温度与pH对生物合成施氏矿物在酸性环境中溶解行为及对Cu2+吸附效果的影响

探析施氏矿物在不同温度、pH下的溶解行为,对其在酸性煤矿废水(ACMD)重金属去除领域的应用具有重要的工程指导意义.本研究通过摇瓶实验,在0.16mol·L-1FeSO4·7H2O,初始pH为2.5的酸性体系中,采用氧化亚铁硫杆菌A.ferrooxidans催化合成施氏矿物.考察了15℃与30℃,pH为2.0$6.0环境条件下矿物的溶解行为,及生物合成施氏矿物对酸性体系Cu2+的吸附去除效果.研究结果表明,经过24h反应,施氏矿物合成体系pH从原始2.50降低至2.18,体系Fe2+氧化完全,27.3%的铁离子参与矿物的合成,矿物分子式可表示为Fe8O8(OH)4.22(SO4)1.89.生物合成施氏矿物在温度为15℃,pH分别为3.2、3.0、2.8、2.6、2.4、2.2与2.0液态体系中振荡72h,矿物溶解率分别为1.92%、3.34%、5.90%、13.09%、28.74%、44.53%与61.46%.在温度为30℃的上述酸度体系中,矿物溶解率在相应时间却达到2.04%、3.98%、8.34%、20.53%、43.50%、96.74%与99.92%.在pH≥3.5的不同温度液态体系中该矿物无溶解迹象.在15℃,pH为6.0、5.0、4.5、4.0与3.5,Cu2+浓度为40mg·g-1的液态体系中,生物合成施氏矿物对Cu2+的吸附量为(50.9±2.2)、(47.3±13.3)、(40.5±4.7)、(31.1±5.0)及(16.9±6.5)mg·g-1.体系酸度一定,施氏矿物在15℃与30℃条件下对Cu2+的吸附效果无显著差异.本研究结果对生物合成施氏矿物在ACMD重金属去除工程应用提供必要的参数支撑.     

生物催化合成的施氏矿物对废水中Cr(VI)的吸附

在模拟多种金属离子[Cr(VI),Cu²⁺,Zn²⁺和Cd²⁺共存的电镀废水中,采用新型生物催化合成矿物无定型羟基硫酸高铁(Schwertmannite,施氏矿物)去除废水中的Cr(VI).实验结果表明,施氏矿物对Cr(VI)络阴离子具有很强的选择性吸附,整个吸附过程符合Langmiur方程.吸附的最佳pH值为6.0～7.0,最大吸附量为55mg/g,且当Cr(VI)初始浓度≤100mg/L时,去除率达90%以上.在温度20～50℃范围内,温度变化对吸附的影响较小.一价阴离子(如Cl^-和NO₃^-)对Cr(VI)的去除干扰极小,而仅当介质中SO₄^2-和PO₄^3-与Cr(VI)的摩尔比分别超过5:1和1:5时,2种无机阴离子才影响施氏矿物对Cr(VI)的吸附.     

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.     

Thiocyanate-induced labilization of schwertmannite: Impacts and mechanisms

Schwertmannite is an amorphous iron(III)-oxyhydroxysulfate that forms in acid mine drainage(AMD) environments. The characteristic of high heavy metal adsorption capability makes schwertmannite a potentially useful, environmentally friendly material in wastewater treatment. Unstable schwertmannite is prone to recrystallization.Understanding the mechanisms that induce schwertmannite labilization and affect its capacity to remove heavy metals are of great environmental and geochemical significance.Thiocyanate(SCNˉ) is a hazardous pseudohalide that is also normally found in AMD.However, little is known about the impact of Fe(III)-binding ligand SCNˉ on schwertmannite stability and its subsequent capacity to bind trace elements. Here, we investigated the adsorption of SCNˉ on schwertmannite and subsequent mineral transformation to characterize this little-known process. The appearance of Fe2+indicated that the interactions between schwertmannite and SCNˉ may involve complexation and reduction reactions. Results showed that the majority of the adsorbed-SCNˉ was immobilized on schwertmannite during the 60-days transformation. The transformation rates of schwertmannite increased with increasing concentrations of SCNˉ. Goethite was detected as the dominant transformation product with or without SCNˉ. The mechanisms of SCNˉ-promoted dissolution of schwertmannite can be described as follows:(1) formation of Fe(III)–NCS complexes on the schwertmannite surface and in solution, a process which increases the reactivity of solid phase Fe(III);(2) the extraction of Fe(III) from schwertmannite by SCNˉ and subsequent schwertmannite dissolution; and(3) the formation of secondary minerals from extracted Fe(III). These findings may improve AMD treatment strategies and provide insight into the use and potential reuse of schwertmannite as a trace element sorbent.     

Formation and transformation of schwertmannite in the classic Fenton process

The massive amount of sludge generated by the classic Fenton process, which has often been hypothesized to consist of ferric hydroxide, remains a major obstacle to its large-scale application. Therefore, reutilization of Fenton sludge has recently gained more attention.Understanding the formation, transformation, and properties of Fenton sludge combined with the stages of the Fenton reaction is pivotal, but not well illustrated yet. In this study,SEM-EDS, FT-IR, XRD, and XPS were applied to study the morphology, crystallinity,elemental composition, and valence state of Fenton sludge. The authors report that schwertmannite and 2-line ferrihydrite were generated and transformed in the oxidation phase and the neutralization phase of the Fenton process. SO_4~(2-) in the solution decreased by8.7%–26.0% at different molar ratios of Fe(II) to H_2 O_2; meanwhile, iron ion precipitated completely at pH 3.70 with the formation of schwertmannite containing sulfate groups in the Fenton sludge. The structural sulfate(Fe-SO_4) in schwertmannite was released from the precipitate with the addition of OH-, and the production of Fenton sludge decreased with increasing pH when pH 3.70. Goethite was found to form when the final p H was adjusted to 12 or at a reaction temperature of 80°C. Moreover, the possible thermal transformation to goethite and hematite indicated that Fenton sludge can be reused as a raw material for synthesizing more stable iron(hydro)oxides. The results provide useful insights into the formation and transformation of Fenton sludge, with implications for regulating the crystal type of Fenton sludge for further reuse.     

TiO2/Schwertmannite nanocomposites as superior co-catalysts in heterogeneous photo-Fenton process

The heterogeneous photo-Fenton reaction is an effective technique in combating organic contaminants for both soil and water remediation,and extensive studies have focused on enhancing its efficiency and reducing its costs.In this work,we developed novel photoFenton catalysts by simply milling commercially available TiO_2(P25)with Schwertmannite(Sh),a natural iron-oxyhydroxysulfate nanomineral.We expect that the photo-generated electrons from TiO_2could continuously migrate to Sh,which then could enhance the separation of electron-hole pairs on TiO_2and accelerate the reduction of Fe(III)to Fe(II)on Sh,leading to high degradation efficiency of the target organic contaminants.SEM and TEM results showed the distribution of TiO_2on Sh surface for the nanocomposites(TiO_2/Sh).Under simulated sunlight irradiation,the much higher content of Fe(II)was determined on TiO_2/Sh than on Sh via a common method in the iron ore,and the consumption of H_2O_2and the production of·OH were more significant in the TiO_2/Sh system than those in the TiO_2and Sh systems.These results well support our hypothesis that the photo-generated electrons could migrate from TiO_2to Sh on the composites,and can also explain the much higher degradation efficiency of Rhodamine B(RhB)in the TiO_2/Sh system.Besides,TiO_2/Sh had lower Fe dissolution as compared with Sh,and retained high catalytic stability after four repeated cycles.Above merits of the TiO_2/Sh composites,in combining with their simple synthesis method and low-cost property,indicated that they should have promising applications as heterogeneous photo-Fenton catalysts.     

载银施氏矿物的制备及其对甲基橙的催化还原降解

采用硼氢化钠还原方法制备了不同载银量的银纳米粒子/施氏矿物复合催化剂（AgNPs/Sch）,利用扫描电镜（SEM）、X射线能谱（EDS）和X射线衍射（XRD）等测试方法对所制备催化剂的表面形貌、元素组成和物相组成进行了表征,证明了Ag成功负载于施氏矿物上.以甲基橙为目标污染物,硼氢化钠为还原剂,考察了不同载银量施氏矿物对甲基橙的催化降解性能,并探究了载银施氏矿物的投加量、硼氢化钠浓度、 甲基橙初始浓度、溶液初始pH等因素对甲基橙的催化还原降解效果的影响.结果表明,在甲基橙浓度为20 mg?L^-1、NaBH₄浓度为10 mmol?L^-1、初始pH=6条件下,反应90 min后,未载银的施氏矿物对甲基橙的降解率仅为7.5%,然而硝酸银添加量为0.10 g制备的AgNPs/Sch对甲基橙的降解率可达97.0%,该催化剂作为电子介质,能够将电子从还原剂（NaBH₄）转移到甲基橙中,进而加速甲基橙的降解.AgNPs/Sch在最佳的实验条件下5次循环性反应后,仍具有较高的催化稳定性.由此可见,载银施氏矿物作为一种新型的催化剂,在有机染料废水净化方面具有良好的应用前景.     

柠檬酸-施氏矿物复合体对Cd和Pb的吸附研究

施氏矿物(Schwertmannite)是酸性矿区废水污染环境中典型的铁硫酸盐次生矿物,由于其较好的吸附能力成为矿区多种重金属的沉积库.环境中同时广泛存在着各种有机质,易与矿物结合形成有机质矿物复合体,从而影响矿物对重金属的吸附行为.目前关于有机质与施氏矿物形成的复合体对重金属的吸附研究相对较少.因此,本研究选取柠檬酸作为天然有机质的代表,研究不同环境条件下柠檬酸施氏矿物复合体对重金属Cd、Pb的吸附.结果表明,复合体保持着施氏矿物基本的矿物学特征,对重金属Cd和Pb的吸附行为表现出不同的趋势:复合体对Cd的吸附量整体上随着Cd浓度和pH值的升高而上升;相反,复合体对Pb的吸附量均比纯施氏矿物要低,并且随着柠檬酸含量的升高吸附量下降越明显;体系中共存的硫酸根离子(SO₄^2-)抑制了复合体对Cd的吸附,而对Pb的吸附则起到促进作用.XRD分析表明柠檬酸抑制了高pH下Pb在矿物表面形成PbSO₄沉淀.FTIR红外谱图进一步证明结合在复合体上的柠檬酸参与了对Cd和Pb的吸附过程.本研究结果有助于更好地预测Cd和Pb在矿区的迁移和归宿.