天然铁细菌生物矿化针铁矿吸附铬离子的研究

针铁矿,特别是生物成因的针铁矿,具有较大的比表面积和较强的吸附能力,是一种良好的环境修复材料。铬在环境中常以Cr()和Cr()存在,是一种能持久存在具有氧化还原活性的毒性金属离子。本文以水体中铁细菌矿化形成的针铁矿为材料,研究了Cr()和Cr()在该生物矿化针铁矿上的吸附行为,发现其符合Langmuir与Freundlich等温吸附模型。扫描电镜、透射电镜显微成分分析表明铬在该针铁矿上的吸附存在不均匀性,明显受其显微结构影响。显微球团结构的针铁矿比螺旋状针铁矿具有更强的结合铬离子的能力。X射线光电子能谱结果表明吸附在生物矿化针铁矿表…     

β-FeOOH的水热法合成及其去除Cr(Ⅵ)实验研究

采用水热法成功合成四方纤铁矿(β-FeOOH),并结合XRD、SEM、zeta电位分析等对合成物进行系列表征。重点考察Cr(Ⅵ)初始浓度、pH值以及不同光照条件等因素下,β-FeOOH对Cr(Ⅵ)去除效果的影响。实验结果表明:合成得到的β-FeOOH为纺锤形晶体,长径200nm~250nm,端面直径30nm~50nm。Cr(Ⅵ)初始浓度、pH值以及光照条件对β-FeOOH去除Cr(Ⅵ)均存在重要影响。随着Cr(Ⅵ)初始浓度的升高,β-FeOOH吸附Cr(Ⅵ)量呈先递增后降低的趋势,当Cr(Ⅵ)初始浓度为50.07 mg/L时,β-FeOOH吸附Cr(Ⅵ)量达到最大值12.05mg/g,且吸附特征符合Langmuir方程吸附模型,饱和吸附量为16.35mg/g;β-FeOOH宜在弱酸性环境下去除Cr(Ⅵ),随着污染液pH的升高,β-FeOOH对Cr(Ⅵ)去除率呈现先增加后减小的趋势,在pH为6.24时去除率达到最大,为96.67%;光照条件会影响β-FeOOH对Cr(Ⅵ)的去除,β-FeOOH对Cr(Ⅵ)的去除效率呈现出黑暗环境自然环境紫外光照射。     

生物矿化针铁矿对造纸废水的吸附和热解吸研究

利用生物矿化针铁矿对造纸废水进行吸附实验,对吸附动力学、影响因素、以及吸附等温线等进行了研究,通过DTA和XRD研究了不同煅烧温度条件下生物矿化针铁矿的物质形态变化,分析了不同再生条件对生物矿化针铁矿的吸附容量的影响。结果表明:生物矿化针铁矿对造纸废水中的污染物吸附速度较快,具有良好的吸附性能;生物矿化针铁矿吸附污染物后经过煅烧可以实现再生,经310℃煅烧后的第一次再生吸附率为原针铁矿的97.3%,多次加热再生后仍然具有很高的吸附能力。     

光照作用对水铁矿去除Cr(Ⅵ)的影响

Cr在环境中释放易导致重金属污染,其所造成的环境危害与Cr存在形态紧密相关。Cr(Ⅵ)多以CrO₄^2-或Cr₂O₇^2-形式存在,在水体中具有较高溶解度和迁移性,且具有较大的毒性。水铁矿具有大比表面积和高反应活性,是环境中Cr(Ⅵ)的重要吸附剂;同时,水铁矿也是一种天然半导体矿物,在光照诱导作用下可产生光电子并转移电子。然而,水铁矿表面的光化学反应对Cr(Ⅵ)地球化学行为的影响尚不清楚。因此,本研究探讨了光照对水铁矿去除Cr(Ⅵ)的影响。结果表明:在黑暗条件下,水铁矿通过吸附作用去除了57%的Cr(Ⅵ);在光照有氧条件下,水铁矿对Cr(Ⅵ)的去除率上升到67%;在厌氧条件下,光照效应的增强作用更加明显水溶液中Cr(Ⅵ)几乎完全被去除。结合傅里叶变换衰减全反射红外光谱(ATR-FTIR)和X射线光电子能谱(XPS)分析发现,水铁矿能够快速吸附Cr(Ⅵ),其中有62%的Cr在水铁矿表面被还原,占总去除率的41.5%。因此光照能够通过还原作用增强水铁矿对Cr(Ⅵ)的去除,从而降低Cr(...     

铬酸根离子在羟基铁离子一蒙脱石体系中的吸附行为研究

采矿，电镀，制革等行业废物排放及含Cr矿物风化可造成一些地区土壤和地下水的Cr污染，Cr主要以三价和六价形式存在，其中Cr(Ⅵ）有强的迁移能力，对动植物均有很强的毒害性。研究了在氧化，酸性条件下，土壤及土壤溶液中的蒙脱石和羟基铁离子共存时对铬酸根离子（主要以HCrO4^2-)和CrO4^2-等Cr(Ⅵ）形式存在）的吸附行为，进行了蒙脱石，羟基铁离子，Cr(Ⅵ）离子添加顺序不同的3个系列的实验，重点研究了Cr的初始质量浓度，溶液pH值，环境温度，吸附时间，溶液离子强度对3个系列Cr吸附行为的影响，并与羟基铁离子体系进行了对比。结果表明，蒙脱石－羟基铁离子体系的Cr吸附能力明显强于蒙脱石而低于羟基铁离子，其Cr吸附率随Cr初始质量浓度，温度的升高和吸附时间的延长而降低，随离子强度的升高而升高，而pH值对不同系列的Cr吸附率有不尽相同的影响。     

溶解性有机质协同针铁矿光催化还原Cr(Ⅵ)的行为与机理研究

在上覆水体中，太阳光驱动下溶解性有机质与矿物之间的相互作用对污染物迁移转化行为的影响及其机制尚未引起足够的重视。本文以富里酸和针铁矿分别作为溶解性有机质和半导体矿物的代表，建立实验室光催化体系，系统探究了富里酸影响针铁矿光催化还原六价铬[Cr(Ⅵ)]的行为和机理。结果表明，与光照-针铁矿体系相比，光照-针铁矿-富里酸体系对Cr(Ⅵ)的去除率由19.8%提高至68.7%,故富里酸显著提高了针铁矿光催化还原Cr(Ⅵ)的能力，增强机制主要归结于富里酸提高了针铁矿产生光生电子的能力。此外，被还原的部分Cr(Ⅲ)与针铁矿表面羟基结合形成稳定的CrO(OH),并固定在针铁矿表面。这一成果可为半导体矿物在酸性矿山废水治理中的应用提供理论依据。     

天然含铅黄铁矿试样处理含Cr(Ⅵ)废水的机理研究

天然黄铁矿对Cr (Ⅵ)具有较强的处理能力。本研究选取湖北十堰某天然含铅黄铁矿试样处理含Cr (Ⅵ)的废水,利用X射线衍射、X射线荧光光谱对样品进行结构与成分分析,考察了去除Cr(Ⅵ)反应的影响因素。结果表明,天然含铅黄铁矿样品对Cr (Ⅵ)具有较好的去除能力,其对浓度为50mg/L的含Cr(Ⅵ)废水去除率达95%~99%。并系统研究了黄铁矿颗粒粒度、反应时长、pH值对处理含Cr(Ⅵ)废水性能的影响,发现Cr(Ⅵ)主要吸附在黄铁矿颗粒表面形成絮状物质,对反应后产物的SEM和XRD分析结果表明,反应形成的絮状沉淀物为含铬、铅元素的针状铬铅矿,这对生成次生矿物沉淀从而除铬的新方法具有进一步的研究意义。     

铬酸根离子在羟基铁离子-蒙脱石体系中的吸附行为研究

采矿、电镀、制革等行业废物排放及含Cr矿物风化可造成一些地区土壤和地下水的Cr污染 .Cr主要以三价和六价形式存在 ,其中Cr(Ⅵ )有强的迁移能力 ,对动植物均有很强的毒害性 .研究了在氧化、酸性条件下 ,土壤及土壤溶液中的蒙脱石和羟基铁离子共存时对铬酸根离子 (主要以HCrO2 - 4和CrO2 - 4等Cr(Ⅵ )形式存在 )的吸附行为 .进行了蒙脱石、羟基铁离子、Cr(Ⅵ )离子添加顺序不同的 3个系列的实验 ,重点研究了Cr的初始质量浓度、溶液 pH值、环境温度、吸附时间、溶液离子强度对 3个系列Cr吸附行为的影响 ,并与羟基铁离子体系进行了对比 .结果表明 ,蒙脱石 -羟基铁离子体系的Cr吸附能力明显强于蒙脱石而低于羟基铁离子 ,其Cr吸附率随Cr初始质量浓度、温度的升高和吸附时间的延长而降低 ,随离子强度的升高而升高 ,而pH值对不同系列的Cr吸附率有不尽相同的影响 .     

Mn-Cr(Ⅵ)在岩溶水系统内的交互作用

采用窄缝槽实验装置, 分别模拟岩溶水系统内单一Mn、Cr(Ⅵ)以及Mn-Cr(Ⅵ)复合体系的动态吸附、物理解吸、化学解吸3个阶段的行为特征, 分析含锰、铬污水对地下水的污染规律及其相互作用.结果表明: 土壤对单一体系Mn的吸附率远大于Cr(Ⅵ), 但两者均以专性吸附为主, 不易活化、迁移; 在复合体系内均出现吸附率降低、解吸率升高, 表现为以物理吸附为主, 易活化、迁移, 从而引起水体重金属污染; 两者表现为显著的协同作用, 但Mn对Cr(Ⅵ)的影响远小于Cr(Ⅵ)对Mn的影响; 在酸性环境下, Mn对Cr(Ⅵ)的化学活性有轻微的抑制作用.      

镍钛改性膨润土对铬的吸附性能研究

以钠基膨润土为原料,制备镍钛交联改性膨润土、镍钛有机复合改性膨润土,并应用于含铬模拟废水的处理。探讨了改性膨润土的用量、pH值、吸附时间等最佳使用条件,比较了原土、交联改性土、有机复合改性土对铬的吸附效果。结果表明改性土的吸附效果明显优于原土,在最佳实验条件下,交联改性土、有机复合改性土对Cr(Ⅵ)的去除率分别达到了87%和96%。两种改性土对铬吸附行为均符合Langmuir吸附等温方程,饱和吸附量和Lang-muir常数分别为3.1827mg/g、8.5543mg/g和3.5007、1.2738。     

零价铁去除Cr（Ⅵ）的批实验研究

零价铁去除Cr(Ⅵ)的一系列批实验结果表明：水溶液中发生的氧化还原反应符合准一级反应；对于相同粒度的铁屑(比表面积2．89m^2／g)，固液比由05g／100mL增加到2．0g／100mL，Cr(Ⅵ)质量浓度达到排放标准所需反应时间从26．7min降为3．6min；在固液比相同、原水中Cr(Ⅵ)质量浓度不超过30mg／L时，原水质量浓度增大，达到饮用水标准的反应时间增加；其他条件相同，升高温度可提高零价铁与Cr(Ⅵ)的反应速率。     

硅藻土负载羟基氧化铁对铬（VI）吸附的固体浓度效应研究

利用硅藻土负载羟基氧化铁颗粒作吸附剂对六价铬进行吸附和解吸附实验,探讨了硅藻土负载羟基氧化铁对六价铬的吸附机制和固体浓度效应。实验结果表明：在实验条件下,当吸附剂的用量从0.05 g增加到0.2 g时,六价铬的吸附量从23940.124μg/g降低到8575.415μg/g,吸附剂对Cr6＋的吸附存在明显的固体浓度（Cs）效应。吸附滞后角随着Cs 的增加而减小,吸附反应的可逆性增大。将实验数据分别用Languir和Freundlich吸附模型进行拟合,发现Freundl-ich吸附模型对实验数据拟合效果较好,表明该吸附反应以单分子层吸附为主。     

Decontamination of hexavalent chromium and tri-ethyl phosphate stimulants through photacatalytic oxidation

In this paper, the photocatalytic decontamination of hexavalent chromium and tri-ethyl phosphate, two important wastewater contaminants, are studied by the ultraviolet / nano-titanium dioxide process. The pH value and synergic effect between the oxidation of tri-ethyl phosphate and the reduction of hexavalent chromium were investigated in different concentrations of tri-ethyl phosphate and hexavalent chromium. Furthermore, the effects of ultraviolet and nano-titanium dioxide were investigated in a solution which contained tri-ethyl phosphate and hexavalent chromium. Results of adsorptions showed that hexavalent chromium was adsorbed better in acidic pH while the better adsorption for tri-ethyl phosphate was occurred in alkalinity pH. The reduction rate of hexavalent chromium was higher in acidic solutions while it was obtained at natural pH for tri-ethyl phosphate. In co-adsorption of hexavalent chromium and triethyl phosphate pollutants, tri-ethyl phosphate slightly increased adsorption of hexavalent chromium, but hexavalent chromium had no influence on the adsorption of tri-ethyl phosphate on nano-titanium dioxide particles. In contrast, triethyl phosphate has an improving effect on the reduction reaction rate of hexavalent chromium which increases with the interaction of the concentration of tri-ethyl phosphate in mixture. The same is true for the oxidation rate of tri-ethyl phosphate.     

Functionalized nanobiomaterials: high-performance sorbents for chromium remediation from water streams

In present work, fabrication of functionally tailored nanobiomaterials paraben-modified nanocellulose (PNC) and (2,3-epoxypropyl) trimethylammonium chloride-modified nanocellulose (EPTMAC-NC) for the remediation of trivalent and hexavalent chromium, respectively, from water streams has been done. The resulting PNC and EPTMAC-NC were characterized before and after sorption of chromium using spectroscopic and microscopic techniques. The sorption performance of PNC (23.92 mg/g; 95.67 %) and EPTMAC-NC (23.99 mg/g; 95.94 %) was evaluated for trivalent and hexavalent chromium, respectively, at 0.5 g biosorbent dose; 500 mL sample volume; 25 mg/L chromium conc.; 40 min kinetic time; pH (6.5 for trivalent and 2.5 for hexavalent chromium) and 298 K temperature. From isothermic, kinetic and thermodynamic modeling, the sorption of trivalent and hexavalent chromium was physisorption, spontaneous, feasible and endothermic in nature. These findings expose new path in the line of high performance, scalable and economic nanobiomaterials for the abatement of toxic metals from water streams.     

Biosorption of hexavalent chromium from aqueous solution onto pomegranate seeds: kinetic modeling studies

Hexavalent chromium has been proved to be the reason of several health hazards. This study aimed at evaluating the application of pomegranate seeds powder for chromium adsorption (VI) from aqueous solution. Chromium adsorption percentage (VI) increased with increasing the adsorbent dosage. Chromium adsorption capacity (VI), at pH = 2 and 10 mg/L initial metal concentration, decreased from 3.313 to 1.6 mg/g through increasing dosage of adsorbent from 0.2 to 0.6 g/100 ml. The adsorption rate increased through increase in chromium initial concentration (VI). However, there was a removal percentage reduction of chromium (VI). Chromium adsorption kinetics by different models (pseudo-first-order, modified pseudo-first-order, pseudo-second-order, Elovich, intraparticle diffusion, Boyd kinetic) was investigated as well. Studies on adsorption kinetic indicated that the experimental data were matched by pseudo-second-order model (R ² = 0.999) better. Obtained results demonstrated the pomegranate seeds can be used as an effective biomaterial and biosorbent for hexavalent chromium adsorption from aqueous solutions.     

Soft X-ray spectroscopic studies of the reaction of fractured pyrite surfaces with Cr(VI)-containing aqueous solutions

We have used synchrotron-based soft X-ray core-level photoemission and adsorption spectroscopies to study the reaction of aqueous sodium chromate solutions with freshly fractured pyrite surfaces. Pyrite surfaces were reacted with 50 μM sodium chromate solution at pH 7 for reaction times between 1 min and 37 hr. Additional experiments were performed at pH 2 and pH 4 with 50 μM sodium chromate solutions and at pH 7 with 5 mM solutions. At chromate concentrations of 50 μM, all chromium present on the pyrite surface was in the form of Cr(III), while at 5 mM, both Cr(III) and Cr(VI) were present at the pyrite surface. Minor quantities of oxidized sulfur species (sulfate, sulfite, and zero-valent sulfur) were identified as reaction products on the pyrite surface. The amount of oxidized sulfur species observed on the surface was greater when pyrite was reacted with 5 mM Cr(VI) solutions because the rate of chromium deposition exceeded the rate of dissolution of pyrite oxidation products, effectively trapping Cr(VI) and oxidized sulfur species in an overlayer of iron(III)-containing Cr(III)-hydroxide. This work shows that pyrite, an extremely cheap and readily available waste material, may be suitable for the removal of hexavalent chromium from acidic to circumneutral waste streams. The reduced chromium ultimately forms a coating on the pyrite surface, which passivates the pyrite surface towards further oxidation.     

Removal of airborne hexavalent chromium mist using chitosan gel beads as a new control approach

Airborne hexavalent chromium is a known human respiratory carcinogen and allergen. Many workers are exposed to hexavalent chromium in various processes which chromium electroplating plants are the most common. In this study, the feasibility of a new control approach to remove this pollutant using chitosan beads as a biosorbent was investigated. Hexavalent chromium sorption was studied relative to pH, pollution concentration, sorbent concentration, temperature, and air velocity using one factor at a time approach and Taguchi experimental design. Polluted air with different chromium mist concentrations (10–5000 μg/m³) was contacted to chitosan beads (3.3–20 g/L), floating in distilled water with adjusted pH (3–7), using an impinger at different temperatures (20 and 35 °C), and various velocities (1.12 and 2.24 m/s). The ANOVA test result showed that, there were statistical significant differences between factor levels except optimized pH levels. The higher ions removal efficiencies were achieved at lower levels of air velocities, pollution concentrations, and higher levels of solution pH values, temperatures, and sorbent concentrations.     

微波碱性体系消解-电感耦合等离子体发射光谱法测定固体废物中的六价铬

六价铬Cr(Ⅵ)是建设用地土壤及固体废物环境监测的必测指标之一,为了配套现行土壤环境质量标准,建立操作简便、准确精密的Cr(Ⅵ)前处理和分析测定方法势在必行。本文采用0.1mol/L磷酸氢二钠溶液(pH=9.0)作为提取剂,微波炉消解,在优化的微波消解温度和时间内,保证了对固体样品基体的破坏作用,将晶格中的Cr(Ⅵ)全部释放到溶液中,并有效抑制了Cr(Ⅲ)氧化。用0.45μm滤膜在pH=9.0条件进行过滤后,可以将六价铬(溶液)与三价铬(沉淀)分离,借助电感耦合等离子体发射光谱法(ICP-OES)完成样品溶液中Cr(Ⅵ)的定量。结果表明:当样品量为1.00g,微波消解温度为90℃,消解时间为20min时能够保证固体废物中Cr(Ⅵ)的完全提取及准确测定。方法检出限为0.057mg/kg,相对标准偏差(n=7)低于3.20%,与HJ 687标准方法进行比对,测得的相对偏差介于-5.6%~7.6%;实际固体废物中Cr(Ⅵ)的加标回收率为94.3%~96.6%。与前人相关的电感耦合等离子体发射光谱法(检出限0.83mg/kg,加标回收率均值87.2%)相比,本方法的检出限更低,样品前处理时间更短,自动化程度高,可应用于环境监测领域。     

Adsorption of chromium (VI) from aqueous solution by the iron (III)-impregnated sorbent prepared from sugarcane bagasse

An iron (III)-impregnated sorbent was prepared from sugarcane bagasse and ferric chloride solution via carbonization/activation in a muffle furnace at 500?°C for 4?h. The adsorption removal of chromium (VI) from aqueous solution by the iron (III)-impregnated sorbent was then studied in a batch system. With increasing initial chromium (VI) concentration from 25 to 130?mg/L at an adsorbent dose of 300?mg/50?mL, the amount of adsorbed chromium (VI) increased from 4.15 to 12.20?mg/g at 20?°C, from 4.16 to 12.50?mg/g at 30?°C, and from 4.16 to 13.72?mg/g at 40?°C. The dynamical data fit very well with the pseudo-second-order kinetic model, and the calculated adsorption capacities of 4.16, 8.37, and 13.37?mg/g were equal to the actual values of the experiments at the initial chromium (VI) concentrations of 25, 50, and 100?mg/L, respectively. The Langmuir isotherm could yield better fits than the Freundlich isotherm. The calculated isotherm parameters confirmed the favorable adsorption of chromium (VI) on the iron (III)-impregnated sorbent.     

Hexavalent chromium removal from aqueous solutions by using low-cost biological wastes: equilibrium and kinetic studies

The batch removal of hexavalent chromium from aqueous solutions using almond shell, activated sawdust, and activated carbon, which are low-cost biological wastes under different experimental conditions, was investigated in this study. The influences of initial concentration, adsorbent dose, adsorbent particle size, agitation speed, temperature, contact time, and pH of solution were investigated. The adsorption was solution pH dependent and the maximum adsorption was observed at a solution pH of 2.0. The capacity of chromium adsorption under equilibrium conditions increased with the decrease in particle sizes. The equilibrium was achieved for chromium ion after 30?min. Experimental results showed that low-cost biosorbents are effective for the removal of pollutants from aqueous solution. The pseudo-second-order kinetic model gave a better fit of the experimental data as compared to the pseudo-first-order kinetic model. Experimental data showed a good fit with the Freundlich isotherm model. Changes in the thermodynamic parameters, including Gibbs free energy (??G_o), enthalpy (??H_o), and entropy (??S_o), indicated that the biosorption of hexavalent chromium onto almond shell, activated sawdust, and activated carbon was feasible, spontaneous, and endothermic in the temperature range 28?C50?°C.