Fenton氧化法修复石油污染土壤的研究进展

传统的Fenton氧化法（Fe2＋/H2O2）因反应速度过快、需要定期补充Fe2＋、控制pH值≤3等方面的限制而影响到石油烃类污染土壤的修复效果.本文综述了近年来Fenton反应中氧化剂、催化剂的改进及其对土壤中石油污染物的去除效率,揭示了土壤性质、反应条件、污染物结构及非均相催化剂比表面积等因素对去除效率的影响,介绍了超声波前置处理后,Fenton试剂与土壤上解吸的石油污染物接触几率的增加及石油烃类可生物降解性的提高,促进了微生物的后续处理效果,并对该领域的研究趋势进行了展望.     

五氧化二钒类Fenton降解邻苯二甲酸二乙酯的机制研究

发展了基于五氧化二钒(V_2O_5)和过氧化氢(H_2O_2)的新型类Fenton体系,探索了此体系产生羟基(·OH)的机制及降解邻苯二甲酸二乙酯(DEP)的效率;并考察了V_2O_5投加量、H_2O_2浓度,以及草酸对DEP降解的影响。结果表明,当V_2O_5投加量为0.1 g·L-1,H_2O_2浓度为2.0 mmol·L-1,反应24 h后,对DEP(25 mg·L-1)的降解率可达61.1%,增加或降低V_2O_5投加量和H_2O_2浓度均不利于DEP的降解。利用电子顺磁共振技术(Electron Paramagnetic Resonance,EPR)耦合5,5-二甲基-1-吡咯啉氮氧化物(DMPO)为捕获剂对反应体系中的主导自由基进行鉴定,发现·OH是体系降解DEP的主要活性物种,利用苯甲酸作为探针分子实现了·OH的间接定量,并初步推测了V_2O_5活化H_2O_2的过程。     

类Fenton氧化在污染土壤修复中的应用

传统的Fenton氧化要在酸性条件下进行,使用传统的方法处理污染土壤会造成土壤生态环境的破坏.为了保护生态环境,在不改变土壤pH值的条件下,利用铁盐和铁的氧化物矿石作催化剂催化H2O2氧化去除土壤中的污染物.研究结果表明:不同的催化剂催化氧化去除污染物的能力不同,可溶态的亚铁盐和铁盐催化效果比不可溶的固态铁矿石要好,其中可溶态的硫酸亚铁催化反应的效果最好,反应60 min后,污染物的最大去除率能达到65%以上;不可溶的铁矿石中磁铁矿的催化效果比赤铁矿要好些,污染物的去除率能达到55%以上.     

氯代苯类化合物在土壤中的微生物降解

本文采用土柱装置对某地区城市污水中所含的氯苯、对-二氯苯和1,2,3-三氯苯在该地区土壤中的微生物降解进行了动态研究,并通过对-二氯苯在土壤及水中的降解实验,筛选出了可降解对-二氯苯的一株细菌,经鉴定为芽孢杆菌(Bacillus SP.),在对-二氯苯降解的同时,有氯苯出现并得到确证.     

铁锰矿类Fenton异相光催化降解有毒有机染料

选取6种天然铁锰矿石为光催化剂,以可见光(λ420nm)照射下活化H2O2降解有机染料罗丹明B(RhodamineB,RhB)为探针反应,筛选出活性较高的天然矿石(磁赤铁矿)催化降解RhB及2,4-二氯苯酚(2,4-Dichlorophenol,DCP).实验表明,可见光下磁赤铁矿在pH=7.0的介质体系,H2O2浓度为3×10-3mol·l-1条件下可有效降解RhB.通过反射紫外光谱、原子吸收分光光度法、XRD初步表征了磁赤铁矿组成结构;采用紫外-可见吸收光谱(UV-vis)、红外光谱(IR)、总有机碳(TOC)测定等方法,研究了其可见光照射下对RhB光催化降解特性.结果表明,在实验条件下RhB矿化率达60%,DCP矿化率达到63.93%.利用电子自旋捕捉技术(ESR)跟踪测定RhB降解过程中氧化物种,表明催化降解过程涉及羟基自由基(·OH)氧化过程.拟定异相矿石类Fenton体系与传统均相Fenton体系相比,具有反应介质pH范围宽(3.0—7.0)、可见光激发及催化剂易得廉价等优势。     

酸沉降下加速土壤酸化的影响因素

酸沉降对土壤和水域的酸化影响是土壤环境化学研究前沿的热点问题之一。酸沉降的化学组成对酸性土壤的进一步酸化起着催化剂的作用。在酸雨影响下,SO42-、NO-3、有机阴离子是加速土壤酸化和盐基淋溶损失的主要阴离子,外源H+的进入会加速铝离子水解。自然因素与人为因素导致土壤酸化的实际酸化速率差异表明:HCO3-、RCOO-在土壤剖面中的淋失状况可反映自然土壤的酸化速率,而SO42-和NO-3淋溶产生的质子负荷揭示土壤受人为因素影响的酸化速率。通过计算酸沉降的主要化学成分进入土壤前后的质子负荷平衡,与酸中和容量(ANC)相结合,反映酸沉降加速土壤酸化的进程。     

苯并[a]芘和二苯并[a,h]蒽的土壤降解特性及其影响因素

实验室条件下,研究了不同土壤性质、水分含量、通气条件、外加营养元素比例与外源微生物等条件下,苯并[a]芘(BaP)和二苯并[a,h]蒽(DBA)在土壤中的降解特性.结果表明,当土壤中BaP和DBA的添加水平分别为2.5 mg·kg-1时,至125 d时,BaP在pH较低的江西红壤中降解最快,降解率达87.3%;而DBA在有机质含量较高的中性太湖水稻土中降解较快,降解率为52.0%.土著微生物对BaP和DBA在土壤中的降解起重要作用;合适的土壤C/N比值能明显加快降解速率;好气条件有利于BaP和DBA的降解.     

Fenton试剂氧化法修复2,4-二氯酚污染土壤的研究

在泥浆体系中采用Fenton试剂氧化法修复2,4-二氯酚(2,4-DCP)污染的土壤.在恒温、避光条件下,研究2,4-DCP在泥浆体系中的解吸作用,并考察过氧化氢、硫酸亚铁、pH值、水土比、磷酸二氢钾、腐殖酸(HA)等因素对2,4-二氯酚去除效率的影响.试验结果显示,2,4-DCP在泥浆体系中有较高的解吸速率;2,4-DCP的解吸效率与水土比有关,水土比越大,解吸效率越高.研究表明:Fenton试剂氧化法能够有效地去除土壤中的2,4-DCP,过氧化氢和铁的最佳质量比为5:1,最佳pH值范围为2-3;水土比越大,2,4-DCP的去除效果越好;在pH=3时,磷酸二氢钾浓度、腐殖酸投加量和催化剂种类对2,4-DCP的去除效率影响很小.     

Fenton法降解水中布洛芬

采用Fenton法降解水中布洛芬,考察了H2O2投加量、FeSO.47H2O与H2O2的比值、初始pH、反应时间等因素对布洛芬去除率的影响,通过正交实验确定影响作用大小依次为:[Fe2+]∶[H2O2]的物质的量之比>H2O2的投加量>pH值,最佳的反应工艺条件为:H2O2的投加量为3 mL.L-1,[Fe2+]∶[H2O2]的物质的量之比为1∶10,反应初始pH值为3,反应时间为40 min.在最佳条件下布洛芬的去除率达到86%以上.同时对布洛芬降解反应动力学进行了研究,发现Fenton降解布洛芬符合二级反应动力学规律.     

Sorption mechanisms of diphenylarsinic acid on natural magnetite and siderite: Evidence from sorption kinetics,sequential extraction and extended X-ray absorption fine-structure spectroscopy analysis

• DPAA sorption followed pseudo-secondary and intra-particle diffusion models. • Chemical bonding and intra-particle diffusion were dominant rate-limiting steps. • DPAA simultaneously formed inner- and outer-sphere complexes on siderite. • DPAA predominantly formed occluded inner-sphere complexes on magnetite. • Bidentate binuclear bond was identified for DPAA on siderite and magnetite. Diphenylarsinic acid (DPAA) is both the prime starting material and major metabolite of chemical weapons (CWs). Because of its toxicity and the widespread distribution of abandoned CWs in burial site, DPAA sorption by natural Fe minerals is of considerable interest. Here we report the first study on DPAA sorption by natural magnetite and siderite using macroscopic sorption kinetics, sequential extraction procedure (SEP) and microscopic extended X-ray absorption fine-structure spectroscopy (EXAFS). Our results show that the sorption pseudo-equilibrated in 60 minutes and that close to 50% and 20%–30% removal can be achieved for magnetite and siderite, respectively, at the initial DPAA concentrations of 4–100 mg/L. DPAA sorption followed pseudo-secondary and intra-particle diffusion kinetics models, and the whole process was mainly governed by intra-particle diffusion and chemical bonding. SEP and EXAFS results revealed that DPAA mainly formed inner-sphere complexes on magnetite (>80%), while on siderite it simultaneously resulted in outer-sphere and inner-sphere complexes. EXAFS analysis further confirmed the formation of inner-sphere bidentate binuclear corner-sharing complexes (²C) for DPAA. Comparison of these results with previous studies suggests that phenyl groups are likely to impact the sorption capacity and structure of DPAA by increasing steric hindrance or affecting the way the central arsenic (As) atom maintains charge balance. These results improve our knowledge of DPAA interactions with Fe minerals, which will help to develop remediation technology and predict the fate of DPAA in soil-water environments.     

Fenton氧化处理对土壤中芘的生物可利用性的影响

研究发现蚯蚓吸收土壤中污染物芘的速率很快,10 d后蚯蚓体内富集污染物浓度基本达到稳定态;土壤中的有机质是影响污染物迁移的重要因素,土壤有机质的含量越高对芘滞留(吸附)能力越强,蚯蚓富集芘的量越低,蚯蚓富集到体内污染物的浓度越低.这也说明土壤对污染物的吸附/解吸行为决定了土壤中污染物的生态风险;氧化处理降低了土壤中的有机质含量,改变土壤有机质的组成,氧化处理也降低了土壤中被吸附污染物芘对蚯蚓的生物有效性.     

Degradation of refractory organics in concentrated leachate by the Fenton process: Central composite design for process optimization

• 90% total COD, 95.3% inert COD and 97.2% UV₂₅₄ were removed. • High R² values (over 95%) for all responses were obtained with CCD. • Operational cost was calculated to be 0.238 €/g COD_removed for total COD removal. • Fenton oxidation was highly-efficient method for inert COD removal. • BOD₅/COD ratio of leachate concentrate raised from 0.04 to 0.4. The primary aim of this study is inert COD removal from leachate nanofiltration concentrate because of its high concentration of resistant organic pollutants. Within this framework, this study focuses on the treatability of leachate nanofiltration concentrate through Fenton oxidation and optimization of process parameters to reach the maximum pollutant removal by using response surface methodology (RSM). Initial pH, Fe²⁺ concentration, H₂O₂/Fe²⁺ molar ratio and oxidation time are selected as the independent variables, whereas total COD, color, inert COD and UV₂₅₄ removal are selected as the responses. According to the ANOVA results, the R² values of all responses are found to be over 95%. Under the optimum conditions determined by the model (pH: 3.99, Fe²⁺: 150 mmol/L, H₂O₂/Fe²⁺: 3.27 and oxidation time: 84.8 min), the maximum COD removal efficiency is determined as 91.4% by the model. The color, inert COD and UV₂₅₄ removal efficiencies are determined to be 99.9%, 97.2% and 99.5%, respectively, by the model, whereas the total COD, color, inert COD and UV₂₅₄ removal efficiencies are found respectively to be 90%, 96.5%, 95.3% and 97.2%, experimentally under the optimum operating conditions. The Fenton process improves the biodegradability of the leachate NF concentrate, increasing the BOD₅/COD ratio from the value of 0.04 to the value of 0.4. The operational cost of the process is calculated to be 0.238 €/g COD_removed. The results indicate that the Fenton oxidation process is an efficient and economical technology in improvement of the biological degradability of leachate nanofiltration concentrate and in removal of resistant organic pollutants.     

Degradation of the herbicide imazapyr by Fenton reactions

The degradation of the herbicide imazapyr has been carried out by three advanced oxidation processes involving iron ions as catalysts: Fentons reagent, photo-Fenton and electro-Fenton. We show that all processes are rapid and efficient. The kinetic rate constant was found to be k=5.4×10⁹ M^–1 s^–1. The mineralization of imazapyr is almost complete using the photo-Fenton and electro-Fenton processes.     

土壤中总石油烃污染（TPH）的微生物降解与修复研究进展

微生物降解和修复是处理土壤中总石油烃(TPH)污染最简单、有效的方法之一.论文阐述了土壤TPH污染的产生、危害以及物理、化学、生物等修复方法的各自特点,其中重点介绍了微生物修复方法,论述了土壤中TPH在微生物表面的吸附、转运,在微生物体内的降解以及相关降解酶及基因;详细介绍了电子受体、温度、pH、营养元素等外界因素对微生物修复TPH污染的影响,在此基础上对土壤TPH污染的微生物修复现状和发展趋势进行了讨论.     

微波法不同影响因素对土壤中氯丹降解的影响

以农药生产企业搬迁遗留场地土壤为研究对象,研究了微波修复土壤技术的各影响因素对氯丹降解的影响.结果表明:在土壤含水率20％、pH值8.5、活性炭投加量50 g·kg-1、微波功率600 W和辐照时间20 min条件下,微波法对氯丹去除率达到89％;若土壤中氯丹去除温度保持在300 ℃以上,可使氯丹大幅度去除.各因素对微波法去除氯丹的影响由大到小依次为微波功率、辐照时间、活性炭投加量和含水率.修复过程中氯丹降解的中间产物有六氯、七氯和九氯等,推测其降解过程存在加氯和脱氯反应.     

Effects of sepiolite on stabilization remediation of heavy metal-contaminated soil and its ecological evaluation

Stabilization in the remediation of heavy metal contaminated soils has been gaining prominence because of its cost-effectiveness and rapid implementation. In this study, microbial properties such as microbial community and enzyme activities, chemical properties such as soil pH and metal fraction, and heavy metal accumulation in spinach (Spinacia oleracea) were considered in assessing stabilization remediation effectiveness using sepiolite. Results showed that soil pH values increased with rising sepiolite concentration. Sequential extraction results indicated that the addition of sepiolite converted significant amounts of exchangeable fraction of Cd and Pb into residual form. Treatments of sepiolite were observed to reduce Cd and Pb translocation from the soil to the roots and shoots of spinach. Concentrations of Cd and Pb exhibited 12.6%–51.0% and 11.5%–46.0% reduction for the roots, respectively, and 0.9%–46.2% and 43.0%–65.8% reduction for the shoots, respectively, compared with the control group. Increase in fungi and actinomycete counts, as well as in catalase activities, indicated that soil metabolic recovery occurred after sepiolite treatments.     

In situ immobilisation remediation of cadmium in artificially contaminated soil: a chemical and ecotoxicological evaluation

A pot experiment was conducted to evaluate the effectiveness of sepiolite-induced immobilisation remediation of Cd contaminated soil. The results demonstrated that adding sepiolite significantly increased the soil pH and resulted in 35.1–66.0%, 30.3–48.9%, and 31.6–51.6% reduction in toxicity characteristic leaching procedure of Cd (TCLP-Cd), respectively, for the Cd levels of 1.25, 2.5, and 5?mg/kg compared with the no-sepiolite controls. These decreases in TCLP-Cd were associated with reductions in plant phyotoxicity and Cd absorption, and sepiolite-treated soils resulted in increases of 3.2–38.0%, 34.2–52.3%, and 8.4–51.5% in shoot biomass, respectively, and in decreases of 26.7–39.6%, 17.3–28.5%, and 6.1–21.8% in shoot Cd contents, respectively, under soil Cd concentration of 1.25, 2.5 and 5?mg/kg compared to the unamended soils. The greater microbial biomass and catalase and urease activities after applying sepiolite implied a certain degree of recovery in metabolic function recovery during soil remediation. These results demonstrated that the application of sepiolite not only was effective at reducing Cd bioavailability and the rate of Cd accumulation in plants, but also improved soil environmental quality.