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.     

Solubilization and degradation of perchloroethylene （PCE） in cationic and nonionic surfactant solutions

Solubilization of perchloroethylene (PCE) in a nonionic (Triton X-100) and a cationic (cetyltrimethylammonium bromide (CTAB)) surfactant solutions and the degradation of surfactant solubilized PCE using fine to nanosize Fe and bi-metallic Fe-Ni particles were investigated. Micelle partition coefficients (Km) and molar solubility ratio (MSR) for PCE in 10 g/L of surfactant solutions have been quantified and the solubility of PCE (100 mg/L in water) in the surfactant solutions increased by about ten fold. Of the two surfactants studied, Triton X-100 solubilized the higher amount of PCE per gram of surfactant. To degrade solubilized PCE, both iron and bimetallic Fe-Ni particles were used in continuously stirred batch reactors. The iron and bi-metallic particles were synthesized using the solution method and the particles were characterized using the SEM, EDS, TEM and XRD. The PCE solubilized up to 500 mg/L in both surfactant solutions were totally degraded at various rates by 200 g/L of bi-metallic Fe-Ni particles in less than 20 hr, which is the highest concentration of PCE degraded in the shortest time compared to data in the literature. The degradations of PCE solubilized in surfactant solutions were represented by nonlinear kinetic relationships which depended on the type of surfactant used for solubilizing the PCE.     

Sorption of Triton X-100 on soil organic matter fractions：Kinetics and isotherms

Kinetics and isotherms of Triton X-100 sorption on soil,base-extracted soil(BE),humic acid (HA) and humin (HM) were investigated respectively to get better understanding on characteristics of the surfactant sorptiun onto different soil organic matters(SOMs).It was demonstrated that the kinetics results could be satisfactorily described by the pseudo-second order model.The half of the time to reach equilibrium(t1/2) for different sorbents followed the sequence of soil>HA>BE>HM.Furthermore,the calculated equilibrium sorption capacity(Ceq) was found in the sequence of HA>BE>HM>soil,which agreed well with the experimental results.The isotherms of Triton X-100 sorption on soil and HA could be well described by the S-type isotherm,but BE and HM by the L-type.The isotherms of all the four sorbents were found reasonably fitted to the Langmuir equation.The Kd value,defined as the ratio of Triton X-100 in sorbent and in the equilibrium solution for given concentrations,generally followed the order of HM>HA>soil>BE.Separated HM and HA showed high affinity for Triton X-100,but the HA and HM in soil and BE were tightly bounded by the minerals.Thus,the HA on the soil surface might dominate the sorption,whereas the bounded HM would play a key role upon the surfactants being penetrated inside the soil.     

表面活性剂对土壤中多氯联苯的洗脱研究

采用实验室配置的PCBs污染土壤,以曲拉通X-100、吐温-80、SDS、SDBS 4种表面活性剂进行洗脱试验研究。结果表明:对于单一表面活性剂,SDS对污染土壤中多氯联苯的洗脱效果最好;采用1:20的固液比,进行2~3次洗脱,洗脱率可达50%以上;洗脱时间对洗脱效果影响不大;SDS—吐温-80混合表面活性剂对多氯联苯有协同增溶作用,且在土壤上的吸附损失较小,SDS和吐温-80的最佳质量比为5:5,在此条件下,浓度为7 000 mg/L的混合表面活性剂对多氯联苯污染土壤进行3次洗脱,洗脱率可高达97.89%。     

五种表面活性剂对柴油污染土壤清洗效果的比较

研究了十二烷基硫酸钠(SDS)、十二烷基苯磺酸钠(SDBS)、皂苷(saponin)、月桂醇聚氧乙烯(23)醚(Brij35)、Triton X-100五种表面活性剂对中度柴油污染土壤的清洗效果,考察柴油和土壤混合后在不同时间段的挥发特点,认为污染时长会直接影响表面活性剂清洗修复的效果,增大清洗剂浓度可以提高对新污染土壤的洗脱率,但对老化污染土壤的效果并不明显;对不同含油量的污染土壤清洗,研究污染程度对洗脱率变化的影响,当达到一定含油量后洗脱效果产生突变。不同表面活性剂在相同CMC倍数下清洗能力存在差异,其顺序为SDS>SDBS>Triton X-100>皂苷>Brij35。     

表面活性剂对苯并[a]芘在黑炭表面吸附解吸的影响

通过静态吸附实验,研究了3种不同类型的表面活性剂(阳离子∶十六烷基三甲基溴化铵,CTAB;阴离子∶十二烷基苯磺酸钠,SDBS∶非离子,曲拉通100,TX100)对苯并[a]芘(BaP)在黑炭表面吸附解吸的影响.结果表明,3种表面活性剂的存在均会增加BaP在黑炭表面吸附的非线性程度.CTAB的存在可以促进BaP在黑炭表面的吸附同时抑制了BaP的解吸,然而SDBS的存在降低了BaP在黑炭表面的吸附并增加了吸附过程的可逆性.与CTAB和SDBS不同,TX100对BaP在黑炭表面吸附解吸的影响取决于其添加浓度.低浓度的TX100(50 mg.L-1)能够促进BaP在黑炭上的吸附并抑制BaP的解吸,吸附能力参数Kd值(在ce=50μg.L-1下)从188 062 mL.g-1增大到264 179 mL.g-1,解吸滞后指数HI从0.44降低到0.39.随着TX100浓度增加到150 mg.L-1和200 mg.L-1,TX100对BaP的吸附表现出抑制作用并能够促进BaP的解吸,Kd值(在ce=50μg.L-1下)从188 062 mL.g-1分别降低到182 751 mL.g-1和178 730 mL.g-1,解吸滞后指数从0.44分别升高到0.65和0.70.本研究为预测多环芳烃在表面活性剂污染的环境中的分布特征和最终归趋提供了理论依据.     

Triton X-100对土壤中柴油的解吸特征及影响因素

为考察非离子表面活性剂Triton X-100对土壤中柴油解吸特性及土壤理化性质对其解吸的影响,通过振荡平衡法研究Triton X-100对浙江水稻土、重庆紫壤、江西红壤、海南沙土、青海灰漠土和黑龙江黑土中柴油解吸行为及其影响因素.结果表明,Triton X-100对浙江水稻土、重庆紫壤、江西红壤、海南沙土、青海灰漠土和黑龙江黑土中柴油的解吸均符合先快后慢、最后达到解吸平衡的规律,平衡时解吸量分别1.61、1.85、1.80、2.29、2.01和1.13 mg/g.其解吸动力学过程均符合准二级动力学模型（R2>0.99）;6种典型土壤中柴油的等温解吸特征可较好地用修正的米氏方程模型进行描述（R2>0.92）.Q_max（柴油最大解吸量）介于1.81~2.23 mg/g之间,浙江水稻土、重庆紫壤、江西红壤、海南沙土、青海灰漠土和黑龙江黑土中ρ_max（柴油最大解吸率）分别为73.20%、78.06%、75.63%、90.36%、79.89%和62.92%;土壤各理化性质对Triton X-100解吸土壤中柴油的影响起综合作用,其中土壤w（砂粒）与ρ_max呈显著正相关（R2=0.993 6,P < 0.01）,对Triton X-100解吸柴油的影响最大;而CEC（阳离子交换量）、w（OM）、w（黏粒）均与ρ_max呈显著负相关（P < 0.05）.研究显示,修正的米氏方程可用于描述柴油在土壤-水-表面活性剂Triton X-100系统中的解吸行为,w（砂粒）是影响不同土壤中柴油解吸的关键因子,可为应用Triton X-100修复柴油污染土壤提供理论基础.      

表面活性剂对热带假丝酵母降解苯酚的影响

通过液态发酵培养法探讨了添加2种化学表面活性剂十六烷基三甲基溴化铵(CTAB)、曲拉通X-100(Triton X-100)以及生物表面活性剂二鼠李糖脂(dirhamnolipid,diRL)对1株热带假丝酵母(Candida tropicalis)降解苯酚的影响.结果表明,发酵液中苯酚的分解和菌体生长的不同步,反映了苯酚对该菌的毒性作用以及苯酚降解过程中中间产物的形成.CTAB对热带假丝酵母具有毒性作用,抑制菌体对苯酚的降解.低浓度(0.1、0.3CMC)的Triton X-100对C.tropicalis的生长及对苯酚的降解有一定的促进作用,分别将苯酚降解完全的时间由空白的48h提前至24h和36h;随着Triton X-100浓度增大(1.0、3.0CMC),降解初期菌体的衰亡减缓,但使菌体生长滞后,苯酚分解完全的时间延长.生物表面活性剂diRL促进菌体对苯酚降解的同时显著地促进了C.tropicalis的生长,且促进作用随着加入diRL浓度的增大而增强,1.0、3.0CMC的diRL将苯酚降解完全的时间都提前到24h;而diRL在发酵过程中浓度也逐渐降低,这表明diRL很大程度上减弱了苯酚对菌体的毒性,并且可以共同作为碳源促进菌体的生长.     

Adsorption of mixed cationic-nonionic surfactant and its effect on bentonite structure

The adsorption of cationic-nonionic mixed surfactant onto bentonite and its effect on bentonite structure were investigated. The objective was to improve the understanding of surfactant behavior on clay mineral for its possible use in remediation technologies of soil and groundwater contaminated by toxic organic compounds. The cationic surfactant used was hexadecylpyridinium bromide (HDPB), and the nonionic surfactant was Triton X-100 (TX100). Adsorption of TX100 was enhanced significantly by the addition of HDPB, but this enhancement decreased with an increase in the fraction of the cationic surfactant. Part of HDPB was replaced by TX100 which decreased the adsorption of HDPB. However, the total adsorbed amount of the mixed surfactant was still increased substantially, indicating the synergistic effect between the cationic and nonionic surfactants. The surfactant-modified bentonite was characterized by Brunauer-Emmett-Teller specific surface area measurement, Fourier transform infrared spectroscopy, and thermogravimetric-derivative thermogravimetric/differential thermal analyses. Surfactant intercalation was found to decrease the bentonite specific surface area, pore volume, and surface roughness and irregularities, as calculated by nitrogen adsorption-desorption isotherms. The co-adsorption of the cationic and nonionic surfactants increased the ordering conformation of the adsorbed surfactants on bentonite, but decreased the thermal stability of the organobentonite system.     

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.      

表面活性剂对热带假丝酵母降解十六烷的影响

研究了Triton X-100、鼠李糖脂二糖脂(di-RL)和CTAB等3种表面活性剂对1株热带假丝酵母菌株Candida tropicalis降解十六烷的影响.结果表明,低浓度的Triton X-100对菌的生长及其十六烷的降解无明显影响,而高浓度的Triton X-100则抑制菌的生长及其对十六烷的降解,96h后Triton X-100浓度分别为0, 0.1, 0.3, 0.5, 1.0和3.0CMC时,对应的十六烷的平均残留率分别为20.5%, 20.2%, 22.0%, 54.4%, 71.2%和68.8%.di-RL促进菌的生长及十六烷的降解,且促进作用随着di-RL浓度的增加而增大,96h后浓度为0.1, 0.3, 0.5, 1.0和3.0CMC的di-RL分别促使十六烷的平均残留率降低到17.4%, 16.6%, 9.9%, 8.8%和7.8%;di-RL在发酵过程中被降解,且添加的di-RL的浓度越大,其被降解的比例越大.CTAB完全抑制菌体的生长和十六烷的降解,表明其具有毒性作用.     

生物表面活性剂皂角苷对菲在水和土壤间分配行为影响

文章比较研究了皂角苷(saponin)、Triton X-100以及二者的混合物对多环芳烃菲在土壤和水相间分配行为的影响。结果表明,在所选择的表面活性剂中,皂角苷对菲在水和土壤间的分配具有最强的增溶能力。在竞争吸附的作用下,随着加入的表面活性剂的量不同,菲在水和土壤间的分配行为也有差异。当表面活性剂的浓度较低时,促进菲在土壤上的吸附;当加入的表面活性剂的量超过其临界胶束浓度(CMC)时,菲在水和土壤间的分配系数随着表面活性剂浓度的增大出现持续减小的趋势。并且在相同浓度下,皂角苷和TritonX-100组成的混合表面活性剂的增溶能力比单独使用非离子表面活性剂Triton X-100强。同样在混合表面活性剂的协同增溶作用下,菲在水和土壤间的分配系数随着表面活性剂浓度的增加出现持续减小的趋势。     

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).     

Triton X-100在黄土上的吸附行为及影响因素

水土体系下,应用批实验法研究了Triton X-100在天然黄土上的吸附行为与平衡时间、Triton X-100浓度、溶液离子强度和pH值的关系.结果表明,Triton X-100在黄土中的吸附平衡时间约为30 min,其吸附动力学符合一级动力学模型,相应拟合参数Qe、k1、r2分别为3.041 mg·g-1、0.102 min-1、0.993 4.吸附等温线明显为非线性,在利用的4种等温吸附模型中,Sips模型对实验数据提供了最佳的拟合,其拟合参数Qmax和r2分别为3.202 mg·g-1和0.998 7.溶液离子强度和pH值对Triton X-100在黄土上的吸附有显著的影响,其吸附量随NaCl浓度的增加而明显增加,随pH增加而降低.     

Enhancing plant-microbe associated bioremediation of phenanthrene and pyrene contaminated soil by SDBS-Tween 80 mixed surfactants

The use of surfactants to enhance plant-microbe associated dissipation in soils contaminated with polycyclic aromatic hydrocarbons(PAHs) is a promising bioremediation technology. This comparative study was conducted on the effects of plant-microbe treatment on the removal of phenanthrene and pyrene from contaminated soil, in the presence of low concentration single anionic, nonionic and anionic-nonionic mixed surfactants. Sodium dodecyl benzene sulfonate(SDBS) and Tween 80 were chosen as representative anionic and nonionic surfactants, respectively. We found that mixed surfactants with concentrations less than 150 mg/kg were more effective in promoting plant-microbe associated bioremediation than the same amount of single surfactants. Only about(m/m) of mixed surfactants was needed to remove the same amount of phenanthrene and pyrene from either the planted or unplanted soils, when compared to Tween 80. Mixed surfactants( 150 mg/kg) better enhanced the degradation efficiency of phenanthrene and pyrene via microbe or plant-microbe routes in the soils. In the concentration range of 60–150 mg/kg, both ryegrass roots and shoots could accumulate 2–3 times the phenanthrene and pyrene with mixed surfactants than with Tween 80. These results may be explained by the lower sorption loss and reduced interfacial tension of mixed surfactants relative to Tween 80, which enhanced the bioavailability of PAHs in soil and the microbial degradation efficiency. The higher remediation efficiency of low dosage SDBS-Tween 80 mixed surfactants thus advanced the technology of surfactant-enhanced plant-microbe associated bioremediation.     

阳-非离子混合表面活性剂对沉积物吸附硝基苯的影响

研究了非离子表面活性剂Triton X-100、阳离子表面活性剂氯化十六烷基吡啶(CPC)及其混合物在沉积物上的吸附行为,探讨了它们对沉积物吸附硝基苯的影响.结果表明,CPC和Triton X-100在沉积物上的吸附等温线均为非线性,吸附量随着平衡浓度的增加急剧增加,并迅速达到最大吸附量.低浓度CPC能明显增加Triton X-100在沉积物上的吸附,而高浓度的CPC则显著降低Triton X-100在沉积物上的吸附.Triton X-100略微降低CPC在沉积物上的吸附.在表面活性剂浓度较低的实际环境中,无论是阳离子或非离子表面活性剂,将主要被土壤或沉积物吸附并固定.硝基苯在沉积物上的吸附等温线为线性.CPC和Triton X-100促进沉积物对硝基苯的吸附,CPC-Triton X-100混合表面活性剂溶液能进一步增强沉积物对硝基苯的吸附.因此,阳离子和非离子混合表面活性剂可增强土壤或沉积物对有机污染物的吸附固定能力,也可以用来制备有机膨润土以提高其吸附处理废水的性能.     

Mobilization of arsenic from contaminated sediment by anionic and nonionic surfactants

The increasing manufacture of surfactants and their wide application in industry,agriculture and household detergents have resulted in large amounts of surfactant residuals being discharged into water and distributed into sediment. Surfactants have the potential to enhance arsenic mobility, leading to risks to the environment and even human beings. In this study, batch and column experiments were conducted to investigate arsenic mobilization from contaminated sediment by the commercial anionic surfactants sodium dodecylbenzenesulfonate(SDBS), sodium dodecyl sulfate(SDS), sodium laureth sulfate(AES)and nonionic surfactants phenyl-polyethylene glycol(Triton X-100) and polyethylene glycol sorbitan monooleate(Tween-80). The ability of surfactants to mobilize arsenic followed the order AES SDBS SDS ≈ Triton X-100 Tween 80. Arsenic mobilization by AES and Triton X-100 increased greatly with the increase of surfactant concentration and p H, while arsenic release by SDBS, SDS and Tween-80 slightly increased. The divalent ion Ca~(2+) caused greater reduction of arsenic mobilization than Na~+. Sequential extraction experiments showed that the main fraction of arsenic mobilized was the specifically adsorbed fraction. Solid phase extraction showed that arsenate(As(V)) was the main species mobilized by surfactants,accounting for 65.05%–77.68% of the total mobilized arsenic. The mobilization of arsenic was positively correlated with the mobilization of iron species. The main fraction of mobilized arsenic was the dissolved fraction, accounting for 70% of total mobilized arsenic.     

Effects of surfactants on graphene oxide nanoparticles transport in saturated porous media

Transport behaviors of graphene oxide nanoparticles (GONPs) in saturated porous media were examined as a function of the presence and concentration of anionic surfactant (SDBS) and non-ionic surfactant (Triton X-100) under different ionic strength (IS). The results showed that the GONPs were retained obviously in the sand columns at both IS of 50 and 200 mmol/L, and they were more mobile at lower IS. The presence and concentration of surfactants could enhance the GONP transport, particularly as observed at higher IS. It was interesting to see that the GONP transport was surfactant type dependent, and SDBS was more effective to facilitate GONP transport than Triton X-100 in our experimental conditions. The advection–dispersion–retention numerical modeling followed this trend and depicted the difference quantitatively. Derjaguin–Landau–Verwey–Overbeek (DLVO) interaction calculations also were performed to interpret these effects, indicating that secondary minimum deposition was critical in this study.     

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.     

Electrochemical remediation of copper contaminated kaolinite by conditioning anolyte and catholyte pH simultaneously

This report examined electrochemical remediation of copper contaminated kaojinite by controlling electrolytes‘ pH for both of anolyte and catholyte simultaneously.Results showed the electrokinetic process and remediation efficiency varied obviously when different buffer systems,including citric acid(test 1),nitric acid EDTA(test 2)and nitric acid(test 3),were used to control catholyte pH AND Na2CO3 was used at the same time to control all anolyte one.It was found that under such pH condition soil‘s pH in soil column kept at 3.0-7.0 successfully,and correspondingly no copper precipitation and decrease of soil electroconductivity appeared.which are usually observed in electrokinetic process due to OH^- introduction into soil cojumn by electrochemical reaction occurred in cathode.Electroosmosis flow rates were almost equal for these three tests,indicating that these buffers did not affect Zeta-potential of kaolinite within the examined duration.More acid and basic solution was added into electrokinetic cell when nitric acid was used as buffer than when nitric acid EDTA and then citric acid were used.Due to introduction of large amounts of ions into soil column,significant higher current was observed for test 3 than other two.Analysis of copper speciation and total quantity in kaolinite indicated that 22.5%,23.74%and 55.65% Cu were removed from kaolinite for test 1,test 2 and test 3 respectively after only 10 days‘ electrokinetic remediation.