monod model was modified to effectively describe the partition, phenanthrene biodegradation and biopolymer production. The results showed that Tween 80 and sodium dodecyl benzene sulfonate （each at 50 rag/L） enhanced phenanthrene metabolism and poly-β-hydroxybutyrate production as indicated by the increasing amounts of intermediates Coy 17.2% to 47.9%）, and percentages of poly-β- hydroxybutyrate （by 107.3% and 33.1%） within the cell dry weight when compared to their absence. The modified Monod model was capable of predicting microbial growth, phenanthrene depletion and biopolymer production. Furthermore, the Monod kinetic coefficients were largely determined by the surfactant-enhanced partition, suggesting that partitioning is a critical process in surfactant-enhanced bioremediation of hydro- phobic organic compounds.