比较两种表面活性剂淋洗去除土壤中的重金属

以停车场和湿地2种土壤为研究对象,分别使用表面活性剂鼠李糖脂和月桂基醚硫酸钠对土壤样品进行淋洗,考察2种表面活性剂对这2种土壤中重金属的去除能力差异及形态分布的影响,并分析淋洗后残留在土壤中表面活性剂的生物毒性。结果表明,2种表面活性剂均可在一定程度上去除2种土壤中的Cu、Cd、Pb和Zn。与湿地土壤相比,2种表面活性剂对停车场土壤中重金属的去除率均较高,且月桂基醚硫酸钠的去除能力优于鼠李糖脂。2种表面活性剂对可交换态重金属的去除效果最好,对残渣态重金属去除率较低。淋洗后2种土样中残留的鼠李糖脂及停车场土样中残留的月桂基醚硫酸钠的生物毒性低,湿地土壤中残留的月桂基醚硫酸钠具有一定生物毒性。     

有机酸土柱淋洗法修复重金属污染土壤

通过室内模拟实验,采用土柱淋洗方法,研究草酸、柠檬酸、乙酸和酒石酸溶液对某电镀厂附近土壤中重金属的去除效果。探讨了淋洗剂浓度、淋洗次数和淋洗时间等对淋洗效果的影响,研究草酸淋洗前后土壤中重金属形态的变化。结果表明,淋洗过程中铬的去除效果明显滞后于铜、锌和镍3种重金属离子。1 mol/L的草酸在土水比为1∶1,淋洗5h,淋洗4次的条件下可以达到最佳淋洗效果,Cu、Zn、Ni和Cr的去除率分别是99.6%、66.98%、88.7%和18.23%。     

3种植物水浸提液对工业园区污水处理厂污泥中重金属的淋洗效果

为探讨植物材料淋洗去除工业园区污水污泥中重金属的可行性,选用马桑(Coriaria nepalensis)、枳椇子(Hovenia acerba)和乌药(Lindera aggregata)的水浸提液作为淋洗剂,采用振荡淋洗实验研究了不同淋洗剂浓度和pH、淋洗时间和温度对其去除供试污泥中重金属的影响,并确定淋洗的最佳参数。结果表明,当3种淋洗剂浓度从20 g·L~(-1)上升到80 g·L~(-1)或淋洗温度从15℃增至55℃时,重金属去除率均呈先升高后稳定的趋势。同时,淋洗效果还受淋洗剂pH和淋洗时间的影响。基于淋洗效果、技术应用和经济成本,枳椇子、乌药和马桑水浸提液淋洗的最佳参数分别为pH 7、80 g·L~(-1)、25℃、180 min,pH 4、100 g·L~(-1)、25℃、180 min和pH 4、80 g·L~(-1)、25℃、180min,此时各淋洗剂重金属去除率总体表现为CdCuPbNi。其中枳椇子和乌药对Cd去除率较高,分别为73.12%和82.60%,但Ni去除率仅为23.34%和19.42%;与前2种植物材料相比,马桑对Pb(36.40%)和Ni(27.88%)的去除率高,但对Cd(30.11%)和Cu(30.38%)的去除率相对较低。淋洗后污泥中Cu和Pb含量均可达农用污泥A级标准(CJ/T 309-2009),乌药淋洗后Cd及马桑淋洗后Ni含量可达到A级标准,其他淋洗剂情况下Cd和Ni含量可达到B级标准。此外,植物水浸提液淋洗污泥还能有效保留甚至增加其养分,降低可交换态、碳酸盐结合态和铁锰结合态重金属含量。研究表明,马桑、枳椇子和乌药在淋洗去除污泥中重金属和实现污泥土地应用上有一定潜力。     

重金属污染土壤的草酸和EDTA混合淋洗研究

采用不同浓度的草酸(oxalic acid,OX)和乙二胺四乙酸(EDTA)混合的淋洗方法研究重金属污染土壤的最佳混合淋洗方式,探讨了液固比、淋洗时间及pH对淋洗效果的影响,并分析了0.2 mol/L OX+0.2 mol/L EDTA处理前后土壤中重金属形态的变化。结果表明,采用0.2 mol/L OX+0.2 mol/L EDTA混合的淋洗法可同时去除多种重金属,且对Cu、Zn、Ni和Cr的去除率明显高于单用OX和EDTA,去除率分别为Cu 41.29%、Zn 84.73%、Ni 54.2%和Cr 66.01%。0.2mol/L OX+0.2 mol/L EDTA在液固比为5∶1、淋洗时间为4 h、pH为6时可分别达到最佳淋洗效果,且分别为Cu 62.59%、Zn 93.48%、Ni 55.95%和Cr 71.57%;Cu 50.47%、Zn 86.67%、Ni 61.53%和Cr 72.68%;Cu 44.40%、Zn 81.82%、Ni68.76%和Cr 74.93%。形态分析结果表明,0.2 mol/L OX+0.2 mol/L EDTA能较好地改变土壤中重金属形态的分布。     

环境友好型淋洗剂对重金属污染土壤的修复效果

以广西某废弃铅锌冶炼企业重金属复合污染土壤为对象,采用土柱淋洗的方法,分别将自制的茶皂素、柠檬酸和EDTA 3种淋洗剂进行复合淋洗,并对复合淋洗的最佳配比、淋洗剂添加方式和淋洗时间进行研究,得到对环境友好且淋洗效果好的复合淋洗剂。最后,对淋洗前后土壤中Cu、Pb和Zn的赋存形态进行研究,探讨淋洗机理。研究结果表明,茶皂素和柠檬酸复合时对重金属Cu、Pb、Zn的去除率分别达到了77.00%、52.09%和58.66%,综合考虑淋洗效率以及经济环保等因素,选择将茶皂素和柠檬酸复合进行淋洗。复合淋洗实验结果表明,柠檬酸和茶皂素体积比为3∶1复合方式淋洗30 h,淋洗效果最佳,对重金属Cu、Pb和Zn的去除率分别达到82.77%、65.49%和78.12%。茶皂素和柠檬酸复合淋洗能有效的去除土壤中酸可提取态和有机结合态的重金属,氧化物结合态的Pb和Zn也有较大程度的降低,同时还发现,茶皂素和柠檬酸共同作用对残余态的Pb去除效果也较好,可达到50%以上。从茶籽饼中提取茶皂素与天然有机酸柠檬酸复合淋洗,用于修复污染面积小、污染浓度高且污染比较集中的重金属污染土壤,效果好且对环境友好。     

生物淋滤对城市污泥重金属去除及形态变化的影响研究

以氧化亚铁硫杆菌(Acidithiobacillus ferrooxidans)为淋滤菌,对城市污泥进行生物淋滤,考察淋滤过程中污泥重金属(Cu、Zn、Ni、Cr)的去除及其形态变化规律,并根据淋滤前后重金属形态分布探讨重金属的淋滤去除机制。结果表明,生物淋滤可有效去除城市污泥中的Cu、Zn和Ni,对Cr几乎没有去除。生物淋滤后,Cu、Zn、Ni、Cr 4种重金属的去除率分别为55.97%、47.66%、26.10%、2.10%。pH是影响Zn和Ni去除的主要因素,而Cu在低pH和高氧化还原电位(ORP)条件下更易去除。BCR形态分析表明,生物淋滤之后污泥中Cu、Zn和Ni的4种形态含量均发生了不同程度的改变,其生物有效性和迁移性得到有效控制。通过重金属形态变化规律间接得出,Cu的生物淋滤过程以直接机制为主,Zn和Ni的生物淋滤过程是直接机制和间接机制共同作用的结果。     

表面活性剂增效电动技术修复多环芳烃污染土壤

研究了电动修复过程中修复时间和表面活性剂Triton X-100、鼠李糖脂对多环芳烃芘污染土壤的修复效果的影响。结果表明,在电动修复过程中,随着修复时间的增加,芘的去除率相应提高。通过向电解液中添加表面活性剂Triton X-100,芘的去除率从11.64%提高到了23.42%,当在电解液中添加浓度为40倍CMC的鼠李糖脂后去除率升高至36.29%,阳极附近土壤甚至达到了92.49%,这表明Triton X-100和鼠李糖脂均能促进土壤中芘的溶解和迁移,鼠李糖脂的促进作用高于Triton X-100。     

Pseudomonas sp. BS-1发酵产物对土壤中钍的淋洗作用

从焦化废水污泥中筛选出一株产生物表面活性剂的菌株,将其命名为BS-1,16SrDNA系统发育学分析确定其属于假单胞菌属(Pesudomonas sp.)。该菌株发酵产物初步鉴定为鼠李糖脂,在其临界胶束浓度为0.56g·L~(-1)时,可将水溶液的表面张力从76.8mN·m~(-1)降至38.5mN·m~(-1)。将菌株发酵产物溶液作为淋洗剂,采用浸提和土柱淋洗的方法研究了BS-1发酵产物对污染土壤中钍的去除效果,结果表明:当pH为10,浓度为3 g·L~(-1),振荡时间为72h时,钍的去除率可达70.14%;在柱状动态实验中,当淋洗量达到800mL时,发酵产物溶液对钍的累积去除量最大为65.03 mg·kg~(-1),发酵产物溶液对钍的累积去除量明显优于去离子水。对比淋洗后土壤中钍的形态占比可知,残渣态增加10.16%,氧化结合态减少了11.41%。对比淋洗前后土壤中钍的形态含量可知,酸可提取态、氧化结合态、有机结合态分别减少了83.25%、75.22%、60.70%。淋洗后钍的稳定性增强。     

超声强化淋洗修复Pb、Cd、Cu复合污染土壤

针对传统淋洗法修复土壤中重金属效率较低的问题,研究了超声强化淋洗技术以提高重金属去除率。以铅(Pb)、镉(Cd)、铜(Cu)为目标污染物,在0.05 mol·L~(-1)柠檬酸、0.05 mol·L~(-1)EDTA和0.05 mol·L~(-1)皂角苷作为淋洗剂条件下,使用传统振荡、超声强化以及超声波加振荡3种不同的作用方式,对Pb、Cd、Cu的去除率进行比较,并对3种不同淋洗方式后Pb、Cd、Cu的形态变化进行了探讨。结果表明,当使用柠檬酸和皂角苷作为淋洗剂进行振荡淋洗时,重金属洗脱效果不理想。超声对于强化柠檬酸洗脱效果并不明显,而对于强化皂角苷洗脱重金属效果明显,平均去除率提高了120.47%。当淋洗剂为EDTA时,土壤样品在传统振荡2 h作用下,对Pb、Cd、Cu的去除率依次为50.33%、76.65%和47.35%,而在超声波30 min条件下对Pb、Cd、Cu的去除率依次为82.19%、83.31%和53.89%,平均去除率高出28.60%,可显著提高重金属去除率,缩短淋洗时间。但超声波30 min加传统振荡2 h相较于单纯超声强化效果提升不明显。通过对比3种淋洗方式后土壤中的Pb、Cd、Cu形态发现,酸可提取态的重金属在超声强化作用后有明显降低,同时超声强化对于铁锰氧化物结合态、有机物结合态和残渣态也具有较好的去除能力。因此,超声强化在化学淋洗中的应用具有一定的可行性,是一种简单、极快速去除污染场地中重金属Pb、Cd、Cu的增效手段。     

有机酸对成都平原镉污染土壤的淋洗效果

以成都平原某化工厂附近受Cd污染的2种土壤为对象,采用振荡淋洗技术,研究了有机酸在不同浓度、固液比、振荡时间和复合淋洗条件下对重金属Cd的去除效果。实验结果表明:柠檬酸和酒石酸对Cd含量为22.78 mg·kg~(-1)的SLT-01土壤具有更好的去除效果,分别达到73%和62%,而乙酸和草酸的去除能力较低;随着固液比的降低,有机酸对Cd的去除率逐步提高;随着时间的增加,Cd的去除率波动增加;柠檬酸和酒石酸复合淋洗并没有提高Cd的去除率;振荡淋洗前后土壤结构未发生明显变化。综合考虑土壤中Cd的去除效果和成本,选择柠檬酸作为最佳淋洗剂;最佳实验条件:溶液浓度为0.10 mol·L~(-1),固液比为1∶20,淋洗时间为8 h。     

Investigation of the removal of heavy metals from sediments using rhamnolipid in a continuous flow configuration

Heavy metal contamination of sediments is hazardous to benthic organisms and needs more attention in order to prevent entry of these heavy metals into the food chain. Biosurfactants have shown the capability to remove heavy metals from soils and sediments. The objective of this research was to evaluate the performance of rhamnolipid, a glycolipid biosurfactant, in a continuous flow configuration (CFC) for removal of heavy metals (copper, zinc, and nickel) from the sediments taken from Lachine Canal, Canada, to simulate a flow through remediation technique. In this configuration, rhamnolipid solution with a constant rate was passed through the sediment sample within a column. Important parameters such as the concentration of rhamnolipid and the additives, time and the flow rate were investigated. The removal of heavy metals from sediments was up to 37% of Cu, 13% of Zn, and 27% of Ni when rhamnolipid without additives was applied. Adding 1% NaOH to 0.5% rhamnolipid improved the removal of copper by up to 4 times compared with 0.5% rhamnolipid alone. This information is valuable for designing a remediation protocol for sediment washing.     

Heavy metal (Cu,Cd, Pb,Cr) washing from river sediment using biosurfactant rhamnolipid

Heavy metal-contaminated sediments posed a serious threat to both human beings and environment. A biosurfactant, rhamnolipid, was employed as the washing agent to remove heavy metals in river sediment. Batch experiments were conducted to test the removal capability. The effects of rhamnolipid concentration, washing time, solution pH, and liquid/solid ratio were investigated. The speciation of heavy metals before and after washing in sediment was also analyzed. Heavy metal washing was favored at high concentration, long washing time, and high pH. In addition, the efficiency of washing was closely related to the original speciation of heavy metals in sediment. Rhamnolipid mainly targeted metals in exchangeable, carbonate-bound or Fe-Mn oxide-bound fractions. Overall, rhamnolipid biosurfactant as a washing agent could effectively remove heavy metals from sediment.

     

Removal of heavy metals from anaerobically digested sewage sludge by isolated indigenous iron-oxidizing bacteria

The removal of heavy metals (Cr, Cu, Zn, Ni and Pb) from anaerobically digested sludge from the Yuen Long wastewater treatment plant, Hong Kong, has been studied in a batch system using isolated indigenous iron-oxidizing bacteria. The inoculation of indigenous iron-oxidizing bacteria and the addition of FeSO4 accelerated the solubilization of Cr, Cu, Zn, Ni and Pb from the sludge. pH of the sludge decreased with an increase in Fe2+ concentrations and reached a low pH of 2-2.5 for treatments receiving both bacterial inoculation and FeSO4. After 16 days of bioleaching, the following heavy metal removal efficiencies were obtained: Cr 55.3%, Cu 91.5%, Zn 83.3%, Ni 54.4%, and Pb 16.2%. In contrast, only 2.6% of Cr, 42.9% of Cu, 72.1% of Zn, 22.8% of Ni and 0.56% of Pb were extracted from the control without the bacterial inoculation and addition of FeSO4. The residual heavy metal content in the leached sludge was acceptable for unrestricted use for agriculture. The experimental results confirmed the effectiveness of using the isolated iron-oxidizing bacteria for the removal of heavy metals from sewage sludge.     

复合酸化剂对电镀污泥中铬、铜的去除效果

以电镀加工厂产生的污水污泥作为主要研究对象,研究了柠檬酸、硝酸、过氧化氢为复合酸化剂,Fe3+为增效剂对电镀污泥中铬和铜的去除效果,考察了酸化剂的浓度、反应时间、摇床转速、污泥pH、Fe3+浓度等因素对污泥中重金属去除效率的影响。结果表明:在室温下,含0.15 mol/L柠檬酸、1.5%过氧化氢、0.25 mol/L硝酸的复合酸化剂与增效剂2.0g/L Fe3+溶液共同处理污泥,固液比为1∶10,以150 r/min的转速振荡4 h,对污泥中Cr的去除效率达到80.02%,Cu的去除效率可达到92.89%,使污泥中残留Cr、Cu含量均符合国家污泥农用标准。     

Electrokinetic enhancement removal of heavy metals from industrial wastewater sludge

An enhanced electrokinetic process for removal of metals (Cr, Cu, Fe, Ni, Pb, Zn) from an industrial wastewater sludge was performed. The electrokinetic experiments were conducted under a constant potential gradient (1.25 V cm(-1)) with processing fluids of tap water (TW), sodium dodecylsulfate (SDS) and citric acid (CA) for 5 days. Results showed that metal removal efficiency of heavy metals for EK-TW, EK-SDS and EK-CA systems are 11.2-60.0%, 37.2-76.5%, and 43.4-78.0%, respectively. A highest metal removal performance was found in EK-CA system. The removal priority of investigated metals from sludge by EK process was found as: Cu > Pb > Ni > Fe > Zn > Cr. The results of sequential extraction analysis revealed that the binding forms of heavy metals with sludge after electrokinetic process were highly depend upon the processing fluid operated. It was found that the binding forms of metals with sludge were changed from the more difficult extraction type (residual and sulfate fractions) to easier extraction types (exchangeable, sorbed, and organic fraction) after treatment by electrokinetic process. Results imply that if a proper treatment technology is followed by this EK process to remove metals more effectively, this treated sludge will be more beneficial for sludge utilization afterwards. Before it was reused, the risk associated with metals of more mobile forms to the environment need to be further investigated. The cost analysis was also evaluated for the investigated electrokinetic systems.     

Hybrid process for heavy metal removal from wastewater sludge.

Bioleaching processes have been demonstrated to be effective technologies in removing heavy metals from wastewater sludge, but long hydraulic retention times are typically required to operate these bioprocesses. A hybrid process (coupling biological and chemical processes) has been explored in laboratory pilot-scale experiments for heavy metals (cadmium [Cd], copper [Cu], chromium [Cr], and zinc [Zn]) removal from three types of sludge (primary sludge, secondary activated sludge, and a mixture of primary and secondary sludge). The hybrid process consisted of producing a concentrate ferric ion solution followed by chemical treatment of sludges. Ferric iron solution was produced biologically via oxidation of ferrous iron by A. ferrooxidans in a continuous-flow stirred tank (5.2 L) reactor (CSTR). Wastewater sludge filtrate (WSF) containing nutrients (phosphorus and nitrogen) has been used as culture media to support the growth and activity of indigenous iron-oxidizing bacteria. Results showed that total organic carbon (TOC) concentrations of the culture media in excess of 235 mg/L were found to be inhibitory to bacterial growth. The oxidation rate increased as ferrous iron concentrations ranged from 10 to 40 g Fe2+/L. The percentage of ferrous iron (Fe2+) oxidized to ferric iron (Fe3+) increased as the hydraulic retention time (HRT) increased from 12 to 48 h. Successful and complete Fe2+ oxidation was recorded at a HRT of 48 h using 10 g Fe2+/L. Subsequently, ferric ion solution produced by A. ferrooxidans in sludge filtrate was used to solubilize heavy metals contained in wastewater sludge. The best solubilization was obtained with a mixture of primary and secondary sludge, demonstrating a removal efficiency of 63, 71, 49, and 80% for Cd, Cu, Cr, and Zn, respectively.     

Multi-component adsorption of copper,nickel and zinc from aqueous solutions onto activated carbon prepared from date stones

The removal of Cu²⁺, Ni²⁺, and Zn²⁺ ions from their multi-component aqueous mixture by sorption on activated carbon prepared from date stones was investigated. In the batch tests, experimental parameters were studied, including solution pH, contact time, initial metal ions concentration, and temperature. Adsorption efficiency of the heavy metals was pH-dependent and the maximum adsorption was found to occur at around 5.5 for Cu, Zn, and Ni. The maximum sorption capacities calculated by applying the Langmuir isotherm were 18.68 mg/g for Cu, 16.12 mg/g for Ni, and 12.19 mg/g for Zn. The competitive adsorption studies showed that the adsorption affinity order of the three heavy metals was Cu²⁺?>?Ni²⁺?>?Zn²⁺. The test results using real wastewater indicated that the prepared activated carbon could be used as a cheap adsorbent for the removal of heavy metals in aqueous solutions.     

鼠李糖脂洗脱氯丹和灭蚁灵污染场地土壤的工艺参数

优化了鼠李糖脂洗脱氯丹、灭蚁灵污染土壤的工艺条件,为开展有机氯农药污染场地土壤洗脱修复工程实践提供科学依据和技术参数。实验结果表明,随着洗脱剂———鼠李糖脂浓度的增加,氯丹和灭蚁灵的洗脱量呈现先增加后降低的趋势;洗脱时间和液固比对洗脱效果的影响趋势与浓度相同;在0~120 r/min范围内,氯丹和灭蚁灵洗脱量随着搅拌速度的增加而增大,80、120和200 r/min的洗脱量间差异不显著;单次洗脱量随洗脱次数的增加而降低,累计洗脱量则逐渐增大。综上所述,氯丹、灭蚁灵污染场地土壤鼠李糖脂洗脱的适宜工艺参数为鼠李糖浓度10 mmol/L,搅拌速度80 r/min,固液比1∶10,洗脱时间20 min,洗脱3次。     

Change of PCBs and forms of heavy metals in sewage sludge during thermophilic anaerobic digestion

Determination of seven congeners of PCBs was carried out for sewage sludge before, during and after thermophilic digestion. The overall content of heavy metals (Zn, Cu, Ni, Cd, Pb, Cr) in sludge before and after digestion was determined. Moreover the concentration of heavy metals in particular chemical fractions of the sludge was analyzed. After the thermophilic digestion total concentration of seven PCBs was reduced by 47%, which suggests that thermophilic digestion affects PCB reduction positively. On the 10th d of the process, concentration of lower chlorinated PCBs increased, whereas those of higher chlorinated PCBs decreased. The thermophilic digestion process showed no accumulation of the studied heavy metals in the mobile fractions (exchangeable and carbonate) of the stabilized sewage sludge, except for nickel. The highest increase in zinc, copper, cadmium, and chromium concentration was observed in the organic-sulfide fraction, whereas the highest increase in lead was found in the residual fraction of the sludge. In case of nickel both fractions of organic-sulfide and exchangeable-carbonate fractions were enriched.