Fe~0对土壤中3-硝基甲苯的还原作用

研究常温常压下零价铁(ZVI或Fe0)对土壤中3-硝基甲苯(MNT)的还原作用.结果表明:零价铁能够有效地将土壤中的MNT还原为3-甲基苯胺.在MNT为2.5×10-6mol·-1,铁粉加入量为25mg·g-1,土壤初始pH值为6.8,含水量为75%,温度为25℃的条件下,反应5h后MNT的还原率可达95%.随着体系反应时间的延长,温度的升高,土壤含水量的增大和铁粉用量的增加,MNT的还原率均增大.将土壤初始pH值控制在偏酸性有利于反应的进行.     

Fe^0对土壤中对氯硝基苯和对硝基甲苯的还原

采用零价铁(Fe0)还原技术,在25℃和常压下修复受对氯硝基苯(PCNB)和对硝基甲苯(PNT)混合污染的土壤,研究不同反应条件对还原反应的影响及产物在反应历程中的变化.实验结果表明:零价铁能够有效地将土壤中PCNB和PNT还原为其对应的苯胺化合物.在PCNB和PNT的初始含量约为2.5×106mol·g-1,Fe0加人最为25 mg·g-1,土壤水分含量为0.75 mL·g-1,土壤初始pH值为6.8,于25℃下反应5 h,PCNB和PNT的还原率都可达93%以上.Fe0用量、土壤初始pH值、温度和土壤含水量均对Fe0还原硝基苯类化合物有较明显影响,偏酸性的土壤、较高的温度、增加Fe0用量和饱和的土壤含水量能显著提高还原率.     

零价铁对土壤中4-氯苯酚还原脱氯研究

氯苯酚是常见的环境污染物，它们在土壤中的加速分解可以减少对人类健康的危害。以恒温培养为方法，GC-MS为检测手段，研究了在常温常压下土壤中4-氯苯酚(4-CP)在零价铁作用下的还原脱氯反应。结果表明：4-CP可以被来自零价铁的电子还原，零价铁能够有效促进土壤中的4-CP脱除苯环上的氯原子，从而达到降低毒性、增加可生化性目的。反应条件如初始pH、时间、零价铁用量等均对4-CP还原脱氯效率有重要影响，特别是当初始pH值控制在偏酸时更有利于反应的进行。在零价铁加入量500mg、初始pH=4、反应时间7d的条件下，零价铁对土壤中4-CP还原脱氯效率最高可以达到65％。利用实验数据，对零价铁作用下4-CP还原脱氯的反应机理也进行了初步探讨。     

零价铁还原脱氯污染土壤中PCBs的实验研究

利用零价铁或铁的双金属对模拟污染土中多氯联苯(PCBs)在常温常压下的还原脱氯情况进行实验研究.采用高效离子色谱分析样本,结果表明:零价铁或者镍(Ni)铁双金属对土壤中浓度为5 mg·g-1的PCBs有一定的脱氯效果;当PCBs浓度降低为1 mg·g-1时只有钯(Pd)含量为0.05%的钯铁处理具有显著的脱氯效果;升高土壤温度到45℃,或者简单加入醋酸、活性炭、石墨以及硫粉等处理均不能有效提高脱氯效果;先添加硫粉和水培养,使土壤氧化还原电位降低后,添加含铜(Cu)为2%的铜铁及含钴(Co)为1%的钴铁双金属对土壤中的PCBs有明显的脱氯效果.     

水热合成silicalite-2分子筛及对对硝基苯酚的吸附与脱附性能

以硅溶胶为硅源、四丁基氢氧化铵(TBAOH)为模板剂,按1SiO2∶0.35TBAOH∶25H2O的物质的量之比,170℃下水热晶化48 h合成silicalite-2分子筛,并用XRD、SEM等方法对其进行了表征.考察了pH、温度、投加量、NaCl浓度对模拟的对硝基苯酚废水吸附效果的影响.结果表明,在对硝基苯酚废水浓度为20 mg·L-1,pH=4,投加量为0.3g·L-1,温度25℃,NaCl浓度580 mg·L-1时,吸附量为98.4 mg·g-1.采用1.44%氢氧化钠脱附剂对吸附饱和的silicalite-2分子筛进行脱附110 min,脱附率达到85%以上.     

五氯酚催化湿式氧化降解反应及动力学研究

以高温老化法制备了ZrO2载体,其比表面积为251.6 m.2g-1,采用等体积浸渍法制备了Ru/ZrO2催化剂,用于催化湿式氧化法处理五氯酚.研究了反应温度、氧气分压、PCP初始浓度及时间对PCP转化率的影响.研究结果表明,提高反应温度、增加氧气分压、减小PCP初始浓度及延长反应时间均可提高五氯酚的转化率.在C0PC...     

氧化锌表面的Fe(Ⅱ)对三氯乙烯的还原脱氯研究

通过批量实验研究了在氧化锌-Fe(Ⅱ)混合体系中,束缚在氧化锌表面的Fe(Ⅱ)对三氯乙烯的还原脱氯作用。结果表明,这种束缚在氧化锌表面的Fe(Ⅱ)对三氯乙烯有一定的还原脱氯作用,且脱氯反应符合准一级反应动力学方程。与均质溶液中的Fe(Ⅱ)相比,束缚在氧化锌表面的Fe(Ⅱ)对三氯乙烯有更强的还原脱氯作用。实验还发现三氯乙烯在氧化锌-Fe(Ⅱ)混合体系中的还原脱氯速率受pH值和Fe(Ⅱ)浓度的影响。Fe(Ⅱ)浓度为1mmol·L-1,在pH值5.0～9.0范围内,还原脱氯反应速率常数kobs及三氯乙烯去除率随着pH值的升高而增大。维持pH值7.0不变,在Fe(Ⅱ)浓度1～4mmol·L-1范围内,kobs及三氯乙烯去除率随Fe(Ⅱ)浓度的增大而增大,但是Fe(Ⅱ)浓度进一步升高,kobs及三氯乙烯去除率反而降低。当Fe(Ⅱ)初始浓度为4mmol·L-1、pH=7.0时,三氯乙烯在氧化锌-Fe(Ⅱ)混合体系中的kobs及三氯乙烯去除率均达到最大值,分别为0.260h-1、71.7%。     

两种土壤中对硝基氯苯被Fe~0还原的对比研究

利用零价铁(Fe~0)还原技术修复受对氯硝基苯(p-CNB)污染的土壤,研究常温常压下松砂土和中壤土两种不同土壤的理化性质对还原反应的影响.结果表明:Fe0能有效还原松砂土和中壤土中的p-CNB,生成对应的苯胺化合物,降低毒性;当土壤中p-CNB的含量约为2.5×10~(-6)mol·g~(-1),Fe~0用量为25 mg·g~(-1),反应体系中水分含量为0.75 mL·g~(-1)时,于25℃反应2 h后,松砂土和中壤土中p-CNB的还原率均超过93%;还原反应在中壤土中进行得较快.污染物在土壤中的老化时间对Fe~0还原降解效果影响很小,而土壤粒径、土壤是否灭菌以及土壤有机质含量等因素则对还原有较明显影响;还原降解反应在没有灭菌、有机质含量较高且粒径偏小的壤土中进行得最彻底.     

土壤还原过程对氯代有机污染物还原脱氯的影响与机制

自然环境中,大多数氯代有机污染物厌氧还原脱氯反应是与土壤环境中一些生源要素的生物化学还原过程相伴生。有机污染物的种类、生物有效性以及毒性能够显著影响这些生源要素的转化,反过来,土壤中活跃的氧化还原反应也可以显著影响有机污染物的动力学转化过程。本文从氧化还原顺序上综述了反硝化过程、铁还原过程、硫酸盐还原过程和产甲烷过程对氯代有机污染物厌氧还原脱氯过程的影响与作用机制,旨在为氯代有机污染物在厌氧环境中还原脱氯的过程与机理的进一步研究、以及还原脱氯与微生物介导的生源要素氧化还原过程的耦合作用机制的揭示提供参考。     

人居生活废弃物生物黑炭对水溶液中Cd2+的吸附研究

以人居生活废弃物生物黑炭为材料,探讨生物黑炭对Cd2+的吸附动力学及热力学特性,通过平衡吸附法研究吸附时间、Cd2+初始质量浓度、吸附剂投加量、溶液pH值以及黑炭粒径对Cd2+吸附率的影响.结果表明,吸附时间为2h时基本达到吸附平衡,准二级动力学方程能很好地描述生物黑炭对Cd2+的吸附过程.Langmuir模型能较好地描述生物黑炭对Cd2+的等温吸附过程,根据该模型模拟得到25℃条件下Cd2+最大吸附量为6.22mg·g-1.Cd2+去除率随生物黑炭投加量的增加而增大;生物黑炭对Cd2+吸附量随其粒径减小而增大;溶液初始pH值为4.0～7.5时,pH值变化对Cd2+吸附量的影响不显著.采用人居生活废弃物生物黑炭去除水溶液中Cd2+时,控制溶液Cd2+初始质量浓度30mg·L-1,粒径小于0.25 mm,投加水平8g·L-1,反应温度25℃,反应时间1～2h,Cd2+去除率可达80％.人居生活废弃物生物黑炭可以作为去除污染水体中Cd2+的吸附剂.     

土壤中取代硝基苯化合物被零价铁还原的机理

以气相色谱-质谱联用仪(GC-MS)分析和密度泛函理论(DFT)计算,探讨了土壤中甲基、氯代硝基苯混合物在常温常压下被零价铁还原的机理.GC-MS数据证明,取代硝基苯在土壤中被零价铁还原的主要产物是苯胺,同时还检测到微量的亚硝基苯、甲基苯二氮烯(对二甲基偶氮苯)、氯苯二氮烯(对二氯偶氮苯)等分解和缩合中间产物.理论计算表明:随还原程度的加深,对硝基甲苯和对氯硝基苯反应体系的能量从高到低,还原反应通过逐步添加质子和电子到硝基而进行,质子亲和力、电子亲和力起主导作用.逐步还原的机理合理地解释了实验中还原反应对土壤pH值的敏感以及微量中间产物的生成过程.苯环上的氯或甲基对还原反应的影响没有明显的差异.     

Ameliorants to immobilize Cd in rice paddy soils contaminated by abandoned metal mines in Korea

The cadmium (Cd) content of rice grain grown in metal-contaminated paddy soils near abandoned metal mines in South Korea was found to exceed safety guidelines (0.2 mg Cd kg?1) set by the Korea Food and Drug Administration (KFDA). However, current remediation technologies for heavy metal-contaminated soils have limited application with respect to rice paddy soils. Laboratory and greenhouse experiments were conducted to assess the effects of amending contaminated rice paddy soils with zerovalent iron (ZVI), lime, humus, compost, and combinations of these compounds to immobilize Cd and inhibit Cd translocation to rice grain. Sequential extraction analysis revealed that treatment with the ameliorants induced a 50-90% decrease in the bioavailable Cd fractions when compared to the untreated control soil. When compared to the control, Cd uptake by rice was decreased in response to treatment with ZVI + humus (69%), lime (65%), ZVI + compost (61%), compost (46%), ZVI (42%), and humus (14%). In addition, ameliorants did not influence rice yield when compared to that of the control. Overall, the results of this study indicated that remediation technologies using ameliorants effectively reduce Cd bioavailability and uptake in contaminated rice paddy soils.     

Remediation of arsenic contaminated soil by sulfidated zero-valent iron

• Sulfidation significantly enhanced As(V) immobilization in soil by zerovalent iron. • S-ZVI promoted the conversion of exchangeable As to less mobile Fe-Mn bound As. • Column test further confirmed the feasibility of sulfidated ZVI on As retention. • S-ZVI amendment and magnetic separation markedly reduced TCLP leachability of As. In this study, the influences of sulfidation on zero-valent iron (ZVI) performance toward As(V) immobilization in soil were systemically investigated. It was found that, compared to unamended ZVI, sulfidated ZVI (S-ZVI) is more favorable to immobilize As(V) in soil and promote the conversion of water soluble As to less mobile Fe-Mn bound As. Specifically, under the optimal S/Fe molar ratio of 0.05, almost all of the leached As could be sequestrated by>0.5 wt.% S-ZVI within 3 h. Although the presence of HA could decrease the desorption of As from soil, HA inhibited the reactivity of S-ZVI to a greater extent. Column experiments further proved the feasibility of applying S-ZVI on soil As(V) immobilization. More importantly, to achieve a good As retention performance, S-ZVI should be fully mixed with soil or located on the downstream side of As migration. The test simulating the flooding conditions in rice culture revealed there was also a good long-term stability of soil As(V) after S-ZVI remediation, where only 0.7% of As was desorbed after 30 days of incubation. Magnetic separation was employed to separate the immobilized As(V) from soil after S-ZVI amendment, where the separation efficiency was found to be dependent of the iron dosage, liquid to soil ratio, and reaction time. Toxicity characteristic leaching procedure (TCLP) tests revealed that the leachability of As from soil was significantly reduced after the S-ZVI amendment and magnetic separation treatment. All these findings provided some insights into the remediation of As(V)-polluted soil by ZVI.     

Arsenic mobility in the amended mine tailings and its impact on soil enzyme activity

The objectives of this study were to elucidate the effects of soil amendments [Ferrous sulfate (Fe^II), red mud, Fe^II with calcium carbonate (Fe^II/L) or red mud (RM/F), zero-valent iron (ZVI), furnace slag, spent mushroom waste and by-product fertilizer] on arsenic (As) stabilization and to establish relationships between soil properties, As fractions and soil enzyme activities in amended As-rich gold mine tailings (Kangwon and Keumkey). Following the application of amendments, a sequential extraction test and evaluation of the soil enzyme activities (dehydrogenase and β-glucosidase) were conducted. Weak and negative relationships were observed between water-soluble As fractions (As_WS) and oxalate extractable iron, while As_WS was mainly affected by dissolved organic carbon in alkaline tailings sample (Kangwon) and by soil pH in acidic tailings sample (Keumkey). The soil enzyme activities in both tailings were mainly associated with As_WS. Principal component and multiple regression analyses confirmed that As_WS was the most important factor to soil enzyme activities. However, with some of the treatments in Keumkey, contrary results were observed due to increased water-soluble heavy metals and carbon sources. In conclusion, our results suggest that to simultaneously achieve decreased As_WS and increased soil enzyme activities, Kangwon tailings should be amended with Fe^II, Fe^II/L or ZVI, while only ZVI or RM/F would be suitable for Keumkey tailings. Despite the limitations of specific soil samples, this result can be expected to provide useful information on developing a successful remediation strategy of As-contaminated soils.     

温度和砷酸根对砖红壤中Cd（II）吸附动力学的影响

土壤中砷和镉同时存在的现象普遍存在,但目前对砷酸根与Cd(II)在可变电荷土壤表面协同作用的机制还了解不多。用一次平衡法研究了288 K和308 K温度条件下Cd(II)在昆明砖红壤表面的吸附动力学,比较了加入砷酸根对Cd(II)吸附动力学的影响。结果显示,加As(V)和升高温度均不仅增加Cd(II)的吸附量,而且提高了吸附反应的速率。Cd(II)在砖红壤表面的吸附反应进行的特别快,几乎在30 min内达到准平衡,假二级动力学方程能很好拟合30 min内的吸附动力学数据(r2>0.999 5)。从反应速率常数计算得到的活化能的结果表明,加As(V)显著降低了Cd(II)吸附反应的活化能,这是As(V)促进可变电荷土壤吸附Cd(II)的根本原因。     

新疆盐渍化土壤氮肥氨挥发损失特征初步研究

在室温下应用“静态吸收法”,研究不同盐渍化程度的盐化土壤和碱化土壤上氮肥氨挥发损失特征。结果表明:(1)除碱土外碱化土壤上氮肥氨挥发量随时间延长呈现下降趋势,在盐化土壤上氨挥发量随时间呈现先上升后下降趋势。(2)供试9个典型盐渍化土壤样品上氮肥氨挥发量(Y)与时间(t)关系均符合Y=at2 bt c动力学方程,相关性呈极显著水平。(3)氨挥发总量(Y)、氨挥发速率(Yi)与土壤含盐量(x)呈极显著正相关;氨挥发持续时间随着盐渍化程度的增加而延长。(4)氨挥发总量、挥发速率与盐渍土pH相关性未达到显著水平;盐渍土上pH值对氨挥发的影响需要进一步研究。以上结果表明,盐渍化耕作土壤上氮肥氨挥发的控制要依据盐渍化类型的不同而制定相应的措施。     

Rapid and long-effective removal of broad-spectrum pollutants from aqueous system by ZVI/oxidants

• The coupling of oxidants with ZVI overcome the impedance of ZVI passive layer. • ZVI/oxidants system achieved fast and long-effective removal of contaminants. • Multiple mechanisms are involved in contaminants removal by ZVI/oxidant system. • ZVI/Oxidants did not change the reducing property of ORP in the fixed-bed system. Zero-valent iron (ZVI) technology has recently gained significant interest in the efficient sequestration of a wide variety of contaminants. However, surface passivation of ZVI because of its intrinsic passive layer would lead to the inferior reactivity of ZVI and its lower efficacy in contaminant removal. Therefore, to activate the ZVI surface cheaply, continuously, and efficiently is an important challenge that ZVI technology must overcome before its wide-scale application. To date, several physical and chemical approaches have been extensively applied to increase the reactivity of the ZVI surface toward the elimination of broad-spectrum pollutants. Nevertheless, these techniques have several limitations such as low efficacy, narrow working pH, eco-toxicity, and high installation cost. The objective of this mini-review paper is to identify the critical role of oxygen in determining the reactivity of ZVI toward contaminant removal. Subsequently, the effect of three typical oxidants (H₂O₂, KMnO₄, and NaClO) on broad-spectrum contaminants removal by ZVI has been documented and discussed. The reaction mechanism and sequestration efficacies of the ZVI/oxidant system were evaluated and reviewed. The technical basis of the ZVI/oxidant approach is based on the half-reaction of the cathodic reduction of the oxidants. The oxidants commonly used in the water treatment industry, i.e., NaClO, O₃, and H₂O₂, can be served as an ideal coupling electron receptor. With the combination of these oxidants, the surface corrosion of ZVI can be continuously driven. The ZVI/oxidants technology has been compared with other conventional technologies and conclusions have been drawn.     

The coupling of sand with ZVI/oxidants achieved proportional and highly efficient removal of arsenic

• Simply doping sands with ZVI achieved an even activation of ZVI by oxidants. • Sand doping facilitated proportional As trapping along the ZVI/oxidants column. • ZVI/sand/oxidants are highly efficient for arsenic removal. • ZVI/sand/oxidants reduced significantly the Fe²⁺ leaching and effluent turbidity. • More than 54% of arsenic was reduced to As(III) in ZVI/sand/oxidants system. The coupling of zero-valent iron (ZVI) with common oxidants has recently achieved very rapid and highly efficient removal of Heavy metals from wastewater. However, the uniform activation of ZVI throughout the column and the proportional removal of target contaminants are urgently required for the prevention of premature filter clogging and the extension of the effective column operational time. In this study, we successfully achieved this objective by simply doping granular sand with ZVI at appropriate weight ratios. When pure ZVI packed column was spiked with oxidants, the majority of As trapping occurred between the column inlet and the first sampling point. In a packed column with a 1:20 mixture of ZVI and sand, the average As removal efficiency was 36 (1st), 13.1 (2nd), 18.5 (3rd), 19.2 (4th) and 5.9% (5th outlet). The overall arsenic removal performance of the composite filling system of ZVI/sand was equally as efficient as that of the previous pure ZVI-packed system. Moreover, the leaching of Fe was significantly reduced with an increased sand ratio, resulting in clearer water with less turbidity. The results of X-ray photoelectron spectroscopy (XPS) demonstrated that more than 54% of the arsenic was reduced to As(III). X-ray diffraction (XRD) and scanning electron microscopy (SEM) confirmed the extensive corrosion of the ZVI surface, which resulted in various species of iron oxyhydroxides responsible for the highly efficient sequester of arsenic through reduction, adsorption, and coprecipitation.