Advanced treatment of biologically pretreated coking wastewater by intensified zero-valent iron process(IZVI) combined with anaerobic filter and biological aerated filter(AF/BAF)

Experiments were conducted to investigate the behavior of the sequential system of intensified zero-valent iron process(IZVI) and anaerobic filter and biological aerated filter(AF/BAF) reactors for advanced treatment of biologically pretreated coking wastewater. Particular attention was paid to the performance of the integrated system for the removal of chemical oxygen demand(COD), ammonia nitrogen(NH3-N) and total nitrogen(TN). The average removal efficiencies of COD, NH3-N and TN were 76.28%, 96.76% and 59.97%, with the average effluent mass concentrations of 56, 0.53 and 18.83 mg/L, respectively, reaching the first grade of the national discharge standard. Moreover, the results of gas chromatography/mass spectrum(GC/MS) and gel permeation chromatography(GPC) analysis demonstrated that the refractory organic compounds with high relative molecular mass were partly removed in IZVI process by the function of oxidation-reduction, flocculation and adsorption which could also enhance the biodegradability of the system effluent. The removal efficiencies of NH3-N and TN were achieved mainly in the subsequent AF/BAF reactors by nitrification and denitrification. Overall, the results obtained show that the application of IZVI in combination with AF/BAF is a promising technology for advanced treatment of biologically pretreated coking wastewater.

Synthesis of nanoscale zero-valent iron supported on exfoliated graphite for removal of nitrate

Nano ZVI particles supported on micro-scale exfoliated graphite were prepared by using KBH4 as reducing agent in the H2O/ethanol system. The supported ZVI materials generally have higher activity and greater flexibility for environmental remediation applications. The exfoliated graphite as the support was treated beforehand to hydrophilic material. Nano iron particles are deposited onto the rough graphite surface while those were formed by borohydride reduction. The possible nitrate reduction pathways were proposed. The TEM image shows that iron particles are highly dispersed on the surface of graphite and several of iron particles are imbedded in the pit of support surface. In this synthesis, iron particles have a nearly spherical shape with a grain size of 50?100 nm. The surface areas of materials with different iron loadings of 3.5%, 7.0%, 10.0%, 15.0% and 20.0%(mass fraction) are 2.89, 9.55, 8.45, 23.8 and 6.18 m2·g?1 by BET surface analyzer. The chemical reduction of nitrate by supported nano ZVI in aqueous solution were tested in series batch experiments. Experiment results suggest that NO3? can be more rapidly reduced to NH4+ at neutral pH and anaerobic conditions by supported nano ZVI than unsupported nano ZVI or ZVI scraps. The 15% nano Fe/graphite shows the best reduction efficiency contrasted with other Fe loading particles.

Treatment of simulated wastewater containing Reactive Red 195 by zero-valent iron/activated carbon combined with microwave discharge electrodeless lamp/sodium hypochlorite

A comparative study of treatment of simulated wastewater containing Reactive Red 195 using zero-valent iron/activated carbon （ZVI/AC）, microwave discharge electrodeless lamp/sodium hypochlorite （MDEL/NaCIO） and the combination of ZVI/AC- MDEL/NaCIO was conducted. The preliminary results showed the two steps method of ZVI/AC-MDEL/NaCIO had much higher degradation efficiency than both single steps. The final color removal percentage was nearly up to 100% and the chemical oxygen demand reduction percentage was up to approximately 82%. The effects of operational parameters, including initial pH value of simulated wastewater, ZVI/AC ratio and particle size of ZVI were also investigated. In addition, from the discussion of synergistic effect between ZVI/AC and MEDL/NaCIO, we found that in the ZVI/AC-MEDL/NaCIO process, ZVI/AC could break the azo bond firstly and then MEDLfNaCIO degraded the aromatic amine products effectively. Reversing the order would reduce the degradation efficiency.

Degradation of nitrobenzene-containing wastewater by sequential nanoscale zero valent iron-persulfate process

As nitrobenzene(NB)is structurally stable and difficult to degrade due to the presence of an electron withdrawing group(nitro group).The sequential nanoscale zero valent iron-persulfate(NZVI-Na_(2)S_(2)O_(8))process was proposed in this study for the degradation NB-containing wastewater.The results showed that the NB degradation efficiency and the total organic carbon removal efficiency in the sequential NZVINa_(2)S_(2)O_(8)process were 100%and 49.25%,respectively,at a NB concentration of 200 mg L^(-1),a NZVI concentration of 0.75 g L^(-1),a Na_(2)S_(2)O_(8)concentration of 26.8 mmol L^(-1),an initial pH of 5,and a reaction time of 30 min,which were higher than those(88.53%and 35.24%,respectively)obtained in the NZVI/Na_(2)S_(2)O_(8)process.Sulfate radicals(SO_(4)·-)and hydroxyl radicals(·OH)generated in the reaction were identified directly by electron paramagnetic resonance spectroscopy and indirectly by radical capture experiments,and it was shown that both SO_(4)^(·-)and·OH played a major role in the sequential NZVI-Na_(2)S_(2)O_(8)process.The possible pathways involved in the reduction of NB to aniline(AN)and the further oxidative degradation of AN were determined by gas chromatography-mass spectrometry.

Sorption Kinetic of Arsenate as Water Contaminant on Zero Valent Iron

This study investigates the sorption of arsenate from water using zero-valent iron ZVI as sorbent. Batch experiments were carried out to study the sorption kinetics of arsenate under different concentrations of arsenate varies from 0.5 to 200 mg/l. A kinetic model was considered to describe the arsenates sorption on ZVI material. The kinetics of the arsenate sorption processes were described by the Langmuir kinetic model. The sorption capacity increases with high initial concentration which obtained the maximum sorption 2.1 mg/g at 200 mg/l of arsenate initial concentration. The results show that the rapid initial sorption rates of arsenate were occurred at the beginning of experiments running time, followed by a slower removal that gradually approaches an equilibrium condition. The data from laboratory batch experiments were used to verify the simulation results of the kinetic model resulting in good agreement between measured and modeled results. The results indicate that ZVI could be employed as sorbent materials to enhance the sorption processes and increase the removal rate of arsenate from water.

Remediation of Malathion Contaminated Soil Using Zero Valent Iron Nano-Particles

In this study, iron nano-particles were used to remediate malathion contaminated soil in the concentration range of 1 - 10 μg?g–1. The zero valent iron nano-particles were prepared by reducing ferric chloride solution with sodium boro- hydride for remediation of the soil. The optimized quantity of iron nano particles was found to be 0.1 g?kg–1 of soil con- taminated with 10 μg?g–1 of malathion. Malathion was determined in the soil after leaching to water at pH 8.2 and fol- lowed by its oxidation with slight excess of N-bromosuccinimide (NBS). The unconsumed NBS was estimated by measuring the decrease in the color intensity of rhodamine B. Degradation product formed during the oxidation of ma-lathion by zero valent iron was monitored by the Attenuated Total Reflectance Fourier Transform Infrared Spectros- copy (ATR-FTIR). The results clearly showed that quantitative oxidation of malathion was achieved within eight min- utes after the addition of zero valent iron nano particles.

Evaluating Effectiveness and Permanence of Selenium Treatment in a Solid Matrix via Aqueous-Mediated Zero Valent Iron Reaction

Increasingly, as regulatory limits become more stringent, selenium has become a parameter of concern. Selenium is a naturally occurring element that is largely mobilized by anthropogenic activity such as mining for fuel and subsequent combustion, metal ore refining and processing, and agricultural irrigation. Of concern is removing selenium liquid matrices and immobilizing it from leachable solid matrices. Chemical reduction and stabilization using zero valent iron (ZVI) is applicable to both concerns. The solid matrix case study is applicable to ash ponds solids or industrial bag house dust solids. This paper presents data for treatment and stabilization of selenium within a solid matrix using ZVI. The methodology uses an aqueous mediate reaction to promote a stable solid matrix of non-leachable selenium. The paper describes matrix challenges and key variables that effected successful treatment. Testing with simulated and real bag house dust solids were used to establish data to support the permeance of the reaction. The data show that ZVI converts ionic selenium to a zero valent state in the solid matrix. It was also recognized that a fraction of ionic selenium may fail to react with the ZVI, but the results show that despite the presence of the unreacted ionic selenium, the toxicity characteristic leachate procedure (TCLP) results following treatment do not exceed the 1 mg/L hazardous waste criteria.

H₂Gas Charging of Zero-Valent Iron and TCE Degradation

Granular zero-valent iron (ZVI) has been widely used to construct permeable reactive barriers (PRB) for the in situ remediation of groundwater contaminated with halogenated hydrocarbons. In the anaerobic condition of most groundwater flow systems, iron undergoes corrosion by water and results in hydrogen gas generation. Several studies have shown that some of the hydrogen gas generated at the iron/water interface can diffuse into the iron lattice. Hydrogen gas also can be an electron donor for dechlorination of chlorinated compounds. In this study, the possibility of hydrogen gas bound in the lattice of ZVI playing a role in dehalogenation and improving the degradation efficiency of ZVI was evaluated. Two different granular irons were tested: one obtained from Quebec Metal Powders Ltd (QMP) and the other from Connelly-GPM. Ltd. For each type of iron, two samples were mixed with water and sealed in testing cells. Since the rate of hydrogen entry varies directly with the square root of the hydrogen pressure, one sample was maintained for several weeks under near-vacuum conditions to minimize the amount of hydrogen entering the iron lattice. The other sample was maintained for the same period at a hydrogen pressure of over 400 kPa to maximize the amount of hydrogen entering the iron lattice. The degradation abilities of the reacted ironsand the original iron materials were tested by running several sets of batch tests. The results of this study show little to no improvement of inorganic TCE degradation reactions due to the presence of lattice-stored hydrogen in iron material. This is probably due to the high energiesrequired to release hydrogen trapped in the iron lattice. However, there are certain chemical compounds that can promote hydrogen release from the iron lattice, and there may be bacteria that can utilize lattice-bound hydrogen to carry out dechlorination reactions.

Application of Iron Nanoparticles Synthesized by Green Tea for the Removal of Hexavalent Chromium in Column Tests

Nano zero valent iron particles (nZVI) are popular the last few years because of the numerous applications in remediation of a wide range of pollutants in contaminated soils and aquifers. The nZVI particles can be 10 - 1000 times more reactive than granular or micro-scale ZVI particles due to the small particle size, large specific surface area and high reactivity. An alternative green synthesis procedure was used for the production of nano zero valent iron particles (nZVI) using green tea (GT) extract, which is characterized by its high antioxidant content. Polyphenols in green tea extract possess double role in the synthesis of nZVI, because they not only reduce ferric cations, but also protect nZVI from oxidation and agglomeration as capping agents. The objective of current study was to simulate ata laboratory scale the attachment of GT-nZVI particles on soil material and study the effectiveness of attached nanoparticles for removing hexavalent chromium (Cr(VI)) from contaminated groundwater flowing through the porous soil bed. Column tests were carried out with various flowrates in order to examine the effect of contact time between the attached on porous medium nZVI and the flow-through solution on Cr(VI) reduction. After the completion of column tests the soil material in each column was split in 5 vertical sections, which were further subjected to chemical analyses and leaching tests. According to the results of the study increasing the contact time favors the reduction and removal of Cr(VI) from the aqueous phase. The reductive precipitation of Cr can be described as a reaction that follows a pseudo-first order kinetic law, with rate constant equal to k = 0.0243 ± 0.0011 min-1. Leaching tests indicated that precipitated chromium is not soluble. In the examined soil material, the total amount of precipitated Cr was found to range between 280 and 890 mg/(kg soil), while soluble Cr was less than 1.4 mg/kg and most probably it was due to the presence of residual Cr(VI) solution in the porosity of soil.

LDPE/m-nZVI复合膜的制备及性能

为克服脱氧剂小袋包装与食品混装带来的安全问题,采用硼氢化钾(KBH4)液相还原法制备了油酸钠(NaOl)改性纳米零价铁(m-nZVI),将其与低密度聚乙烯(LDPE)熔融共混后热压成膜,制备了包装用LDPE/m-nZVI阻氧复合膜。利用傅里叶变换红外光谱仪、热重分析仪、差示扫描量热仪、万能拉伸试验机和气体渗透仪对复合膜的结构与性能进行表征和测定。结果表明:m-nZVI和LDPE的复合是物理共混;加入m-nZVI后,LDPE的热稳定性基本不变;随着m-nZVI含量的增加,复合膜的抗拉强度和断后伸长率先增大后减小,m-nZVI质量分数为2%时,抗拉强度和断后伸长率达到最大,较LDPE膜分别提高了41.4%和23.4%;复合膜的氧气透过系数也呈现出先减小后增大,当m-nZVI质量分数为3%时,复合膜的氧气透过系数最小,较LDPE膜降低了40.9%。复合膜结晶过程中,m-nZVI起异相成核的作用,改善了复合膜的结晶行为,使复合膜的结构和性能得到改善,力学性能和阻隔性能都得到提高。

STPP-nZVI修复铀污染地下水的性能及机理研究

铀是一种重要的战略资源,同时也是一种具有化学毒性和放射性毒性的重金属元素。目前,对铀矿山地下水中铀的高效修复仍是环境保护和生态安全面临的巨大挑战。采用三聚磷酸钠对纳米零价铁改性,成功制备了三聚磷酸钠改性纳米零价铁(STPP-nZVI),研究了溶液pH、STPP-nZVI用量、温度、时间、U(Ⅵ)浓度和干扰离子对STPP-nZVI修复地下水中U(Ⅵ)的影响,并采用FTIR、SEM-Mapping和XPS探讨了STPP-nZVI修复铀污染地下水的机理。结果表明,STPP-nZVI适合处理弱酸性和碱性铀污染地下水,在pH=5.0时,STPP-nZVI对U(Ⅵ)的最大吸附量达102.72 mg/g,对U(Ⅵ)的吸附为自发的吸热过程,STPP-nZVI对铀的去除主要归功于吸附和还原作用。STPP-nZVI材料对于处理弱酸性和碱性铀污染地下水具有一定的应用前景。

零价铁(ZVI)工艺处理水中铬、砷污染的研究进展综述

工业和城市活动导致水体中的铬、砷污染物浓度升高,严重威胁人类的健康。近年来,使用零价铁(ZVI)处理地下水和废水中的毒性污染物备受关注,该法被证明有较高的处理效果。该文综述了ZVI处理水中铬、砷污染的研究进展,并对未来的研究方向提出了展望。

ZVI固定床-SBR耦合工艺强化氯代硝基苯的降解

研究了零价铁（ZVI）固定床-序批式生物反应器（SBR）耦合工艺对2-氯硝基苯（2-ClNB）转化与降解强化作用.结果表明,ZVI固定床可稳定还原转化2-ClNB为2-氯苯胺（2-ClAn）,表面积归一化速率常数（Ksa）为（3.20±0.35）×10^-2L·m^-2·h^-1;ZVI固定床出水作为SBR进水,在HRT为20h、2-ClAn负荷为3.6-111.8g·m^-3·d^-1、COD负荷（外加碳源）为130.9-854.4g·m^-3·d^-1条件下稳定运行SBR,其2-ClAn去除率达99.9%以上,COD去除率达92.3%±5.5%,2-ClAn污泥比降解速率达0.31g·g^-1·d^-1;耦合系统在不添加其它碳源、氮源条件下,TOC去除率达95.4%,总氮去除率为46.1%.而以未经ZVI预处理的2-ClNB为进水的SBR对照实验发现,2-ClNB去除率仅为25.3%±10.2%,主要以挥发形式去除.研究结果揭示,ZVI-SBR耦合工艺可强化氯代硝基苯类污染物的降解与矿化.

ZVI还原转化硝基芳烃特性及QSAR的研究

研究了零价铁(ZVI)还原转化硝基芳烃(NAC)的特性以及还原速率与分子连接性指数(MCI)的关系.结果表明:厌氧乙酸/碳酸氢钠缓冲体系(pH 5.0)中,ZVI还原转化硝基芳烃形成氨基芳烃,转化过程遵循准一级反应动力学;ZVI还原转化目标污染物活性受苯环上取代基种类、数目和位置影响,活性大小顺序为3,4-二氯硝基苯(3,4-DCN)>邻氯硝基苯(2-CNB)>对硝基苯胺(4-NA)>对硝基苯酚(4-NP)>对氯硝基苯(4-CNB)>硝基苯(NB);目标污染物一阶分子连接性指数1XV、四阶分子连接性指数4XpVc和非色散力因子Δx与其还原转化速率具有良好的定量的结构-活性关系(QSAR).

纳米零价铁(nZVI)对蚯蚓-微生物-土壤生态系统的毒性效应研究

为解决土壤重金属污染问题,纳米零价铁(nZVI)被广泛应用且备受关注,而nZVI对土壤无脊椎动物、土壤质量、微生物群落等的潜在影响缺乏系统的研究。本文以赤子爱胜蚓(Eisenia foetida)[蚯蚓密度为0、10条∙kg^(−1)(土)]为研究对象,探讨不同浓度nZVI(nZVI土壤质量为0、0.05%、0.25%和0.50%)暴露15 d、30 d和45 d后,蚯蚓-微生物-土壤生态系统的响应,为评价nZVI的环境安全性提供参考。结果表明,暴露45 d后,nZVI对蚯蚓存活率和生物量无显著影响,0.50%nZVI处理的蚯蚓存活率和体内MDA含量与15 d相比分别降低27.66%和0.86 nmol∙g^(−1);而蚯蚓生物量和CAT活性分别增加1.20倍和2.62倍。门或属水平下,nZVI对土壤微生物相对丰度、多样性指数和丰度指数无显著影响;与无添加nZVI处理相比,蚯蚓介导下0.50%nZVI处理土壤中大团聚体(>250μm)所占比例、团聚体平均重量直径和速效磷含量分别显著升高15.69%、12.59%和21.20%。蚯蚓介导下nZVI处理中土壤大团聚体所占比例、团聚体平均重量直径显著高于无蚯蚓投加的nZVI处理,可见,nZVI胁迫下蚯蚓活动极显著提高土壤团聚体结构的稳定性(P<0.01)。本研究发现长期暴露nZVI对土壤微生物群落特征无显著影响,但可以促进蚯蚓的生长,从而进一步提高了土壤营养元素的生物有效性,为nZVI应用于污染修复与治理的环境安全性评估提供了科学依据。

nZVI/PANI/ATP纳米纤维复合材料制备及对Cr(VI)的去除性能

采用原位聚合法合成了硝酸掺杂的纳米零价铁/聚苯胺/凹凸棒黏土(nZVI/PANI/ATP)纳米纤维复合材料,用于去除废水中的Cr(VI)。考察了投料质量、吸附时间和p H值对其吸附性能的影响,对吸附过程进行了动力学和热力学分析。结果表明,PANI/ATP表面负载纳米零价铁(nZVI),解决了nZVI颗粒的团聚及在处理Cr(Ⅵ)时容易被腐蚀和钝化的问题。复合材料制备过程中Fe、An和ATP的质量比为0.74∶1∶4时,所制备的材料吸附容量达到87.95 mg/g,nZVI/PANI/ATP复合材料对Cr(Ⅵ)的吸附符合准二级动力学模型,吸附为化学吸附。

ZVI-SRB协同处理铀(Ⅵ)废水的影响因素

采用还原性铁粉和硫酸盐还原菌协同生物还原沉淀消除铀矿冶废水中的放射性U污染,研究pH值、SO42-和铀的初始浓度对ZVI-SRB协同还原沉淀U的影响。结果表明,溶液中的pH值对U生物沉淀存在显著影响,在pH为6.0时,铀的除去率在24h内高达90.5%,随pH值的降低溶液中铀的除去率降低。铀的初始浓度和SO42-的浓度对ZVI-SRB体系协同还原沉淀U影响比单纯SRB处理要小。利用ZVI-SRB处理溶液中的铀废水的放射性U污染具有重要意义。

不同碳源对ZVI-SRB-SO_4^(2-)体系中生物活性的影响

选取不同有机物作为碳源,考察碳源对于高硫酸盐(SO42-)环境中硫酸盐还原菌(Sulfate-reducing bacteria,SRB)生物活性的影响;通过零价铁(Zero-valent iron,ZVI)的添加考察ZVI对于SRB生物活性的促进作用.结果表明:碳源会对SRB的生物活性产生很大影响,导致产生不同的SO42-还原效率;在SRB分别以柠檬酸钠、乳酸钠和可溶性淀粉为碳源时,通过添加ZVI可以明显提高SRB的生物活性;乳酸钠最适合作为SRB处理高SO42-浓度废水的碳源,当乳酸钠作为碳源时,SRB-ZVI体系对于SO42-初始质量浓度低于8 500 mg/L的废水具有良好的处理效果,即使废水中SO42-初始质量浓度达到11 000 mg/L时,SRB-ZVI体系对于SO42-的还原效率依然可以达到81.8%.

nZVI/BC与(Cu-Pd)/BC协同提高硝酸盐的去除和氮气的选择性

为探明纳米零价铁(nZVI)/BC与(Cu-Pd)/BC联合作用对水中硝酸盐的去除机理,分别负载纳米金属于小麦秸秆生物炭上,制得nZVI/BC与(Cu-Pd)/BC两种复合材料,并通过SEM、TEM、EDS、XRD对材料进行表征分析,从nZVI/BC的SEM中可以看出,纳米零价铁较好地分散在生物炭(BC)上面;从(Cu-Pd)/BC的TEM图中看出,纳米铜钯均有效地负载于BC上且分布均匀。结果表明,nZVI/BC:(Cu-Pd)/BC体系中硝酸盐的去除率可达100%,氮气转化率达到42%。当pH为4.05时硝酸盐去除效果最佳;硝酸盐去除率随着初始浓度的升高而降低;溶解氧的存在会降低硝酸盐去除率;存在PO_(4)^(3-)对去除效率的影响最大,去除率降低至15.8%,而CO_(3)^(2-)和SO_(4)^(2-)的存在对去除氮的影响不大,去除率接近100%。动力学研究表明:在最佳条件下,nZVI/BC与(Cu-Pd)/BC联合作用对NO_(3)^(-)-N、NO_(2)^(-)-N的去除均符合准二级吸附动力学模型,反应过程以还原反应为主。