Fenton试剂氧化苯酚过程中Fe（Ⅱ）浓度的变化

考察了Fenton试剂氧化降解苯酚过程中Fe(Ⅱ)浓度的变化,并通过实验探讨了其变化的原因.实验结果表明,在Fenton反应发生的第1 rain内,Fe(Ⅱ)浓度可降低到初始浓度的60%左右,随着反应的继续Fe(Ⅱ)浓度在大约20min降低到最小值,然后开始增大,说明了Fe(Ⅲ)还原作用的存在;Fenton试剂氧化降解苯酚的中间产物包括对苯二酚、邻苯二酚、间苯二酚和苯醌等,其中前三者能对Fe(Ⅲ)有效还原,是Fenton试剂氧化降解苯酚过程中Fe(Ⅲ)还原的主要途径之一.     

异化铁还原细菌Klebsiella sp.KB52还原重金属Cr(Ⅵ)

以分离自海洋沉积物中异化铁还原细菌Klebsiella sp. KB52为研究对象,分析微生物异化铁还原过程对还原Cr(Ⅵ)的影响。菌株KB52是一株非典型耐铬细菌,在Cr(Ⅵ)浓度10～50 mg·L~(-1)范围内,该菌株生长受到明显抑制。当将Fe(OH)~3添加至培养体系,菌株KB52能够良好生长并具有铁还原性质,同时提高了Cr(Ⅵ)还原效率。Fe(OH)~3浓度为300 mg·L~(-1)时,菌株KB52细胞生长指标OD600和累积产生Fe(Ⅱ)浓度最高,分别是1.4760±0.04和(39.79±1.45)mg·L~(-1),Cr(Ⅵ)还原率(42%)是对照组的5.25倍。当柠檬酸铁作为电子受体,菌株KB52还原Fe(Ⅲ)效率最高,Fe(Ⅱ)累积浓度达到(109.87±1.27)mg·L~(-1),Cr(Ⅵ)还原率提高至67%。上述结果表明,菌株KB52能够利用可溶性和不可溶性Fe(Ⅲ)作为电子受体进行生长,同时其异化铁还原过程偶联Cr(Ⅵ)还原。研究结果可为利用异化铁还原细菌还原Cr(Ⅵ)提供理论依据,拓宽微生物治理重金属污染的应用范围。     

腐殖酸还原Fe(Ⅲ)的影响因素研究

研究了腐殖酸还原溶解性Fe(Ⅲ)反应的影响因素,以及腐殖酸对赤铁矿、磁铁矿、针铁矿和钢渣4种含Fe(Ⅲ)矿物的还原作用,探讨了腐殖酸还原溶解Fe(Ⅲ)的反应机制.结果表明,腐殖酸还原溶解性Fe(Ⅲ)的反应符合零级动力学方程.增加腐殖酸或溶解性Fe(Ⅲ)浓度、降低pH或使用可见光照射均能促进反应进行.腐殖酸能直接还原含Fe(Ⅲ)矿物生成溶解性Fe(Ⅱ),对不同含Fe(Ⅲ)矿物的还原效果依次为针铁矿>赤铁矿>磁铁矿>钢渣.红外光谱分析表明,腐殖酸含有的还原性官能团酚羟基和羧基与溶解性Fe(Ⅲ)络合在一起形成稳定的螯合结构,传递电子给溶解性Fe(Ⅲ).溶解性Fe(Ⅲ)得到电子,生成溶解性Fe(Ⅱ).     

不同条件下Fe(Ⅲ)催化有机酸光化学还原 Cr(Ⅵ)的比较研究

为开发含Cr(Ⅵ)废水处理工艺提供必要资料,对不同条件下Fe(Ⅲ)催化有机酸光化学还原Cr(Ⅵ)进行了比较研究.研究结果表明,Cr(Ⅵ)的还原不仅受pH、Fe(Ⅲ)或有机酸的起始浓度以及共存阳离子的影响,而且还与有机酸种类有关.低pH的酸性条件有利于cr(Ⅵ)的光化学还原,在pH 3.0条件下经3h后的还原率达89.9％,在pH 5.0经3h后其还原率为37.3％.Fe(Ⅲ)或有机酸起始浓度增高会促进Cr(Ⅵ)的还原,在pH3.0和Fe(Ⅲ)浓度高于Cr(Ⅵ)浓度条件下导致在3h后Cr(Ⅵ)的光化学还原率达100％.共存Al(Ⅲ)或Cu(Ⅱ)会抑制Cr(Ⅵ)的光化学还原.由Fe(Ⅲ)催化3种有机酸对Cr(Ⅵ)的光化学还原作用大小次序为:酒石酸＞柠檬酸＞苹果酸.还对不同条件影响Cr(Ⅵ)的光化学还原可能机制作了讨论.     

Fe0钝化膜的生物还原及其脱氮除磷

微生物的异化Fe(Ⅲ)还原是一种能够利用Fe(Ⅲ)作为末端电子受体在无氧条件下氧化有机物的产能过程。结合这一特性,考察了在兼性厌氧/严格厌氧条件下Fe⁰钝化膜作为Fe(Ⅲ)源时的生物还原能力以及对N、P等营养元素的去除效果。结果表明,严格厌氧条件下微生物异化Fe(Ⅲ)还原能力较好,富集培养至7 d,累计Fe(Ⅱ)浓度达到最大,最大产生速率为98.69 mg/(L·d),同时TP去除率高达97.1%以上。而体系对NH₄⁺-N、TN的去除相对滞后,培养至13 d,去除率开始增大,最终分别达到86.6%和76.1%。这为装填有海绵铁+聚氨酯泡沫载体的SBBR中填料的原位再生问题提供了解决思路。     

CaO2及H2O2类Fenton降解土壤石油烃污染

采用H_2O_2/Fe(Ⅲ)/柠檬酸类Fenton体系和CaO_2/Fe(Ⅲ)/柠檬酸类Fenton体系修复土壤石油污染,考察了氧化剂种类、氧化剂投加量、 Fe(Ⅲ)浓度和柠檬酸浓度对柴油降解效果的影响,并进一步研究比较了CaO_2/Fe(Ⅲ)/柠檬酸和H_2O_2/Fe(Ⅲ)/柠檬酸2种修复方式对土壤原著微生物群落变化及豌豆植株生长所带来的生态毒性效应。单因素实验结果表明:在其他条件相同的情况下,CaO_2类Fenton降解柴油效果优于H_2O_2类Fenton降解效果;柴油降解率随着氧化剂投加量、Fe(Ⅲ)和柠檬酸浓度的增大呈现先增后降的趋势。当CaO_2浓度为166.67 mmol·L~(-1)、Fe(Ⅲ)浓度为27.78 mmol·L~(-1)、柠檬酸浓度为27.78 mmol·L~(-1)时,反应24 h后,土壤中柴油降解率达到44.14%。生态毒性实验表明:CaO_2类Fenton处理后土壤微生物群落的丰富度和多样性指数均有所提高,H_2O_2类Fenton处理后均有所降低,2种处理方式均在不同程度上改变了土壤微生物群落的优势菌门构成;CaO_2及H_2O_2类Fenton处理均抑制了豌豆植株的生长,发芽率、植株干重、株高、叶绿素含量等测试指标均下降,其中H_2O_2类Fenton处理的抑制效果更为明显。进一步分析可知,CaO_2类Fenton处理技术比H_2O_2类Fenton处理技术更适用于石油污染土壤修复。     

Fe(Ⅲ)-酒石酸盐配合物对双酚A模拟废水的光处理

主要研究了卤灯光照下,Fe(Ⅲ)-酒石酸盐配合物体系对双酚A(BPA)的光化学降解,考查了光源、初始pH值、各反应物初始浓度等因素对双酚A光降解的影响。结果表明:卤灯或太阳光照射下,BPA在Fe(Ⅲ)-酒石酸盐配合物体系中能够有效地实现光降解;光强从8.8×104Lux增加到1.2×105Lux,BPA降解率从68.9%提高到92.8%;BPA的降解率及Fe(Ⅲ)-酒石酸盐配合物光解过程中产生的.OH浓度均随pH增大而减小;Fe(Ⅲ)-酒石酸盐配合物光氧化BPA过程中溶液的pH逐渐升高;过量的酒石酸盐有利于Fe(Ⅲ)/Fe(Ⅱ)的循环进行。     

Fe(Ⅲ)-酒石酸盐配合物体系的光解特性

以Fe(Ⅲ)-酒石酸配合物体系光化学过程中产生的Fe(Ⅱ)和.OH为主要检测对象,探讨了Fe(Ⅲ)-酒石酸配合物体系光化学反应的基本规律及影响因素。结果表明,体系的光化学过程能产生Fe(Ⅱ)和.OH;产生Fe(Ⅱ)的速率远高于产生.OH的速率;Fe(Ⅱ)生成浓度在pH 3.50时最大,.OH则在pH 3.00时最大;配合物的光化学过程中会伴随pH的升高;在照度为3.6×103Lux的日光灯照射下,Fe(Ⅲ)-酒石酸盐配合物初级光解的速率常数为2.1×10-3S-1;Fe(Ⅱ)是高价重金属的主要还原剂,.OH是有机物的主要氧化剂。     

Fe^0钝化膜的生物还原及其脱氮除磷

微生物的异化Fe（Ⅲ）还原是一种能够利用Fe（III）作为末端电子受体在无氧条件下氧化有机物的产能过程。结合这一特性，考察了在兼性厌氧／严格厌氧条件下Fe^0钝化膜作为Fe（111）源时的生物还原能力以及对N、P等营养元素的去除效果。结果表明，严格厌氧条件下微生物异化Fe（Ⅲ）还原能力较好，富集培养至7d，累计Fe（II）浓度达到最大，最大产生速率为98．69mg／（L·d），同时TP去除率高达97．1％以上。而体系对NH4-N、TN的去除相对滞后，培养至13d，去除率开始增大，最终分别达到86．6％和76．1％。这为装填有海绵铁＋聚氨酯泡沫载体的SBBR中填料的原位再生问题提供了解决思路。     

生物铁泥的Fe（Ⅲ）还原能力及影响因素

以生物铁泥和普通活性污泥为对象,在不同碳源及兼氧/厌氧条件下采用实验室恒温培养的方法考察了不同活性污泥的Fe（Ⅲ）还原性能。研究结果表明,不同活性污泥Fe（Ⅲ）还原能力相差较大,生物铁泥的Fe（Ⅲ）还原性能明显优于普通活性污泥,在兼性厌氧与严格厌氧条件下,分别是普通活性污泥的1.87倍和1.76倍;碳源对生物铁泥的Fe（Ⅲ）还原影响较小,而对普通活性污泥的Fe（Ⅲ）还原过程呈现出较明显的负影响;在实验控制的兼氧/厌氧条件下,2种活性污泥厌氧条件下Fe（Ⅲ）还原能力均大于兼氧条件。为活性污泥Fe（Ⅲ）还原过程的工程实际应用提供了理论依据。     

日光/H_2O_2/草酸铁体系对垃圾渗滤液深度处理的试验研究

以草酸铁络合物/H2O2作光氧化剂,利用日光对垃圾渗滤生化出水进行了光氧化降解试验。结果表明,在溶液的初始体系pH=3.0,H2O2投加量为460mg/L,Fe3+质量浓度为20mg/L条件下,反应60min后,CODCr去除率可达80%以上;溶液初始体系的pH、H2O2和Fe3+的投加量及废水的水质对光解过程有显著影响,而且在太阳光照射下,CODCr去除率比紫外光照射下高。研究表明,在一定试验条件下,用日光/H2O2/草酸铁体系对城市垃圾渗滤液处理效果较好,可作为垃圾渗滤液的深度处理。     

A strategy for aromatic hydrocarbon bioremediation under anaerobic conditions and the impacts of ethanol: a microcosm study

Increased use of ethanol-blended gasoline (gasohol) and its potential release into the subsurface have spurred interest in studying the biodegradation of and interactions between ethanol and gasoline components such as benzene, toluene, ethylbenzene and xylene isomers (BTEX) in groundwater plumes. The preferred substrate status and the high biological oxygen demand (BOD) posed by ethanol and its biodegradation products suggests that anaerobic electron acceptors (EAs) will be required to support in situ bioremediation of BTEX. To develop a strategy for aromatic hydrocarbon bioremediation and to understand the impacts of ethanol on BTEX biodegradation under strictly anaerobic conditions, a microcosm experiment was conducted using pristine aquifer sand and groundwater obtained from Canadian Forces Base Borden, Canada. The initial electron accepter pool included nitrate, sulfate and/or ferric iron. The microcosms typically contained 400 g of sediment, 600 approximately 800 ml of groundwater, and with differing EAs added, and were run under anaerobic conditions. Ethanol was added to some at concentrations of 500 and 5000 mg/L. Trends for biodegradation of aromatic hydrocarbons for the Borden aquifer material were first developed in the absence of ethanol, The results showed that indigenous microorganisms could degrade all aromatic hydrocarbons (BTEX and trimethylbenzene isomers-TMB) under nitrate- and ferric iron-combined conditions, but not under sulfate-reducing conditions. Toluene, ethylbenzene and m/p-xylene were biodegraded under denitrifying conditions. However, the persistence of benzene indicated that enhancing denitrification alone was insufficient. Both benzene and o-xylene biodegraded significantly under iron-reducing conditions, but only after denitrification had removed other aromatics. For the trimethylbenzene isomers, 1,3,5-TMB biodegradation was found under denitrifying and then iron-reducing conditions. Biodegradation of 1,2,3-TMB or 1,2,4-TMB was slower under iron-reducing conditions. This study suggests that addition of excess ferric iron combined with limited nitrate has promise for in situ bioremediation of BTEX and TMB in the Borden aquifer and possibly for other sites contaminated by hydrocarbons. This study is the first to report 1,2,3-TMB biodegradation under strictly anaerobic condition. With the addition of 500 mg/L ethanol but without EA addition, ethanol and its main intermediate, acetate, were quickly biodegraded within 41 d with methane as a major product. Ethanol initially present at 5000 mg/L without EA addition declined slowly with the persistence of unidentified volatile fatty acids, likely propionate and butyrate, but less methane. In contrast, all ethanol disappeared with repeated additions of either nitrate or ferric iron, but acetate and unidentified intermediates persisted under iron-enhanced conditions. With the addition of 500 mg/L ethanol and nitrate, only minor toluene biodegradation was observed under denitrifying conditions and only after ethanol and acetate were utilized. The higher ethanol concentration (5000 mg/L) essentially shut down BTEX biodegradation likely due to high EA demand provided by ethanol and its intermediates. The negative findings for anaerobic BTEX biodegradation in the presence of ethanol and/or its biodegradation products are in contrast to recent research reported by Da Silva et al. [Da Silva, M.L.B., Ruiz-Aguilar, G.M.L., Alvarez, P.J.J., 2005. Enhanced anaerobic biodegradation of BTEX-ethanol mixtures in aquifer columns amended with sulfate, chelated ferric iron or nitrate. Biodegradation. 16, 105-114]. Our results suggest that the apparent conservation of high residual labile carbon as biodegradation products such as acetate makes natural attenuation of aromatics less effective, and makes subsequent addition of EAs to promote in situ BTEX biodegradation problematic.     

生活污水二级生物处理后的铁盐混凝除磷试验研究

以生活污水二级生物处理后的出水为研究对象，考察了铁盐对浓度在2－4mg/L范围内的总磷的混凝去除效果及影响因素。结果表明，铁盐除磷的最佳pH为7.5-8；铁盐投加量较低时，适当提高GT值可使总磷去除率增加15％－20％；在适当的混凝搅拌条件下，三阶铁盐和聚合硫酸铁对总磷的去除率均在70％以上，混凝后过滤可使出水中总磷降至0.5mg/L以下。     

微生物代谢与Fe3+催化氧化脱除烟气中SO2的研究

利用自制的鼓泡反应器,进行了含氧化亚铁硫杆菌的酸性铁溶液脱除烟气中SO2的实验研究.结果表明,细菌直接脱硫的效果较差;Fe3 在脱硫实验过程中既有催化作用,又有氧化作用;细菌主要起氧化Fe2 为Fe3 的作用,再通过Fe3 脱硫.Fe3 存在一个最佳质量浓度,在7～8 g/L左右.当初始Fe3 质量浓度为7.37 g/L时,脱硫10 h,其效率仍高达80%.     

硫铁矿烧渣制备无机复合混凝剂聚合铁盐

对用硫铁矿烧渣制备无机复合混凝剂聚合铁盐进行了试验研究,考察了影响烧渣酸溶和铁聚合的因素。结果表明,硫酸浓度、反应时间和体系温度等是影响硫铁矿烧渣中铁溶出率的主要因素,在烧渣液溶过程中添加适当的助溶剂,不仅能够加快酸浸速度,而且还可以提高产品的混凝性能。     

几种无机混凝剂对酸性红染料的脱色研究

比较了无机混凝剂氯化铁、氯化铝和硫酸铝对染色废水的脱色效果，实验结果表明：氯化剂的絮凝脱色效果最佳，其适宜ｐＨ在２．５￣４．５之间，当加入适量的膨润土，则能拓宽ｐＨ适用范围，稳定脱色效果。     

Hydrogen Sulfide Gas Treatment by a Chemical‐Biological Process: Chemical Absorption and Biological Oxidation Steps

In order to remove high concentrations of hydrogen sulfide (H₂S) gas from anaerobic wastewater treatments in livestock farming, a novel process was evaluated for H₂S gas abatement involving the combination of chemical absorption and biological oxidation processes. In this study, the extensive experiments evaluating the removal efficiency, capacity, and removal characteristics of H₂S gas by the chemical absorption reactor were conducted in a continuous operation. In addition, the effects of initial Fe^2 + concentrations, pH, and glucose concentrations on Fe^2 + oxidation by Thiobacillus ferrooxidans CP9 were also examined. The results showed that the chemical process exhibited high removal efficiencies with H₂S concentrations up to 300 ppm, and nearly no acclimation time was required. The limitation of mass‐transfer was verified as the rate‐determining step in the chemical reaction through model validation. The Fe^2 + production rate was clearly affected by the inlet gas concentration as well as flow rate and a prediction equation of ferrous production was established. The optimal operating conditions for the biological oxidation process were below pH 2.3 and 35°C in which more than 90% Fe^3 + formation ratio was achieved. Interestingly, the optimal glucose concentration in the medium was 0.1%, which favored Fe^2 + oxidation and the growth of T. ferrooxidans CP9.     

Development of a hybrid microbial fuel cell (MFC) and fuel cell (FC) system for improved cathodic efficiency and sustainability: the M2FC reactor

In an effort to improve the efficiency and sustainability of microbial fuel cell (MFC) technology, a novel MFC reactor, the M2FC, was constructed by combining a ferric-based MFC with a ferrous-based fuel cell (FC). In this M2FC reactor, ferric ion, the catholyte in the MFC component, is regenerated by the FC system with the generation of additional electricity. When the MFC component was operated separately, the electricity generation was maintained for only 98 h due to the depletion of ferric ion in the catholyte. In combination with the fuel cell, however, the production of power was sustained because ferric ion was continually replenished from ferrous ion in the FC component. Moreover, the regeneration process of ferric ion by the FC produced additional energy. The M2FC reactor yielded a power density of up to 2 W m⁻² (or time-averaged value of approximately 650 mW m⁻²), density up to 20 times (or approximately six times based on time-averaged value) higher than the corresponding MFC system.     

Colloid transport in a geochemically heterogeneous porous medium: aquifer tank experiment and modeling

To examine colloid transport in geochemically heterogeneous porous media at a scale comparable to field experiments, we monitored the migration of silica-coated zirconia colloids in a two-dimensional layered porous media containing sand coated to three different extents by ferric oxyhydroxides. Transport of the colloids was measured over 1.65 m and 95 days. Colloid transport was modeled by an advection-dispersion-deposition equation incorporating geochemical heterogeneity and colloid deposition dynamics (blocking). Geochemical heterogeneity was represented as favorable (ferric oxyhydroxide-coated) and unfavorable (uncoated sand) deposition surface areas. Blocking was modeled as random sequential adsorption (RSA). Release of deposited colloids was negligible. The time to colloid breakthrough after the onset of blocking increased with increasing ferric oxyhydroxide-coated surface area. As the ferric oxyhydroxide surface area increased, the concentration of colloids in the breakthrough decreased. Model-fits to the experimental data were made by inverse solutions to determine the fraction of surface area favorable for deposition and the deposition rate coefficients for the favorable (ferric oxyhydroxide-coated) and unfavorable sites. The favorable deposition rate coefficient was also calculated by colloid filtration theory. The model described the time to colloid breakthrough and the blocking effect reasonably well and estimated the favorable surface area fraction very well for the two layers with more than 1% ferric oxyhydroxide coating. If mica edges in the uncoated sand were considered as favorable surface area in addition to the ferric oxyhydroxide coatings, the model predicted the favorable surface area fraction accurately for the layer with less than 1% ferric oxyhydroxide coating.     

Biomimetic chemical degradation of polychlorobiphenyls below 100°C

PCBs were rapidly degraded by hydroxy radicals formed in the biomimetic degradation systems of superoxide, ferric chloride, and hydrogen peroxide at high concentrations below 100°C. The degradation rates of Kanechlor KC 300, KC 400, KC 500 and KC 600 were 95.4%, 89.1%, 59.9% and 47.9%, respectively. The generation of carbon dioxide gas was recognized and chloride ion showed 89.9 – 102.7% of the theoretical yield in the degradation of KC 300, KC 400 and KC 500.