利用铁泥或硫铁矿烧渣制取氧化铁颜料

本文详细阐述了铁泥和硫铁矿烧渣的来源及其成分,制备生成优质氧化铁所需的高纯硫酸亚铁溶液的最佳工艺条件.制备氧化铁红工艺流程及最佳控制参数.简述了酸性废水的循环使用.     

天然铁基矿物修复土壤的机制

铁是地球物质循环的重要元素,它在地球环境中以各种铁基矿物的形式广泛存在.在此,介绍天然铁基矿物的基本性质及其在土壤修复中的作用机制,着重阐述铁基矿物的吸附交换作用,氧化还原作用和与微生物交互作用,总结和讨论它们的作用原理,并对铁基矿物在土壤修复领域的应用提出一些值得思考的问题.     

成土母质对土壤团聚体形成的影响

成土母质对土壤团聚体数量及其稳定性的影响与不同母质所含无机胶体（粘粒、游离氧化物）的差别有关．对浙江省八类母质发育的土壤的团聚体组成的研究表明：母质对土壤团聚体及其水稳定性影响顺次为玄武岩＞石灰岩、Q2红土＞花岗岩、石英砂岩＞泥页岩＞紫砂岩＞红砂岩．其中母质对5－1mm粒级的水稳性团聚体的影响最为显著．     

我国环境国际公约履约成效以及“十三五”履约重点研究

我国自20世纪80年代开始环境国际公约缔约进程后,全面完成了发展中国家中最为繁重的履约任务,兑现了对国际社会的承诺,树立和维护了中国负责任大国形象。当前,环境公约呈现总体任务繁重、压力持续增大、公约协同日显、履约条件多变、资源约束趋紧、目标任务硬化的新特征。本文通过研究环保部牵头的多边环境条约实施进展,评估了我国环境国际公约履约成效,查找识别"十三五"履约重点任务。其中,特别针对2013年新缔结的《关于汞的水俣公约》,研究中国的责任和义务,分析该公约对我国相关行业产业的影响,提出"十三五"期间履约的重点任务以及应对措施。     

不同水分条件下铁基氧化物对土壤砷的稳定化效应研究

应用等温吸附试验及室内模拟培养的方法,研究了Fe2O3、Nano-Fe2O3和铁锰双金属氧化物(FMBO)等铁基氧化物对砷的吸附特性和对不同含水量土壤中砷的稳定化效应.从等温吸附试验结果来看,3种铁基氧化物对As(V)和As(Ⅲ)的吸附过程符合准二级动力学方程,12 h后基本达到吸附平衡,吸附等温线符合Langmuir方程,FMBO对As(V)和As(Ⅲ)的吸附容量显著大于Fe2O3和Nano-Fe2O3,且对As(Ⅲ)的饱和吸附容量大于As(V),能够起到氧化和吸附的双重作用.从对不同含水量土壤中砷的稳定化效果来看,Nano-Fe2O3和FMBO在风干和田间持水量土壤中均能达到90%以上的稳定化效率,显著高于Fe2O3;在土壤水分饱和条件下,FMBO的稳定化效率仍保持在93.5%以上,且能够将土壤中As(Ⅲ)氧化成As(V),而Fe2O3和Nano-Fe2O3分别仅为29.4%、81.4%.3种铁基氧化物的添加会使土壤中砷的结合态发生变化,Fe2O3、NanoFe2O3主要使砷由F1非专性吸附态和F2专性吸附态向F4结晶铁锰或铁铝水化氧化物结合态转变,添加FMBO主要向F3无定形或弱结晶铁锰或铁铝水化氧化物结合态转变.总体看来,在非饱和状态的土壤,Nano-Fe2O3和FMBO均为良好的稳定化材料,而对于长期淹水的稻田或地下水位较高的地区,或者由于降雨造成土壤滞水等情况,FMBO可以作为一种优良的稳定化材料用于土壤砷污染修复.     

硫素对氧化还原条件下水稻土氧化铁和砷形态影响

通过充N2和充O2的氧化还原反应装置,在添加外源砷污染的水稻土中,施用不同形态的无机硫(不施硫S0,单质硫S1和硫酸盐S2),模拟水稻田的氧化还原状况.结果表明,通N2时,土壤溶液氧化还原电位(Eh)在-100~-200 mV之间,溶液pH在7.0~8.0之间,pe+pH为4~7之间;通O2时,溶液Eh在200mV左右,溶液pH在6.5~7.5之间,pe+pH为9~12之间.无论通N2还是通O2,土壤溶出铁的浓度在1.2~1.6 mg·L-1,均有处理S0>S1>S2和AsS0>AsS1>AsS2.在通N2时,各处理HCl提取土壤氧化铁的含量比原土[(21.4±0.3)g·kg-1]低5 g·kg-1,有利于结晶态氧化铁向无定形氧化铁转化和形成Fe2+,无定形氧化铁活化度比原土活化度46.8%有所增加,且处理AsS2(49.4%)AsS2(36.1%).通N2时,土壤溶液中砷浓度变化为AsS0[(1.13±0.04)mg·L-1]>AsS1[(0.89±0.01)mg·L-1]>AsS2[(0.77±0.04)mg·L-1];通O2时,土壤溶液中砷浓度变化AsS1[(0.77±0.01)mg·L-1]>AsS0[(0.20±0.09)mg·L-1]>AsS2[(0.09±0.01)mg·L-1].通N2时,不同处理各形态砷占总砷比例变化为残渣态(34.9%~41.4%)≈专性吸附态(37.4%~39.5%)>晶态铁锰结合态(23.3%~25.6%)>非专性吸附态(2.4%~3.3%)>无定形铁锰结合态(0.5%~0.8%).通O2时,各处理形态砷占总砷比例变化为残渣态(30.8%~39.3%)≈专性吸附态(30.3%~34.7%)>晶态铁锰结合态(26.0%~28.7%)>无定形铁锰结合态(9.3%~10.7%)>非专性吸附态(0.5%~1.6%),其中,无定形铁锰氧化物结合态砷比通N2时提高了约9%,也就是无定形铁锰的老化作用对砷形态转化的影响.这表明还原条件能够使氧化铁的活化度升高,砷的移动性增强,但硫酸盐体系降低氧化铁的活化度,单质硫体系的砷移动性要大于硫酸盐体系的砷移动性.     

Removal of arsenate with hydrous ferric oxide coprecipitation：Effect of humic acid

Insights from the adverse effect of humic acid(HA) on arsenate removal with hydrous ferric oxide(HFO) coprecipitation can further our understanding of the fate of As(V) in water treatment process. The motivation of our study is to explore the competitive adsorption mechanisms of humic acid and As(V) on HFO on the molecular scale. Multiple complementary techniques were used including macroscopic adsorption experiments, surface enhanced Raman scattering(SERS), extended X-ray absorption fine structure(EXAFS) spectroscopy, flow-cell attenuated total reflectance Fourier transform infrared(ATR-FTIR) measurement, and charge distribution multisite complexation(CDMUSIC) modeling. The As(V) removal efficiency was reduced from over 95% to about 10% with the increasing HA concentration to 25 times of As(V) mass concentration. The SERS analysis excluded the HA-As(V) complex formation. The EXAFS results indicate that As(V) formed bidentate binuclear surface complexes in the presence of HA as evidenced by an As-Fe distance of 3.26–3.31 ?. The in situ ATR-FTIR measurements show that As(V) replaces surface hydroxyl groups and forms innersphere complex. High concentrations of HA may physically block the surface sites and inhibit the As(V) access. The adsorption of As(V) and HA decreased the point of zero charge of HFO from 7.8 to 5.8 and 6.3, respectively. The CD-MUSIC model described the zeta potential curves and adsorption edges of As(V) and HA reasonably well.     

Antimony(V) removal from water by hydrated ferric oxides supported by calcite sand and polymeric anion exchanger

We fabricated and characterized two hybrid adsorbents originated from hydrated ferric oxides(HFOs) using a polymeric anion exchanger D201 and calcite as host. The resultant adsorbents(denoted as HFO-201 and IOCCS) were employed for Sb(V) removal from water. Increasing solution pH from 3 to 9 apparently weakened Sb(V) removal by both composites, while increasing temperature from 293 to 313 K only improved Sb(V) uptake by IOCCS. HFO-201 exhibited much higher capacity for Sb(V) than for IOCCS in the absence of other anions in solution. Increasing ionic strength from 0.01 to 0.1 mol/L NaNO3would result in a significant drop of the capacity of HFO-201 in the studied pH ranges; however, negligible effect was observed for IOCCS under similar conditions. Similarly, the competing chloride and sulfate pose more negative effect on Sb(V) adsorption by HFO-201 than by IOCCS, and the presence of silicate greatly decreased their adsorption simultaneously, while calcium ions were found to promote the adsorption of both adsorbents. XPS analysis further demonstrated that preferable Sb(V) adsorption by both hybrids was attributed to the inner sphere complexation of Sb(V) and HFO, and Ca(II) induced adsorption enhancement possibly resulted from the formation of HFO-Ca-Sb complexes. Column adsorption runs proved that Sb(V) in the synthetic water could be effectively removed from 30 μg/L to below 5 μg/L(the drinking water standard regulated by China), and the effective treatable volume of IOCCS was around 6 times as that of HFO-201, implying that HFO coatings onto calcite might be a more effective approach than immobilization inside D201.     

Isolation, identification and arsenic-resistance of Acidithiobacillus ferrooxidans HX3 producing schwertmannite

Schwertmannite, a ubiquitous mineral present in iron oxyhydroxides formed in iron- and sulfate-rich acid media, favors incorporation of some toxic anions in its structure. We reported an iron-oxidizing bacterial strain HX3 from a municipal sludge that facilitates the formation of pure schwertmannite in cultures. Ferrous iron oxidation by the isolated strain HX3 was optimum at an initial pH of 2.0-3.3 and temperature of 28-35°C. Pure schwertmannite was found through bacterial oxidation of ferrous iron at an initial pH 2.8and temperature 28°C. Following 16 S rDNA gene sequence analysis the bacterial strain HX3 was identified as Acidithiobacillus ferrooxidans. The arsenic-resistance A. ferrooxidans HX3 showed the potential of environmental application in arsenic removal from the As（Ⅲ）- and iron-rich acid sulfate waters directly by As（Ⅲ） adsorption or the formation of schwertmannite in the environment.     

羟基氧化铁催化臭氧氧化对滤后水卤乙酸生成势的影响

考察了滤后水经过单独臭氧氧化和羟基氧化铁(FeOOH)催化臭氧氧化后5种卤乙酸生成势(HAA5FP)的生成情况.研究了氧化时间、溴离子浓度、滤后水pH值、碱度和O3投量对2种氧化方式下HAA5FP的影响规律.发现该滤后水氯化后的HAA种类为二氯乙酸(DCAA)、三氯乙酸(TCAA)及溴离子存在时有二溴乙酸(DBAA).无溴离子存在时,催化臭氧氧化在5～20min内使得HAA5FP比臭氧氧化后的降低9.5%～18.3%.溴离子浓度增加使HAA5FP减少,催化臭氧氧化后HAA5FP也比臭氧氧化后低更多.中性pH时,催化臭氧氧化比臭氧氧化有更明显的控制HAA5FP的优势.重碳酸盐碱度升高使HAA5FP降低,且2种氧化后HAA5FP的差别减小.O₃/TOC比值为0.45～1.43的臭氧投量范围内,催化臭氧氧化后HAA5FP比臭氧氧化后减少11.2%～28.0%.催化臭氧氧化对滤后水HAA5FP的影响与FeOOH催化臭氧生成羟基自由基的特点密切相关.