过硫酸盐在岩溶管道地下水中的稳定性及其对苯系物的去除效果

原位化学氧化(in situ chemical oxidation,ISCO)是一种高效便捷的去除地下水有机污染物的技术,相比于多孔介质,岩溶地下河中ISCO技术应用还未见报道.为了更好地认识ISCO技术在岩溶地下河石油污染修复中应用的可行性,使用过硫酸盐(persulfate,PS)作为化学氧化剂,在实验室利用碳酸盐...     

基于文献计量的全球活化过硫酸盐氧化技术研究趋势分析

通过激活过硫酸盐(persulfate, PS)产生硫酸根自由基是一种新兴的高级氧化技术,该方法由于无毒、高效、经济且环境友好等优势在水土污染修复中得到广泛关注。基于文献计量学和网络图分析方法,利用Web of Science核心数据库对1986—2019年以来有关过硫酸盐的文献进行回顾和梳理。使用VOSviewer(1.6.13版)软件,分析全球对过硫酸盐研究的国家、机构、作者、期刊、共引用文献及关键词等数据,并且绘制出关键词共现图谱和密度图,以分析过硫酸盐的研究历史、目前的研究热点以及发展前景。结果显示,研究热点集中在过硫酸盐的高级氧化技术、活化方法、氧化动力学和机理以及在修复土壤和地下水中的应用等。同时,基于研究热点系统归纳了过硫酸盐的活化方法及其降解污染物的实际应用,提出了当前活化过硫酸盐研究所存在的问题,并对未来的研究方向进行了展望,以期为活化过硫酸盐氧化技术在环境修复领域进一步发展和研究提供参考。     

pH dependence of persulfate activation by EDTA/Fe(III) for degradation of trichloroethylene

The ability of free ferrous ion activated persulfate (S₂O₈²⁻) to generate sulfate radicals (SO₄⁻) for the oxidation of trichloroethylene (TCE) is limited by the scavenging of SO₄⁻ with excess Fe²⁺ and a quick conversion of Fe²⁺ to Fe³⁺. This study investigated the applicability of ethylene-diamine-tetra-acetic acid (EDTA) chelated Fe³⁺ in activating persulfate for the destruction of TCE in aqueous phase under pH 3, 7 and 10. Fe³⁺ and EDTA alone did not appreciably degrade persulfate. The presence of TCE in the EDTA/Fe³⁺ activated persulfate system can induce faster persulfate and EDTA degradation due to iron recycling to activate persulfate under a higher pH condition. Increasing the pH leads to increases in pseudo-first-order-rate constants for TCE, S₂O₈²⁻ and EDTA degradations, and Cl generation. Accordingly, the experiments at pH 10 with different EDTA/Fe³⁺ molar ratios indicated that a 1/1 ratio resulted in a remarkably higher degradation rate at the early stage of reaction as compared to results by other ratios. Higher persulfate dosage under the EDTA/Fe³⁺ molar ratio of 1/1 resulted in greater TCE degradation rates. However, increases in persulfate concentration may also lead to an increase in the rate of persulfate consumption.     

热活化过硫酸盐对双酚A的降解及其机理

研究了热活化过硫酸盐对双酚A的氧化降解效能及机理,探讨了温度,反应物初始浓度,pH值,阴离子和腐殖酸对双酚A降解的影响。结果表明:在实验范围内,双酚A的降解率随温度和过硫酸钠初始浓度的升高而增加;双酚A在酸性条件下的降解率比在中性和碱性条件下要高;阴离子的存在会抑制溶液中双酚A的降解,抑制作用依次为SO42- >Cl- >NO3-;加入腐殖酸后,双酚A的降解受到抑制。双酚A的降解中间产物主要为对苯二酚、对异-丙烯基苯酚、2-甲基-2,3-二氢苯并呋喃和3-甲基-2,3-二氢苯并呋喃。     

氯离子对过硫酸盐氧化苯胺的影响

在高级氧化工艺(AOPs)降解有机污染物过程中,卤代消毒副产物(DBPs)的形成已引起了广泛的关注。然而,氯离子(Cl⁻)在过硫酸盐(PS)降解污染物的过程中的作用机制仍存在争议。基于此,探究了在不同pH下Cl⁻对PS的作用机理,并对可能的反应途径进行了推断。结果表明：在酸性条件(pH=2.5)下,Cl⁻可以与PS反应生成HClO,从而可促进对苯胺(AN)的去除,但并不能对AN进行有效矿化,在PS溶液中加入10 mmol·L⁻¹的Cl⁻后,AN的去除率升高了47.82%,但TOC去除率仅提高了9.78%,且会生成2, 4, 6-三氯苯胺等有害的氯代副产物;相反,在中性(pH=7.5)或碱性条件(pH=11.5)下PS自身能够有效矿化AN,AN的去除率分别提高了57.90%和74.96%,此时TOC去除率分别升高了44.98%和67.15%,而Cl⁻的作用并不显著。通过加入不同淬灭剂对反应过程中的氧化物质进行了识别,发现PS在碱性条件下会生成羟基自由基(HO·)、硫酸根自由基(${\rm{SO}}_4^{ - \cdot}$)和超氧自由基(${\rm{O}}_2^{ - \cdot }$),且在反应过程中起主要作用的为HO·。在碱性条件下,当苯胺的去除率为74.96%时,HO·、${\rm{SO}}_4^{ - \cdot}$和${\rm{O}}_2^{ - \cdot }$对苯胺去除的贡献率分别为51.36%、11.25%和9.79%。对NaCl/PS体系中的产物进行鉴定,检测到7种中间产物,并在此基础上探讨了PS氧化降解AN的可能途径。以上研究结果有助于更好地理解和优化与PS相关的高级氧化技术在实际应用中的污染控制。     

Fenton试剂和活化过硫酸钠氧化降解土壤中的二氯酚和三氯酚

氯酚类物质（chlorophenols, CPs）在环境介质中广泛存在且具有很强环境毒性。为探究化学氧化修复场地氯酚类污染的可行性,通过室内实验、模拟搅拌实验、现场中试,开展应用Fenton试剂和活化过硫酸钠氧化降解土壤CPs的研究。结果表明,化学氧化可有效降解土壤中的CPs,在氧化剂用量和CPs总量摩尔比为15:1时,CaO活化Na2S2O8能高效降解土壤中的二氯酚（2,4-DCP）和三氯酚（2,4,6-TCP）,室内实验和现场中试的去除率均达90%以上,处理后的2,4-DCP和2,4,6-TCP浓度均低于《展览会用地土壤环境质量评价标准》（HJ 350-2007）A类标准限值。Fenton试剂在室内实验中降解率达90%以上,但现场中试对2,4-DCP和2,4,6-TCP的降解率仅为66.1%、23.8%,处理后2,4-DCP浓度仍超过A类标准限值1倍以上。此外,在修复过程中,约70%的2,4-DCP、2,4,6-TCP会向液相转移,因此,需要关注修复系统引入水后污染物向液相中的转移可能造成的二次污染。研究结果可为氯酚类污染土壤的修复提供新思路,并为实际工程应用提供理论依据。     

铁基污泥炭活化过硫酸盐调理污泥脱水

利用给水厂含铁污泥和污水厂污泥混合热解制备铁基污泥炭 (Iron-SBC) ,作为过硫酸盐活化剂,用于调理污泥脱水。研究了Iron-SBC的最佳制备条件及其活化PDS调理污泥脱水的效果,并探究其活化机制。结果表明,Iron-SBC最佳制备条件为给水厂含铁污泥和污水厂污泥比例3∶1、热解温度800 ℃、热解时间1 h。XRD、FT-IR及BET分析结果表明,与原混合污泥相比,Iron-SBC比表面积和孔容增大,表面负载了Fe⁰和FeO、Fe₂O₃、Fe₃O₄等铁的氧化物,并含有大量官能团。在活化PDS过程中,Iron-SBC表面的Fe⁰、铁的氧化物及官能团等均能有效活化PDS,产生SO₄⁻·和·OH自由基。XPS分析结果表明,Iron-SBC表面部分Fe²⁺被氧化为Fe³⁺,官能团C-C、C-OH和C=O等被氧化,并有Fe-O键生成。经Iron-SBC/PDS调理污泥后,CST、SRF和W_c分别由原泥的19.1 s、14.9×10¹² m·kg⁻¹和85.06%下降到8.4 s、5.4×10¹² m·kg⁻¹和73.48%。本研究结果可为含铁污泥和剩余污泥资源化及污泥深度脱水提供参考。     

无机阴离子及有机物对过硫酸盐去除废水中苯胺的影响

突发排放废水中可能含有大量阴离子和有机物,其会淬灭自由基和限制基于过硫酸盐的高级氧化技术的应用。考察了过硫酸钠投加量、Fe²⁺投加量、pH、Cl⁻、${\rm{HCO}}_3^ - $、${\rm{NO}}_3^ - $和其他有机物对过硫酸盐降解苯胺的影响。结果表明：随着过硫酸盐和Fe²⁺浓度的升高,苯胺的去除率也随之增加,但过量投加反而会导致苯胺的去除率下降,活化过硫酸盐氧化去除苯胺的过程符合一级降解动力学;酸性条件有利于Fe²⁺活化过硫酸盐降解苯胺,但在不投加Fe²⁺时碱性条件可以活化过硫酸盐;${\rm{HCO}}_3^ - $和硝基苯的存在会抑制苯胺的去除,而${\rm{NO}}_3^ - $对苯胺的去除基本没有影响;酚的加入会促进苯胺的去除;Cl⁻的存在可以促进Fe²⁺活化过硫酸盐对苯胺的去除,但其中间产物可能会造成潜在的生态风险,后续需进一步研究。同时,在不投加Fe²⁺时,Cl⁻也可以活化过硫酸盐去除苯胺。通过对自由基的识别,发现${\rm{SO}}_4^ - \cdot $在降解过程中起主要作用。此外,提出了1种计算Fe²⁺/过硫酸盐体系中${\rm{SO}}_4^ - \cdot $和·OH稳态浓度的简单方法。该计算方法可用于估算降解过程中产生的${\rm{SO}}_4^ - \cdot $和·OH的量,并评价不同活化体系下${\rm{SO}}_4^ - \cdot $和·OH的产率,为氧化机理的研究提供参考。     

椰壳颗粒活性炭活化过硫酸钠预处理促进高固污泥水解产酸性能

为探究椰壳颗粒活性炭活化过硫酸钠(PS)预处理对高固污泥厌氧发酵水解产酸性能的影响,通过调节挥发性脂肪酸(VFAs)产量、溶解性化学需氧量(SCOD)、溶解性蛋白质及多糖等指标,探究了不同剂量颗粒活性炭(GAC)与PS预处理对高固污泥产酸发酵的最佳条件。结果表明,当PS和GAC投加量分别为1.50 mmol·g⁻¹(以总固体计)和0.65 g g⁻¹(以总固体计)时,在发酵前期产酸速率相比于对照组提高了341.43%,后续发酵过程中,VFAs最大产量相比于对照组提高了28.43%。其中,乙酸作为优质碳源,其质量浓度增加了48.98%;继续增加GAC剂量时,反应器厌氧发酵性能下降,其原因可能是过量GAC会消耗已生成的SO₄⁻·,降低污泥水解作用,同时GAC表面对VFAs的吸附也导致产酸量下降。三维荧光分析表明,在产酸量较高的反应器中,氨基酸、芳香族蛋白质等溶解性有机物的质量浓度较低,这说明适量椰壳颗粒活性炭活化PS预处理方式可提高高固厌氧发酵中微生物对于水解底物的利用率,从而提高污泥的厌氧产酸性能。本研究结果可为炭活化PS预处理技术在高固污泥厌氧消化中的应用提供参考。     

钒氧化物对过硫酸盐降解2,4-二硝基甲苯的影响

钒是土壤中普遍存在的微量元素,钒氧化物对过硫酸盐(PS)降解有机污染物的影响及作用机制目前还不明确。以三氧化二钒(V₂O₃)、二氧化钒(VO₂)和五氧化二钒(V₂O₅)为研究对象,探究了不同PS/钒氧化物体系对2, 4-二硝基甲苯(2, 4-DNT)的降解性能和相关机理。结果表明：不同PS/钒氧化物体系对2, 4-DNT的降解性能具有显著差别,其中PS/V₂O₃体系表现出较强的氧化能力;在反应10 h后,PS/V₂O₃体系中2, 4-DNT的降解率为77.2%,且准一级动力学模型可以很好地描述PS/V₂O₃体系对2, 4-DNT的降解过程。电子自旋共振分析和自由基淬灭实验结果表明,羟基自由基是降解2, 4-DNT的主要自由基。V₂O₃浓度、PS浓度和初始pH是影响PS/V₂O₃体系降解2, 4-DNT的重要因素。2, 4-DNT的降解率随V₂O₃含量升高而先升高后降低,在V₂O₃ 为5.0 mmol·L⁻¹时,2, 4-DNT的降解率最高(91.70%);随着PS浓度的升高,在PS/V₂O₃体系中2, 4-DNT的降解率亦显著提升;当初始pH分别为3.0、5.0、7.0和9.0时,反应10 h后,V₂O₃活化PS对2, 4-DNT的降解率分别为85.91%、80.07%、80.72%和85.72%。以上研究结果可为进一步明确土壤和地下水基质对过硫酸盐原位化学氧化的影响提供参考。     

Destruction of diphenylarsine chloride (CLARK I) with activated ozone

The new technology of Plasmazon® uses the extremely strong oxidation of radicals to break up the compocunds of organic connections, e.g. chemical warfare agents like Clark I. In making a comparison of oxidation to normal ozone, the factor of the Plasmazon® -technology is available up to 10³. The investigation in an experimental test shows that it is possible to destroy the warfare agent character of Clark I. As the possibility of a large-lot application this technology is the method of choice for other chemical or biological warfare agents.     

Mechanism for the destruction of carbon tetrachloride and chloroform DNAPLs by modified Fenton's reagent

The destruction of a carbon tetrachloride DNAPL and a chloroform DNAPL was investigated in reactions containing 0.5 mL of DNAPL and a solution of modified Fenton's reagent (2M H2O2 and 5mM iron(III)-chelate). Carbon tetrachloride and chloroform masses were followed in the DNAPLs, the aqueous phases, and the off gasses. In addition, the rate of DNAPL destruction was compared to the rate of gas-purge dissolution. Carbon tetrachloride DNAPLs were rapidly destroyed by modified Fenton's reagent at 6.5 times the rate of gas purge dissolution, with 74% of the DNAPL destroyed within 24h. Use of reactions in which a single reactive oxygen species (hydroxyl radical, hydroperoxide anion, or superoxide radical anion) was generated showed that superoxide is the reactive species in modified Fenton's reagent responsible for carbon tetrachloride DNAPL destruction. Chloroform DNAPLs were also destroyed by modified Fenton's reagent, but at a rate slower than the rate of gas purge dissolution. Reactions generating a single reactive oxygen species demonstrated that chloroform destruction was the result of both superoxide and hydroxyl radical activity. Such a mechanism of chloroform DNAPL destruction is in agreement with the slow but relatively equal reactivity of chloroform with both superoxide and hydroxyl radical. The results of this research demonstrate that modified Fenton's reagent can rapidly and effectively destroy DNAPLs of contaminants characterized by minimal reactivity with hydroxyl radical, and should receive more consideration as a DNAPL cleanup technology.     

Influence of activated carbon amendment on the accumulation and elimination of PCBs in the earthworm Eisenia fetida

In this study we investigated the use of activated carbon (AC) as a soil amendment for reducing bioavailability of polychlorinated biphenyls (PCBs) to the earthworm Eisenia fetida. Artificial soil was contaminated with PCBs and used in bioaccumulation experiments fresh or after aging for 19 months. PCB bioaccumulation in earthworms was reduced by 68% when AC was placed as a layer without mixing and by 94% when AC was manually mixed into the soil. Aging of the same AC mixed soil for 19 months resulted in an overall reduction of 99% in PCB biouptake. AC-treated aged soil also showed two orders of magnitude lower equilibrium aqueous concentrations of PCBs compared to untreated aged soils. The findings from this study indicate that application of engineered sorbents like AC to PCB impacted soils may greatly reduce PCB uptake at the base of the terrestrial food chain.     

表面活性剂SDBS和Tween 80强化过硫酸盐氧化后土壤中石油烃的缺氧生物降解

化学氧化和微生物联合修复是去除土壤中石油烃 (PHC) 的有效技术,但氧化后土壤中残留PHC的生物有效性较低,难以进一步生物降解。向过硫酸盐 (PS) 氧化后的土壤中加入不同质量浓度和质量比的表面活性剂十二烷基苯磺酸钠 (SDBS) 和聚氧乙烯山梨醇酐单油酸酯 (Tween 80) ,探究其对PS氧化后土壤中PHC解吸、土著微生物群落结构和丰度、PHC缺氧降解的影响。结果表明,缺氧条件下PS氧化和微生物联合降解去除了土壤中30.84%的ΣPHC (C₁₀~C₃₀) 。向PS氧化后土壤中加入SDBS和Tween 80能够有效促进PHC解吸,解吸效果随表面活性剂质量浓度和混合体系中Tween 80比例的增加而增加。加入3 000 mg·L⁻¹表面活性剂继续缺氧培养120 d后,氧化后土壤中Firmicutes和Proteobacteria的总数量较对照组减少了2.13~2.58个数量级,抑制了土壤中PHC的缺氧降解。加入800 mg·L⁻¹表面活性剂后,土壤中Firmicutes和Proteobacteria的总数量较对照组增加了0.17~0.81个数量级,促进了PHC的缺氧降解,在SDBS∶Tween 80=1∶3时ΣPHC残留率最低 (较对照组降低了15.80%) 。本研究结果可为深层石油污染土壤的微生物修复提供参考。     

Model-based evaluation of controlled-release systems in the remediation of dissolved plumes in groundwater

Controlled-release, semi-passive reactive barrier systems have been recently developed as a long-term treatment option for controlling the spread of contaminant plumes in groundwater. This paper describes a new computer code, and applies it to study coupled processes of solute release, reaction, and mass transport in an in situ remediation scheme using the controlled release of potassium permanganate. Confidence with the modeling approach was developed by model verifications and simulating results of a pilot-scale test-cell experiment. Sensitivity analyses indicated the possibilities of treatment inefficiencies due to inability of transverse dispersion to mix the permanganate (MnO(4)(-)) within the zone of reaction, fluctuations in source strength due to variations in flow velocity, and the small length of treatment zone due to strong soil utilization of MnO(4)(-). Although problems associated with the fluctuating source strength and strong soil utilization can be addressed by optimizing the release rate, the inefficiency of transverse dispersion to create mixing could pose a serious limitation. Through a series of model simulations, a system of injection/withdrawal wells in a doublet arrangement was developed to facilitate lateral spreading and mixing of MnO(4)(-). A well-mixed, stable MnO(4)(-) zone with predetermined size (DxL=8m x 2m) and concentration ranges (1.5-20 mg l(-1)) was created by four 1-day injection/withdrawal pumping periods over 24 d. This type of mixing zone may persist for many years with periodic well mixing and replacements of exhausted controlled-release forms. Coupled use of the generalized code with field hydrologic data will help to optimize the design and operation of controlled-release systems in practice.     

活性炭吸附硫化氢及微波辐照解吸研究

研究了两种活性炭对硫化氢的平衡吸附性能力,并对活性炭床层的穿透性进行了考察;吸附饱和和活性炭在微波辐射的作用下进行解吸。实验表明,解吸效率与微波作用时间及温度有关,在本实验条件下H2S解吸效率达90．1％。     

化学改性对活性炭吸附磺胺甲恶唑和布洛芬的影响

以5种化学改性剂(NH3、HCl、H2SO4、HNO3和H2O2)对活性炭进行改性,考察了化学改性对活性炭吸附磺胺甲恶唑(SMX)和布洛芬(IBP)的影响,并结合活性炭改性前后孔结构和表面化学性质的变化特征,利用Pearson相关性分析法,分析了活性炭各项理化指标与其吸附量之间的相关性。结果表明,与原炭相比,各种改性炭对SMX和IBP的吸附能力均有较大幅度提高,24 h时吸附量分别提高了36%~59%和8%~42%。活性炭的比表面积、孔容等物理性质与吸附量的相关系数绝对值均在0.4以内,表现为弱相关。对于SMX,活性炭的羧基官能团与吸附量相关系数r值在0.6~0.8之间;对于IBP,羧基、内酯基分别在吸附的前期和中后期与吸附量表现为强正相关,r达到0.6~0.8以上。本研究中活性炭的表面含氧官能团对其吸附能力表现出更为显著的影响。     

Modeling in situ ozonation for the remediation of nonvolatile PAH-contaminated unsaturated soils

Mathematical models were developed to investigate the characteristics of gaseous ozone transport under various soil conditions and the feasibility of in situ ozone venting for the remediation of unsaturated soils contaminated with phenanthrene. On the basis of assumptions for the mass transfer and reactions of ozone, three approaches were considered: equilibrium, kinetic, and lump models. Water-saturation-dependent reactions of gaseous ozone with soil organic matter (SOM) and phenanthrene were employed. The models were solved numerically by using the finite-difference method, and the model parameters were determined by using the experimental data of Hsu [The use of gaseous ozone to remediate the organic contaminants in the unsaturated soils, PhD Thesis, Michigan State Univ., East Lansing, MI, 1995]. The transport of gas-phase ozone is significantly retarded by ozone consumption due to reactions with SOM and phenanthrene, in addition to dissolution. An operation time of 156 h was required to completely remove phenanthrene in a 5-m natural soil column. In actual situations, however, the operation time is likely to be longer than the ideal time because of unknown factors including heterogeneity of the porous medium and the distribution of SOM and contaminant. The ozone transport front length was found to be very limited (< 1 m). The sensitivity analysis indicated that SOM is the single most important factor affecting in situ ozonation for the remediation of unsaturated soil contaminated with phenanthrene. Models were found to be insensitive to the reaction mechanisms of phenathrene with either gas-phase ozone or dissolved ozone. More study is required to quantify the effect of OH* formation on the removal of contaminant and on ozone transport in the subsurface.     

活性炭纤维的氧化处理研究

采用静态保干器法测定了活性炭纤维对乙醇、丙酮、N-甲基吡咯烷酮的吸附量.研究了酸氧化处理对活性炭纤维吸附性能的影响,并用电位滴定法确定了活性炭纤维氧化前后表面含氧官能团的变化.结果表明,活性炭纤维对3种吸附质的吸附量均随时间延长而增加,但饱和吸附量及达到饱和吸附的时间因吸附质的不同而不同.氧化处理后,活性炭纤维表面含氧官能团发生变化,对乙醇的吸附量增加18%,而对N-甲基吡咯烷酮的吸附量提高了300%.     

活性炭纤维的氧化处理研究

采用静态保干器法测定了活性炭纤维对乙醇、丙酮、N-甲基吡咯烷酮的吸附量。研究了酸氧化处理对活性炭纤维吸附性能的影响,并用电位滴定法确定了活性炭纤维氧化前后表面含氧官能团的变化。结果表明,活性炭纤维对3种吸附质的吸附量均随时间延长而增加,但饱和吸附量及达到饱和吸附的时间因吸附质的不同而不同。氧化处理后,活性炭纤维表面含氧官能团发生变化,对乙醇的吸附量增加18%,而对N-甲基吡咯烷酮的吸附量提高了300%。