土壤类型及组分对热活化过硫酸盐氧化降解土壤中挥发性氯代烃的影响

为了探究高级氧化技术对土壤中有机氯代烃的氧化降解作用,为ISCO（in situ chemical oxidation）技术体系提供重要的理论依据和数据支撑,考察了热活化过硫酸盐（persulfate,PS）氧化降解不同类型土壤（砂类土壤、黏土类土壤）中挥发性氯代烃污染物（三氯乙烯（TCE）、三氯乙烷（TCA）、顺式-1,2-二氯乙烯（cis-1,2-DCE）、1,2-二氯乙烷（1,2-DCA））的效能;同时,通过硫酸盐与土壤相互作用过程研究,探究了不同土壤介质中有机质和无机组分在过硫酸盐消耗中所占比例。结果表明：在50℃时,热活化过硫酸盐可有效降解土壤中1,2-DCA、cis-1,2-DCE、TCA和TCE,砂类土壤介质中4种氯代烃降解效果依次为25%、89%、5%和61%,黏土类土壤介质中4种氯代烃降解效果依次为35%、86%、8%和63%;4种氯代烃的降解效果从高到低顺序依次为cis-1,2-DCE、TCE、1,2-DCA、TCA,砂类土壤中的氯代烃总体降解效果优于黏土类土壤中氯代烃的降解效果。另外,土壤中过硫酸盐氧化降解氯代烃反应研究发现,砂类和黏土类土壤介质组分中有机质消耗率分别为81.3%和72.6%,铁元素消耗率分别为80.5%和38.6%,表明土壤介质组分与过硫酸盐发生了氧化还原反应,从而导致过硫酸盐自身的大量消耗。由此可知,土壤介质中的有机质、铁元素等矿物质均参与过硫酸盐的消耗过程,且土壤有机质、铁元素与氯代烃之间在消耗过硫酸盐反应上存在竞争关系,土壤组分过多地消耗了过硫酸盐,导致了氯代烃的氧化降解效率较低。因此,针对实际有机氯代烃污染场地,采用过硫酸盐氧化技术进行修复时,过硫酸盐的实际投加量要远高于化学计量值,需充分考虑到土壤组分对过硫酸盐自身的消耗作用。     

二价铁活化过硫酸盐去除水中苯胺

零价铁和硝基苯反应后生成二价铁和苯胺,而苯胺也是地下水污染物。硫酸根自由基具有强氧化性,可以降解苯胺。而二价铁可以活化过硫酸盐产生硫酸根自由基,进而去除苯胺。本文研究了二价铁浓度、过硫酸盐浓度、苯胺初始浓度、体系初始pH、反应温度等因素对二价铁活化过硫酸盐去除水中苯胺处理效率的影响。结果表明:1)Fe2+活化过硫酸盐生成SO-4·能快速并有效氧化降解苯胺,对于目标浓度为1 000 mg/L的苯胺而言,Fe2+浓度为3.3 mmol/L,Na2S2O8浓度为4.4 mmol/L时,对苯胺有较佳降解效果,苯胺的降解率为86.33%。2体系对较低浓度的苯胺降解效果较好,当污染物初始浓度由1 000 mg/L降低到500 mg/L和100 mg/L时,苯胺降解率由86.33%升高为90.27%和97.16%。3初始pH对苯胺的降解率影响较大,中性条件下(pH=7左右)降解率较好,高初始pH(pH=9,11)和低初始pH条件(pH=3,5)下均低于中性条件下苯胺的降解效率。4体系的温度变化对降解率影响不明显。     

臭氧化含苯酚污水投加水镁石沉淀出草酸镁的实验研究

本文通过两组不同水镁石-苯酚投料比的实验,研究固体沉淀物与水质变化的关系。实验显示,水镁石解离出的Mg²⁺与苯酚降解的中间产物能形成难溶盐,并发生沉淀分离,促进含苯酚废水臭氧化降解的效率。当苯酚的初始浓度为47 g/L,初始碳镁原子比(C/Mg)为30时,经3小时充分臭氧化曝气后,投加的水镁石全部耗尽。XRD、TG/DSC结果显示新形成的沉淀物为草酸镁。反应终点的pH值在4以下,TOC去除率为40%。当体系的初始C/Mg(原子比)为1,苯酚的初始浓度为1.5 g/L时,同样的臭氧化曝气过程体系残留的沉淀物仍是水镁石。反应终点的pH值在10左右,TOC去除率为92.8%。研究证明,苯酚臭氧化过程也是体系酸化的过程,至少在高C/Mg比条件下新生的质子能与水镁石解离出的羟基中和,水镁石解离出的Mg²⁺可与草酸根结合沉淀出草酸镁。     

热活化过硫酸盐降解氧氟沙星特性及响应面优化

为了探究热活化过硫酸盐（PS）技术对水中氧氟沙星（OFX）的氧化降解作用,考察了反应温度、体系的初始pH、PS的初始浓度、OFX的初始浓度对OFX降解效果的影响;并在单因素实验的基础上,选取反应时间、体系的初始pH、PS的初始浓度和OFX的初始浓度4个因素进行了响应面优化实验。结果表明：最佳降解条件为,反应温度60℃、PS初始浓度4.0 mmol/L、pH=4.7、OFX初始浓度0.03 mmol/L、反应时间60 min,此时OFX的降解率为81.29%;4个因素对热活化PS降解OFX均有影响,其影响显著性从大到小为反应时间、OFX的初始浓度、PS的初始浓度、初始pH。利用响应曲面法模拟出反应体系的最佳条件,经实验验证,OFX降解率为93.78%,与预测最佳结果95.00%基本相符,表明模型可靠有效。     

电化学循环井耦合氧化 -还原降解地下水中三氯乙烯

三氯乙烯（TCE）是一种地下水中常见的有机污染物,传统的地下水循环井修复技术虽然有效但耗时长,且需配套地面处理。文章研发了一种电化学循环井耦合修复体系,以期通过顺序化学氧化 -还原作用高效快速降解地下水中TCE。以地下水循环井为基础,通过抽水井中的地下水电解,原位提供O2和H2,投加Fe（Ⅱ） -EDTA络合物活化O2产生羟基自由基氧化降解TCE,进而利用钯催化剂催化剩余的H2还原降解TCE。在二维砂槽模拟含水层中评价了该体系的运行效果,含水层中初始TCE浓度为7.50 mg/L,经过13天的连续通电处理后,TCE浓度降低到1.65 mg/L,降解率达到78%。处理后Cl-浓度相应增加118.20 μmol/L,接近于TCE降解量（44.50 μmol/L）的3倍,证明TCE近乎完全脱氯。运行过程中,TCE平均降解速率由0~5 d的0.90 mg/(L·d) 降低到9~13 d的0.10 mg/(L·d),氧化降解主要发生在前期阶段,钯催化还原效率较为稳定,后期两种过程降解效率都逐渐下降,主要原因是溶解态Fe（Ⅱ）浓度减少以及钯催化剂活性降低。该耦合修复体系是基于地下水循环井技术的改进,其氧化 -还原作用机理有望实现地下水中多种不同有机污染物的降解。     

超声强化零价铁活化过硫酸盐降解地下水中二恶烷

本文采用超声强化零价铁活化过硫酸盐氧化降解地下水中的二恶烷污染物。主要探讨了零价铁添加量、超声强化、不同过硫酸盐用量及地下水中不同碳酸根浓度等对二恶烷降解效果的影响,并对零价铁进行了表征分析。结果表明：超声能够促进硫酸根自由基和Fe²⁺的产生,提高二恶烷的降解率;零价铁添加量和过硫酸盐浓度的增加均能促进二恶烷的降解,但零价铁相对过硫酸盐过多时将降低最终降解率;地下水中的碳酸根会消耗硫酸根自由基,因此碳酸根浓度越高,二恶烷降解率越低。超声强化零价铁活化过硫酸盐氧化法能够有效降解二恶烷,并具有应用于处理地下水中二恶烷的潜力。     

Fenton氧化膜-生物反应器出水中丙烯腈的实验研究

采用膜-生物反应器和Fenton氧化组合工艺对丙烯腈废水进行处理。从GC/MS测量结果来看,膜-生物反应器出水中主要物质为2,6双（二甲基-乙基）-4-酚、苯二甲酸和硝基苯二甲酸,均为生物难降解有机物,使出水不能达标。后续Fenton氧化工艺处理膜生物反应器出水,可以使COD含量等指标达到所要求的排放标准。经过膜-生物处理与Fenton法结合的优化工艺,COD去除率达到80%~88%,去除率达到98%,出水水质可达排放标准。Fenton氧化工艺的最佳工艺条件为：pH值为3.4,硫酸亚铁的投加量为700mg/L,双氧水的投加量为600mg/L。     

Fe/Ag催化臭氧氧化降解苯酚的研究

为研究双金属催化剂去除有机污染物的效果,采用自制Fe/Ag催化剂对模拟苯酚废水进行了臭氧催化氧化处理。通过扫描电子显微镜(SEM)、比表面积分析仪(BET)和X射线衍射(XRD)对催化剂进行表征,并考察了催化剂类型、催化剂投加量和溶液初始pH值对降解效果的影响规律。结果表明:与Fe相比,Fe/Ag比表面积减少了22.8%,在Fe/Ag/O₃与含苯酚废水的反应体系中,反应遵循臭氧直接作用和活性自由基(·OH、·O₂、H₂O₂)共同作用的机理;Fe/Ag在反应过程中体现出良好的协同作用;300 mg/L的苯酚模拟废水在pH=6.3、Fe/Ag投加量为1.00 g的最优反应条件下经60 min反应,苯酚与化学需氧量(COD)去除率比单独臭氧氧化分别提高了18.4%和29.4%。     

还原态蒙脱石有氧条件产生羟自由基降解有机污染物

近期见有含二价铁矿物可活化分子氧产生羟自由基而氧化污染物的报道。本文选用土壤/沉积物中的常见组分蒙脱石(含铁约2%),研究了还原态蒙脱石在不同条件下活化分子氧降解苯酚的效果。结果表明,20g/L还原态蒙脱石(还原程度为30%)在pH=6和有氧条件下,可通过产生羟自由基使11μM苯酚的降解率在6h内持续增加至59.1%。苯酚降解率对应的最佳pH为5,当pH>6时降解率则随着p H的升高而急剧降低;苯酚降解效果还随还原态蒙脱石剂量(0~40g/L)增加而提高;苯酚初始浓度为11μM降解率最高,增加或者降低初始浓度均使降解率降低。还原态蒙脱石铁含量低,活化分子氧时其八面体边缘配位和结构内部二价铁共同起作用,而受八面体层Al、Mg等惰性组分阻碍,其结构二价铁难以向边缘位置传递电子,这与前期报道的还原态绿脱石(含铁约20%)不同。     

TiO2-蒙脱石光催化降解苯酚的实验研究

本文采用TiCl4在HCl中水解制备二氧化钛柱撑蒙脱石(TiO2-PILM)纳米材料，通过X射线衍射和BET N2比表面积分析对其进行表征，并研究其对苯酚在紫外光下的催化降解曲线，考察了苯酚的初始浓度、TiO2-PILM投放量、苯酚溶液pH值对光催化降解效果的影响。结果表明，制备的结构稳定的TiO2-PILM具有2．26nm大晶面间距和285．7m^2／g大比表面积。TiO2-PILM对苯酚有一定的光催化降解性，其过程是先吸附后降解。随苯酚初始浓度、TiO2-PILM投入量和苯酚溶液pH值的升高，TiO2-PILM对苯酚降解速率增大。在苯酚初始浓度为5mg／L、投样量为1g／L、pH为10时，TiO2-PILM对苯酚有较好的降解效果。     

Biosorption of 4-chlorophenol by dried anaerobic digested sludge: artificial neural network modeling,equilibrium isotherm,and kinetic study

In this study, dried anaerobic digested sludge (DADS) was utilized to remove 4-chlorophenol (4-CP) from aqueous solutions. Batch biosorption experiments were carried out to investigate the effects of physicochemical parameters such as pH, contact time, biosorbent dosage, and initial concentration. Artificial neural network (ANN) was then used to predict the removal efficiency of the process. The comparison between predicted and experimental results provided a high degree of determination coefficient (R² = 0.98), indicating that the model could predict the biosorption efficiency with reasonable accuracy. Biosorption data were successfully described by the Freundlich isotherm and pseudofirst-order model. The Weber–Morris kinetic model indicated that intraparticle diffusion was not the only rate-controlling step, and other mechanisms may be involved in the biosorption process. The optimum pH was detected to be 3 for DADS. By increasing contact time and biosorbent dosage, the removal efficiency of 4-CP increased. Also, a decreasing trend was observed when initial concentrations were increased. The findings suggested that the results predicted by ANN are very close to the experimental values, and DADS as an available adsorbent can efficiently remove 4-CP from aqueous solutions.     

硫化纳米铁对模拟地下水中Cr(Ⅵ)的去除效果及影响因素

硫化纳米铁（S-nZVI）是一种具有壳核结构的新型纳米铁（nZVI）改性材料,在多种污染物的去除上表现出超越nZVI的反应活性。本文采用两步合成法制备了S-nZVI,并采用透射电镜-能量色散X射线（TEM-EDX）、X射线衍射（XRD）和X射线光电子能谱分析（XPS）方法对S-nZVI和nZVI进行表征,探讨了不同硫铁摩尔比（n（S）/n（Fe））、初始pH值、试剂投加量和地下水化学成分对nZVI及S-nZVI去除Cr（Ⅵ）的影响。结果表明：S-nZVI具有明显的壳核结构,其Fe⁰核外层包覆着非晶的硫化亚铁和多硫化物;S-nZVI去除Cr（Ⅵ）的最佳n（S）/n（Fe）为0.14;增加S-nZVI投加量会提高其对Cr（Ⅵ）的去除率,投加量相同时,S-nZVI对Cr（Ⅵ）的去除率显著高于nZVI;提高初始pH值时,S-nZVI和nZVI对Cr（Ⅵ）的去除率均逐渐降低,但在相同pH值条件下,S-nZVI对Cr（Ⅵ）的去除率和去除速率始终高于nZVI,尤其是在pH=5时,S-nZVI仍能去除100%的Cr（Ⅵ）,而nZVI只能去除85%;K⁺、Na⁺、Ca²⁺、Mg²⁺、SO₄^2-、NO₃^-和Cl^-对S-nZVI和nZVI去除Cr（Ⅵ）均有促进作用,但对S-nZVI体系的促进作用更强;HCO₃^-的存在会使溶液的pH值升高从而抑制S-nZVI和nZVI对Cr（Ⅵ）的去除,对nZVI的抑制作用强于S-nZVI。总体来说,S-nZVI对Cr（Ⅵ）的去除率在不同pH值和多种地下水化学组分影响条件下均高于nZVI,因此具有更广泛的应用前景。     

共存重金属离子对针铁矿活化过硫酸盐去除水中磺胺吡啶的影响

基于硫酸根自由基的高级氧化技术能有效降解水中磺胺类药物残留。由于在自然环境中共存重金属会对环境修复效果产生一定影响,文中重点研究了不同pH环境条件下不同重金属离子对针铁矿活化过硫酸盐(PS)去除水中磺胺吡啶(SPY)的影响。不同类型重金属离子(Cu^2+、Pb^2+、Cd^2+,0.2mmol/L)在反应体系(初始条件:针铁矿,1.0g/L;PS,4mmol/L;SPY,10mg/L;pH=8.2)中对SPY的降解对比研究发现:在无重金属共存的条件下,针铁矿/PS体系降解SPY的去除率为25.2%;Pb^2+和Cd^2+对针铁矿/PS体系的影响较弱,去除率分别为30.8%和34.8%;Cu^2+的促进作用很大,可以使SPY被完全降解(100%)。机理分析认为,在针铁矿/PS体系中Pb^2+和Cd^2+主要通过影响吸附作用导致磺胺吡啶被去除,而Cu^2+主要通过自身活化PS的作用。不同pH条件(3.0,8.0,12.0)实验证实弱碱性条件下,Cu^2+/针铁矿/PS能够发挥较高的活性从而降解SPY。本文结果为采用针铁矿活化过硫酸盐技术修复类似复合污染地下水环境提供了实验依据。     

煤化工渣高效吸附去除水中全氟辛酸

为高效快速去除水中全氟辛酸,选择工业废物煤化工渣对全氟辛酸进行吸附去除探究。采用不同的处理方法制备了4种煤化工渣（粒径从大到小为CGA1、CGA2、CGA3和CGA4）,研究其在水溶液中的全氟辛酸吸附性能。利用扫描电子显微镜（SEM）、拉曼光谱、傅里叶变换红外光谱（FTIR）和X射线光电子能谱（XPS）对4种煤化工渣的结构特征进行表征分析,并考察了全氟辛酸初始质量浓度和初始pH对吸附进程的影响。实验结果表明：煤化工渣对全氟辛酸有高效的吸附能力,伪二级动力学模型和Langmuir等温模型可以较好地描述4种煤化工渣对全氟辛酸的吸附行为及过程,其中CGA4去除全氟辛酸的最大吸附量为25.51 mg/g;随着全氟辛酸溶液初始质量浓度升高,煤化工渣对全氟辛酸的吸附容量逐渐增加;初始pH对CGA3和CGA4的影响微弱,CGA1和CGA2在酸性条件下显示出更优越的吸附性能。由此得出,4种煤化工材料中粒径最小的CGA4具有最优的全氟辛酸去除能力且基本不受pH限制。FTIR分析表明,吸附过程中氢键的形成占主导地位,XPS和Zeta电位检测结果表明,物理吸附和静电吸附在去除过程中也发挥了重要作用。     

Mineralization of organic matter from vinasse using physicochemical treatment coupled with Fe<Superscript>2+</Superscript>-activated persulfate and peroxymonosulfate oxidation

Application of advanced oxidation process for wastewater treatment has gained more attention recently. In this study, the efficiency of coagulation–flocculation pretreatment coupled with sulfate radical-based advanced oxidation process (SR-AOP) in the removal and mineralization of organic matter of sugarcane vinasse was evaluated. For coagulation–flocculation, jar-test experiment was carried out with ferric chloride as coagulant and the removal of TOC, color and UV₂₅₄ was determined. The results revealed that by using 15 g/L of coagulant, 70 % of TOC removal and nearly 100 % of UV₂₅₄ and color removal were achieved. The pretreated vinasse was then subjected to SR-AOP. In this study, sulfate radical was generated using persulfate (PS) and peroxymonosulfate (PMS) activated by Fe(II). The effect of reaction time, oxidants to Fe(II) ratio and pH on the TOC removal efficiency were investigated. For the effect of reaction time, the TOC removal was found to increase significantly for the first 5 min. TOC removal was found to increase with increasing concentration of Fe(II) for PMS. However, for Fe(II)/PS, the TOC removal efficiency was decreased with increasing Fe(II) concentration. Both Fe(II)/PMS and Fe(II)/PS showed the highest TOC removal efficiency when the oxidation was carried out at pH 7. By using the selected optimum condition, nearly 70 and 49 % of TOC removal were achieved for PMS/Fe(II) and PS/Fe(II), respectively. Therefore, it can be concluded that SR-AOP can be a promising alternative method for TOC removal from sugarcane vinasse.     

臭氧-超声联用处理聚乙烯醇废水

本研究采用臭氧-超声（O₃/US）联用技术处理聚乙烯醇（PVA）废水,分别考察了PVA初始质量浓度、初始pH、臭氧通入速率、超声功率、超声频率及反应时间对PVA和COD去除效率的影响,并在此基础上通过正交实验确定了降解PVA和COD的最佳实验条件。研究结果表明,超声频率对去除率有显著影响,PVA初始质量浓度对去除效率的影响较大,反应时间、超声功率、臭氧通入速率和初始pH的影响相对较小。通过影响实验和正交实验确定的最佳降解条件为:PVA初始质量浓度100 mg/L、初始pH=9、臭氧通入速率4 g/h、超声功率320 W、超声频率40 kHz、反应时间20 min,此时COD和PVA的去除效率分别为86.4%和99.3%。超声对臭氧降解聚乙烯醇废水具有明显的协同作用,在最佳条件下,臭氧-超声联用技术比单独臭氧技术对PVA的去除率增加了5.1%,对COD去除率增加了19.4%。     

Biosorption of Cd(II) from synthetic wastewater using dry biofilms from biotrickling filters

Biofilms wasted from biotrickling filters was dried and used as biosorbent for Cd(II) removal from aqueous solutions. The adsorption condition and effect, adsorption isotherms and kinetics of Cd(II) removal were investigated, and the effects of competitive metal ions on Cd(II) removal were also examined. Results showed that the dry waste biofilms reached the maximum adsorption capacity of 42 mg/g of Cd(II) at 25 °C for 120 min when the initial concentration of Cd(II) and their pH were 50 mg/L and 6.0, respectively. Under these conditions, the removal efficiency of Cd(II) reached to 89.3% when the biosorbent dosage was 2.0 g/L. The Langmuir isotherm model correlated with the isotherm data better than the Freundlich isotherm model, and the pseudo-second-order model fitted the kinetic data better than the pseudo-first-order model. These results indicated that the adsorption was monolayer accompanied with chemical adsorption. In the presence of other metal ions, divalent metal ions of Ca and Zn inhibited the performance of Cd(II) biosorption significantly, while Na(I), K(I) and Fe(III) which had a higher or lower valence than Ca(II) affected slightly when containing 50 mg/L Cd(II), 0.5 g/L adsorbent dosage and pH 6.0. The analyses of scanning electron microscopy and Fourier transform infrared spectroscopy illuminated that the biosorbent had porous structures and the amide group was the majorly responsible for Cd(II) removal. Dry biofilms were novel sorbents for effective removal Cd(II), and it could be reused and recycled if necessary.     

Degradation of trace aqueous 4-chloro-2-nitrophenol occurring in pharmaceutical industrial wastewater by ozone

Degradation of 4-chloro-2-nitro phenol by ozonation in aqueous solution was studied in a semi batch reactor under constant ozone dosage and variable pH conditions. The effectiveness of the process was estimated based on the degree of conversion of 4-chloro-2-nitro phenol. It was observed that ozonation is more effective at alkaline reaction of medium than other conditions. The degree of conversion achieved (at the first 5 minutes of the process)at pH 9 was 99.64% compared to 99.03% and 77.35% at pH 7 and 3, respectively. Another parameter used to quantify the 4-chloro-2-nitrophenol during ozonation was the pseudo first order rate constant k [min^?1]. Results showed that the rate constant of the process was approximately much higher at the alkaline pH compared to acidic ones. A considerable improvement in chemical oxygen demand removal was observed at pH above 7. At pH 9, the reduction in chemical oxygen demand at the end of the process reached 56.9 %. The degree of organically bounded nitrogen conversion to nitrate was higher at pH 3. Of the total organic carbon reduction, 15.89 % was observed at pH 9. The 4-chloro-2-nitro phenol degradation intermediate products were analyzed by mass- spectrometry. The main intermediate product was chlorophenol.