表面活性剂对土壤中石油污染物的解吸

采用4种表面活性剂解吸老化石油污染土壤中的污染物,对其解吸动力学特征及残油组分进行了分析。实验结果表明:在表面活性剂质量浓度相同(0.5 g/L)条件下,土壤中石油污染物解吸率的大小顺序为十二烷基硫酸钠(SDS)曲拉通X-100(TX-100)吐温-80(TW-80)十二烷基苯磺酸钠(SDBS);SDS的解吸率最高,经48 h累积解吸后土壤中石油污染物的解吸率为38.7%;表面活性剂对石油污染物的解吸动力学曲线用Elovich方程拟合,效果最好,相关系数为0.970 2~0.995 6;非离子表面活性剂(TX-100、TW-80)对石油污染物中饱和烃组分的解吸率优于阴离子表面活性剂(SDS、SDBS),而对芳香烃组分的解吸率不如阴离子表面活性剂。     

Use of biosurfactants from urban wastes compost in textile dyeing and soil remediation

A compost isolated humic acid-like (cHAL) material was pointed out in previous work for its potential as auxiliary in chemical technology. Its potential is based on its relatively low 0.4gL(-1) critical micellar concentration (cmc) in water, which enables cHAL to enhance the water solubility of hydrophobic substances, like phenanthrene, when used at higher concentrations than 0.4gL(-1). This material could be obtained from a 1:1 v/v mixture of municipal solid and lignocellulosic wastes composted for 15 days. The compost, containing 69.3% volatile solids, 39.6% total organic C and 21C/N ratio, was extracted for 24h at 65 degrees C under N2 with aqueous 0.1molL(-1) NaOH and 0.1molL(-1) Na4P2O7, and the solution was acidified to separate the precipitated cHAL in 12% yield from soluble carbohydrates and other humic and non-humic substances. In this work two typical applications of surfactants, i.e., textile dyeing (TD) and soil remediation by washing (SW), were chosen as grounds for testing the performance of the cHAL biosurfactant against the one of sodium dodecylsulfate (SDS), which is a well established commercial synthetic surfactant. The TD trials were carried out with nylon 6 microfiber and a water insoluble dye, while the SW tests were performed with two soils contaminated by polycyclic aromatic hydrocarbons (PAH) for several decades. Performances were rated in the TD experiments based on the fabric colour intensity (DeltaE) and uniformity (sigmaDeltaE), and in the SW experiments based on the total hydrocarbons concentration (CWPAH) and on the residual surfactant (Cre) concentrations in the washing solution equilibrated with the contaminated soils. The results show that both cHAL and SDS exhibit enhanced performance when applied above their cmc values. However, while in the TD case a significant performance effect was observed at the surfactants cmc value, in the SW case the required surfactants concentration values were equivalent to 25-125xcmc for cHAL and to 4-22xcmc for SDS. The vis-a-vis comparison of the two surfactants gave the following results: in the TD case the cHAL biosurfactant at 0.4gL(-1) yields good colour intensity and equal colour uniformity as SDS at 5gL(-1), in the SW case cHAL was found to enhance CWPAH by a factor of 2-4 relative to SDS with one soil, whereas with the other soil the two surfactants behaved similarly. The Cre data, however, showed that both soils absorbed by far more SDS (68-95%) than cHAL (12-54%). The results point out intriguing technological and environmental perspectives deriving from the use of compost isolated biosurfactants in the place of synthetic surfactants.     

混合表面活性剂-浊点萃取法测定沉积物中多环芳烃的含量

以混合型表面活性剂（十二烷基硫酸钠（SDS）和对叔辛基苯基聚己二醇醚（Triton X-114））为萃取剂，采用浊点萃取法萃取沉积物中的15种多环芳烃（PAHs），并利用HPLC技术测定15种PAHs的含量。实验结果表明，当混合型表面活性剂的加入量 3％（w）、混合型表面活性剂中SDS含量 50%（φ）、Na2SO4含量 8％（w）、萃取温度 60 ℃、超声萃取时间 10 min 时，15种PAHs的线性关系良好，r=0.998 9~0.999 7，检出限0.4~8.2 μg/L，加标回收率71.22%~97.36%，相对标准偏差0.92%~4.36%（n=6）。     

Mercury removal from aqueous solutions by zinc cementation

The main purpose of this research is to study the addition effect of the surfactant and other operating factors on the treatment of wastewater containing mercury ions in aqueous solution by cementation with sacrificing metal, zinc. The removal of mercury ions from aqueous solutions by cementation of zinc powder was found to be a function of solution pH and temperature, amount of zinc, concentration of mercury ion, contact time and the addition of several organic surfactants. Cementation of mercury was shown to be a feasible process to achieve a very high degree of mercury removal over a broad operational range within a fairly reasonable contact time. The reaction rate is approximately first order with respect to the concentration of mercury ion in aqueous solution. Among the surfactants used in this study, only the presence of SDS, an anionic surfactant, slightly enhanced the cementation rate of mercury. The presence of CTAB and Triton-X100 retarded the cementation of mercury by zinc.     

n-Hexane Biodegradation in Trickle Bed Air Biofilters

While hydrophilic compounds are degraded easily in Trickling bed air biofilters (TBABs), hydrophobic compounds are retarded until biological cultures produce a sufficient RNA or enzyme/protein to utilize this compound. Hydrophobic compounds are not readily bio-available which makes them reluctant to biodegradation as mass transfer between the gas and liquid phases is a rate limiting step. To enhance the destruction of hydrophobic compounds in TBABs, the utilization of surfactant was introduced to increase the solubility which helps overcoming the rate limiting step. The surfactant was used as well to limit the growth of excess biomass ensuring smooth flow through the biofilter bed and preventing short circuits. Two different non-ionic non-toxic surfactants were used in this study: Triton X-100 and Tomadol® 25-7. Two lab-scale controlled TBABs were operated for investigating the performance difference for n-Hexane as an example of hydrophobic volatile organic compound (VOC) with and without the addition of surfactant. Operating conditions in both TBABs were as follows: nutrient feed rate (2L/day), air flowrate (1.4L/min), bed depth (60cm), empty bed retention time (120s), bed material (diatomaceous earth pellets) and room-temperature. The inlet concentration was changed from 50 to 100ppmv. Acclimation period, removal profile along biofilter depth, nitrogen consumption, and CO₂ production were compared under continuous loading operation condition. The optimum concentration of surfactant in the nutrient feed was determined by a batch experiment. The effect of different surfactant concentrations on VOC water solubility with time was studied by considering different VOC concentration sets within the TBAB loading rate range.     

表面活性剂与柠檬酸联合洗涤高黏性土壤中的重金属

以一水合柠檬酸（CA）为洗涤剂,分别采用吐温80（TW80）、十二烷基磺酸钠（SDS）、β-环糊精（BCD）和腐植酸（HA）4种表面活性剂与CA联合洗涤高黏性土壤中的重金属,考察表面活性剂与CA的联合洗脱效果。实验结果表明：添加4种表面活性剂均可提高CA对Cu、Zn和Pb的去除率;处理时无需调节体系pH;在表面活性剂与CA的混合液与土壤的液固比为10:1（mL/g）的条件下,采用一次洗涤即可。经4种表面活性剂与CA联合洗涤后,土壤中Cu、Zn和Pb的离子交换态、碳酸盐结合态和铁锰氧化结合态的占比均下降,而硫化物及有机结合态和残渣态的占比有所提升。     

Factors affecting degradation of polyethylene terephthalate (PET) during pre-flotation conditioning

In general, plastics are exposed to different degrading agents in every procedure involved in their recovery from waste mixture and from subsequent recycling. In this study, two methods of pre-flotation conditioning were used to determine how these methods affect the general properties of the pre-conditioned PET particles to be recovered from the PET-PVC mixture. The first method comprised the conditioning of PET samples using an alkaline solution of nonionic surfactant (Triton X-100) based on the patent by the Goodyear Tire and Rubber Company. The second method, developed in this study, was a conditioning process which used an alkali-less solution of the same nonionic surfactant (Triton X-100) used in the first method. The following analytical methods were used to characterize properties of the pre-conditioned PET samples that were correlated to relative degradation of the samples: differential scanning calorimetry (DSC), for thermal behavior of the samples; FT-IR spectroscopy, for functional groups present in the samples; and, Pohl’s method, for carboxyl end-group concentration count. Results show that in addition to water the presence of NaOH in the conditioning solution contributes to the further degradation of the polymer.     

CuMn/ZrAlTi-堇青石蜂窝陶瓷催化氧化法处理含酚废水

选取球状堇青石蜂窝陶瓷作为催化剂基体,制备了CuMn/ZrAlTi-堇青石蜂窝陶瓷催化剂,采用XRD、X射线光电子能谱(XPS)、比表面积测定(BET)等分析方法对其进行了表征,测定了其催化湿式氧化含酚废水的活性及催化剂抗压强度、脱落率、Cu2+溶出浓度等性能指标.实验结果表明:CuMn/ZrAlTi-堇青石蜂窝陶瓷催化剂在反应温度220℃、压力5 MPa、搅拌速率为600 r/min时,催化湿式氧化反应300 min,COD去除率可达94.6％;球状CuMn/ZrAlTi-堇青石蜂窝陶瓷催化剂具有强度高、易装填、易更换、脱落率低等特点,Cu2+溶出浓度低于国家排放标准,适合工业化处理含酚废水.     

Accumulation of Heavy Metals by in vitro cultures of plants

The aim of the project is to study heavy metals accumulation by the selected plants in both laboratory and field conditions. Within the experiments the aspen (Populus tremula × tremuloides), sunflower (Helianthus annuus) and corn (Zea mays) plants were studied. The reasons for this selection were: a fast growth of these plants, an accumulation capacity and an ability to survive in different types of soils. The study was carried out on the aspen plantlets grown in vitro. The plants were exposed to the aqueous solutions having concentrations 0.1 mM, 0.5 mM of Pb²⁺ or Ni²⁺, respectively. The accumulation capacityfor aspen, was about 70% of Pb²⁺ originally present in the solution. The starting concentration of Pb²⁺ (0.5 mM) exhibited no negative impact on the growth. Besides in vitro expositions, a pilot-scale phytoremediation experiment was carried out at the polluted industrial area (Zn – 75000 mg/kg), (Pb – 16000 mg/kg), (Cr – 590 mg/kg), (Cd – 90 mg/kg) and (Cu – 1700 mg/kg).     

Enhanced biodegradation of creosote-contaminated soil

Bioremediation, a viable option for treatment of cresote-contaminated soil, can be enhanced by the use of surfactant. A study was conducted to investigate the effect of a non-ionic surfactant, Triton X-100, on biodegradation of creosote-contaminated soil. Abiotic soil desorption experiments were performed to determine the kinetics of release of selected polynuclear aromatic hydrocarbon (PAH) compounds. Respirometric experiments were also conducted to evaluate the effect of nonionic surfactant on biodegradation. The N-Con system respirometer was used to monitor the oxygen uptake by the microorganisms. The abiotic experiments results indicated that the addition of surfactant to soil/water systems increased the desorption of PAH compounds. It was also observed that the desorption rate of PAH compounds depended on their molecular weight. The 3- and 4-ring PAH compounds showed higher and faster desorption rates than the 5- and 6-ring PAHs. The respirometric experiments indicated that an increase in soil contamination level from 112.5 to 771.8 mg/kg showed an increase in oxygen uptake. But for a soil contamination level of 1102.5 mg/kg, the oxygen uptake was similar to the contamination level of 771.8 mg/kg. This might be due to toxicity by the surfactant or the solubilized PAHs at high concentration or interference with contaminant transport into the cell or to reversible physical-chemical interferences with the activity of enzymes involved in the PAH degradation. The increase in PAH availability to the microorganisms in the aqueous phase produced an increase in oxygen consumption that is proportional to the biodegradation of organic compounds.     

O_3-Ca(OH)_2体系处理苯酚废水

研究了苯酚在新型臭氧氧化体系O_3-Ca(OH)_2体系中的降解与矿化效果。实验结果表明:苯酚及TOC的去除率都随着Ca(OH)_2用量(小于2 g/L)、进气臭氧质量浓度(小于75 mg/L)、进气流量(小于3.0 L/min)的增大以及初始苯酚质量浓度的减小而增加,但受反应压力和液相温度的影响较小;当Ca(OH)_2用量大于3 g/L时,苯酚和TOC的去除率在30 min和55 min时分别达到了100%左右;Ca~(2+)的存在实现了羟基自由基清除剂CO_3~(2-)的实时分离去除,从而强化了臭氧氧化过程中苯酚的降解与矿化。这表明,O_3-Ca(OH)_2体系是一种处理难降解有机废水的高效臭氧氧化新体系。     

Kinetics and thermodynamics of copper ions removal from wastewater by use of zeolite.

Natural Bulgarian zeolite was tested for its ability to remove Cu2+ from model wastewater. Influence of process variables was investigated. It was found that the optimum wastewater to zeolite ratio is 100:1 and the optimum pH value of water to be treated is 5.5 to 7.5. Zeolite with finer particles shows a higher uptake capacity. The simultaneous presence of Ca2+ and Mg2+ in concentrations similar to their concentrations in Bulgarian natural water does not significantly influence the uptake of Cu2+. Zeolite modification by treating it with NaCl, CH3COONa and NaOH increases its uptake ability. Copper ions are strongly immobilized by modified zeolite and secondary pollution of water caused by its contact with preloaded zeolite is very low (1.5-2.5% of Cu2+ preliminary immobilized have been released back into acidified water). Contacting with 2 mol dm(-3) NaCl can easily regenerate loaded zeolite; best results were obtained for zeolite modified with NaCl. Requirements of Bulgarian standards for industrial wastewater can be met by a one-stage process for an initial Cu2+ concentration of 10 mg dm(-3), and by a two stage process for an initial Cu2+ concentration of 50 mg dm(-3). Uptake of Cu2+ by zeolite from neutral wastewater has proved to be as effective as Cu2+ removal by precipitation of copper hydroxide. The process of Cu2+ uptake by natural zeolite is best described by the kinetic equation for adsorption. This fact, together with the correlation found between the Cu2+ uptake and the amount of Na+, Ca2+ and K+ released into solution by zeolite shows that the ion exchange sorption plays the basic role in Cu2+ uptake by natural zeolite. The value obtained for the apparent activation energy (26.112 kJ mol(-1) implies that the process can be easily carried out with a satisfactory rate. The uptake equilibrium is best described by the Langmuir adsorption isotherm, with Langmuir constants KL= 6.4 x 10(-2) dm3 mg(-1) and M = 6.74 mg g(-1). The apparent equilibrium constant found shows moderate affinity of zeolite for Cu2+. Values of deltaG degrees and deltaH degrees found show the spontaneous and endothermic nature of the process of Cu2+ uptake by natural zeolite.     

乳状液膜法处理煤制兰炭废水

以磷酸三丁酯(TBP)为载体、煤油为膜溶剂、NaOH水溶液为内水相，采用乳状液膜法处理兰炭废水。实验结果表明:当TBP体积分数为4%、表面活性剂质量分数为4%、内水相NaOH质量分数为12%、油内比(乳状液的油相与内水相的体积比)为3∶2、乳水比为1∶5、萃取时间为15min时，废水中的酚类(以苯酚计)去除率达到85%以上，COD去除率达83%以上。     

Method to recover and reuse chromated copper arsenate wood preservative from spent treated wood

The volume of chromated copper arsenate (CCA) treated wood products coming out of service is expected to increase dramatically during the next decade. There is a need for an alternative waste management approach to landfilling. This paper investigates the variables affecting extraction of CCA components from wood particles and the potential to oxidize and reuse the recovered chemicals. Most of the CCA components could be extracted by 10% H2O2 at 50 degrees C in 6 h with an average extraction efficiency of 95% for Cr, 94% for Cu and 98% for As. The extract containing Cr(III), Cu(II) and As(V) could be oxidized in several stages by aqueous 2.5% w/w H2O2 in less than 2 h to a condition where it was compatible with CCA treating solutions and could be reused for treating new wood. When the recovered extract was mixed with fresh CCA solution in different ratios, the mixed CCA-C solutions had similar solution stability as freshly prepared CCA-C solution and treated wood had similar leaching properties as wood treated with fresh solution.     

Olive mill solid residues as heavy metal sorbent material: a preliminary study

Biosorption of heavy metals is an innovative and alternative technology to remove these pollutants from aqueous solutions using inactive and dead biomasses such as agricultural and industrial wastes, algae and bacteria. In this study olive mill solid residue was used as heavy metal adsorbent material for its wide availability as agricultural waste and also for its cellulosic matrix, rich of potential metal binding active sites. Preliminary studies concerned with the removal of different heavy metals (Hg, Pb, Cu, Zn and Cd), the effect of pre-treatments by water and n-hexane and the regeneration possibility. Olive mill solid residue resulted able to remove heavy metals from aqueous solutions with an affinity series reflecting the hydrolytic properties of the metallic ions, but also a particular affinity for copper. It can be supposed that biosorption phenomenon occur by a general ion exchange mechanism combined with a specific complexation reaction for copper ions. Water pre-treatment is sufficient to reduce COD release in the effluent according to the law limit, while n-hexane pre-treatment strongly reduces also the adsorption properties of this material. Experimental isotherms obtained under different operating conditions were fitted using a non linear regression method for the estimation of the Langmuir parameters. Moreover a simple Scatchard plot analysis was performed for a preliminary investigation of the active sites, showing the presence of two different site affinities depending on the metal concentration, according to the previous hypothesis of two kinds of uptake mechanisms for copper biosorption. Regeneration tests gave good results in terms of yield of regeneration and also concentration ratios.     

表面活性剂强化超滤法处理亚甲基蓝废水

采用无机陶瓷超滤膜和低浓度阴离子表面活性剂十二烷基苯磺酸钠(SDBS)处理亚甲基蓝(MB)模拟废水,考察了废水中SDBS、MB浓度及废水pH对超滤过程的影响.实验结果表明:SDBS浓度影响MB在最大吸收波长处的吸光度值;当废水中SDBS浓度为1.20 mmol/L(即25℃时的临界胶束浓度)、废水中MB浓度为1.00 mmol/L、废水pH为9.0时,超滤效果最好;在此条件下,透过液中SDBS浓度和MB浓度分别为0.06 mmoL/L和0.01 mmol/L,MB的截留率为99.2%,膜通量为309.6 L/(m~2·h).SDBS对MB超滤过程的强化机理主要为MB与SDBS形成结合体析出及SDBS胶束的增溶作用.     

Surfactant‐Oxidant Co‐Application for Soil and Groundwater Remediation

In situ chemical oxidation (ISCO) typically delivers oxidant solutions into the subsurface for contaminant destruction. Contaminants available to the oxidants, however, are limited by the mass transfer of hydrophobic contaminants into the aqueous phase. ISCO treatments therefore often leave sites with temporarily clean groundwater which is subject to contaminant rebound when sorbed and free phase contaminants leach back into the aqueous phase. Surfactant Enhanced In situ Chemical Oxidation (S‐ISCO^®) uses a combined oxidant‐surfactant solution to provide optimized contaminant delivery to the oxidants for destruction via desorption and emulsification of the contaminants by the surfactants. This article provides an overview of S‐ISCO technology, followed by an implementation case study at a coal tar contaminated site in Queens, New York. Included are data points from the site which demonstrate how S‐ISCO delivers desorbed contaminants without uncontrolled contaminant mobilization, as desorbed and emulsified contaminants are immediately available to the simultaneously injected oxidant for reaction. ©2016 Wiley Periodicals, Inc.     

Biodegradation of Polycyclic Aromatic Hydrocarbons by Exopolymers Synthesized by Moderately Halophilic Bacteria: Chemical Composition and Functional Properties

Three strains of halophilic bioemulsifier-producing bacteria; Bacillus sp. 2BSG-PDA-16, Bacillus sp. DV2-37 and Bacillus licheniformis ABRII6 were isolated from crude oil polluted water samples. Characteristics of exopolymers produced by these strains in media supplemented with various hydrocarbons instead of glucose were studied. Yield production, chemical composition, emulsifying, rheological and flocculating properties of exopolymers varied according to the strain and the carbon source. The highest amount of exopolymers synthesized by Bacillus sp. 2BSG-PDA-16, Bacillus sp. DV2-37 and B. licheniformis ABRII6 was 11, 18.5 and 12.4 g/l, respectively from media amended with glucose, while the most active emulsifiers were those obtained from media added with crude oil. Furthermore, all exopolymers produced were capable of emulsifying crude oil more efficiently than the three chemical surfactants tested as control (Tween 20, Tween 80 and Triton X-100). Respect to chemical composition, exopolymers produced on hydrocarbons always have lower content of carbohydrates and proteins than exopolymers produced in medium amended with glucose, however they showed higher amounts of uronic acids, sulfates and acetyl residues. The rheological study suggested that the exopolymers have characteristics of the pseudoplastic fluids. Efficiency of bacterial strains to remove PAH seems to agree with their potential applicability in oil bioremediation technology.     

Remediation of DDT‐contaminated soil using optimized mixtures of surfactants and a mixing system

Soil contaminated with persistent pesticides, such as DDT, poses a serious risk to humans and to wildlife. A surfactant‐aided soil‐washing technique was studied as an alternative method for remediation of DDT‐contaminated soil. An ex situ soil washing method was investigated using nonionic and anionic surfactants due to the clayey structure of the contaminated soil. A mixture of 1 percent nonionic surfactant (Brij 35) and 1 percent anionic surfactant (SDBS) removed more than 50 percent of DDT from soil in a flow‐through system, whereas individual surfactants or other combinations of the surfactants had a lower removal efficiency. The soil‐washing technique was improved using a mixing system. The mixture of surfactants was optimized in the mixing system, and the combination of 2 percent Brij 35 and 0.1 percent SDBS was found to be optimum, removing 70 to 80 percent of DDT. Prewashing of the soil with tap water decreased the adsorption of surfactants to soil particles by 30 to 40 percent, and postwashing recovered 90 percent of the surfactants. © 2010 Wiley Periodicals, Inc.     

Mobility control: How injected surfactants and biostimulants may be forced into low‐permeability units

Recovering dense nonaqueous‐phase liquid (DNAPL) remains one of the most difficult problems facing the remediation industry. Still, the most common method of recovering DNAPL is to physically remove the contaminants using common technologies such as total fluids recovery pumps, vacuum systems, and “pump‐and‐treat.” Increased DNAPL removal can be attained using surfactants to mobilize and/or solubilize the pollutants. However, very little is understood of the methods developed by petroleum engineers beginning in the 1960s to overcome by‐passed, low‐permeability zones in heterogeneous oil reservoirs. By injecting or causing the formation of viscous fluids in the subsurface, petroleum engineers caused increased in‐situ pressures that forced fluid flow into low permeability units as well as the higher permeability thief zones. Polymer flooding involves injecting a viscous aqueous polymer solution into the contaminated aquifer. Foam flooding involves injecting surfactant to decontaminate the high‐permeability zones and then periodic pulses of air to cause a temporary viscous foam to form in the high‐permeable zones after all DNAPL is removed. Later surfactant pulses are directed by the foam into unswept low‐permeable units. These methods have been applied to DNAPL removal using surfactants but they can also be applied to the injection of bio‐amendments into low‐permeability zones still requiring continued remediation. Here we discuss the principles of mobility control as practiced in an alluvial aquifer contaminated with chlorinated solvent and coal tar DNAPLs as well as some field results. © 2003 Wiley Periodicals, Inc.