Microbial reduction of uranium(Ⅵ) by Bacillus sp.dwc-2:A macroscopic and spectroscopic study

The microbial reduction of U(VI) by Bacillus sp. dwc-2, isolated from soil in Southwest China,was explored using transmission electron microscopy(TEM), X-ray photoelectron spectroscopy(XPS) and X-ray absorption near edge spectroscopy(XANES). Our studies indicated that approximately 16.0% of U(VI) at an initial concentration of 100 mg/L uranium nitrate could be reduced by Bacillus sp. dwc-2 at pH 8.2 under anaerobic conditions at room temperature.Additionally, natural organic matter(NOM) played an important role in enhancing the bioreduction of U(VI) by Bacillus sp. dwc-2. XPS results demonstrated that the uranium presented mixed valence states(U(VI) and U(IV)) after bioreduction, which was subsequently confirmed by XANES. Furthermore, the TEM and high resolution transmission electron microscopy(HRTEM) analysis suggested that the reduced uranium was bioaccumulated mainly within the cell and as a crystalline structure on the cell wall.These observations implied that the reduction of uranium may have a significant effect on its fate in the soil environment in which these bacterial strains occur.     

Uranium speciation in coal bottom ash investigated via X-ray absorption fine structure and X-ray photoelectron spectra

Similar to chromium contamination, the environmental contamination caused by uranium in radioactive coal bottom ash (CBA) is primarily dependent on the chemical speciation of uranium. However, the relationship between uranium speciation and environmental contamination has not been adequately studied. To determine the relationship between uranium speciation and environmental contamination, X-ray absorption fine structure (XAFS) and X-ray photoelectron spectra (XPS) analyses were performed to determine the uranium speciation in CBA exposed to different chemical environments and simulated natural environments. The leachability of the different forms of uranium in the CBA was studied via a simulated acid rain leaching experiment, and the results showed that 57.0% of the total uranium was leached out as U(VI). The results of a linear combination fit (LCF) of the X-ray absorption near edge structure (XANES) spectrum revealed that in the raw CBA, the uranium mainly occurred as U3O8 (71.8%). However, in the iron-rich particles, the uranium mainly occurred as UO2 (91.9%) after magnetic separation. Magnetite is a ubiquitous ferrous-bearing oxide, and it was effective for the sorption of U(IV). The result of FeSO4 leaching experiment indicated that 96.57% of total uranium was reduced from U(VI) to U(IV) when infiltrated with the FeSO4 solution for 6 months. This result clearly demonstrated the changes in chemical valence of uranium in the coal ash and provided a conceptual principle for preventing uranium migration from ash to the surrounding soil and plants.     

Microbial reduction of uranium (VI) by Bacillus sp. dwc-2: A macroscopic and spectroscopic study

The microbial reduction of U(VI) by Bacillus sp. dwc-2, isolated from soil in Southwest China, was explored using transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and X-ray absorption near edge spectroscopy (XANES). Our studies indicated that approximately 16.0% of U(VI) at an initial concentration of 100 mg/L uranium nitrate could be reduced by Bacillus sp. dwc-2 at pH 8.2 under anaerobic conditions at room temperature. Additionally, natural organic matter (NOM) played an important role in enhancing the bioreduction of U(VI) by Bacillus sp. dwc-2. XPS results demonstrated that the uranium presented mixed valence states (U(VI) and U(IV)) after bioreduction, which was subsequently confirmed by XANES. Furthermore, the TEM and high resolution transmission electron microscopy (HRTEM) analysis suggested that the reduced uranium was bioaccumulated mainly within the cell and as a crystalline structure on the cell wall. These observations implied that the reduction of uranium may have a significant effect on its fate in the soil environment in which these bacterial strains occur.     

灭活与非灭活条件下植物乳杆菌去除U(VI)的机理

在不同时间,pH值和生物量浓度条件下,进行了灭活与非灭活植物乳杆菌去除水中铀的对比试验,探讨了二者去除水中铀的机理,通过SEM-EDS、FTIR、XPS及XRD分析了铀与菌体表面的微观作用机理以及菌体表面沉积物的特征.结果表明：植物乳杆菌经灭活后,其吸附铀的能力得到显著的提高,当U（VI）初始浓度为10mg/L、pH值为6.0、37℃条件下,120min内灭活菌体对U（VI）的去除率为94.7%,而活菌体的去除率为88.9%.灭活菌体具有更高的铀吸附容量,在生物量浓度为0.06~0.24mg/L,pH值（3.0~7.0）条件下,灭活菌体与活菌体的U（VI）累积容量比W均大于1.SEM-EDS、FTIR分析结果表明,活细胞和灭活细胞都可通过细胞表面的羟基、酰基及羧基等官能团吸附、配位络合U（VI）.XRD分析表明,活菌体可生物磷酸矿化水中的U（VI）.活菌体的XRD谱图在2θ（18.023,25.492,27.343,40.813°处）有4个明显的磷酸铀酰晶体峰,而灭活菌体的XRD谱图显示为非晶态.XPS结果表明,活菌体可生物还原U（VI）.活菌体能谱图中U4f7/2和U4f5/2轨道出现了结合能为380.20eV和390.65eV的U（VI）分裂峰,而灭活菌体的能谱图中没有出现U（IV）的分裂峰.     

Aspergillus tubingensis介导植酸盐水解促进U(VI)-PO43-生物矿化

从广东某铀尾矿库水下沉积物中分离筛选出了一株能水解植酸盐的真菌M5-1,对其菌落形态、ITS序列、最适生长pH值、对铀的耐受性及其水解植酸盐的效果进行了分析,随后对M5-1生物矿化铀过程中pH值、正磷酸盐浓度、铀浓度、铀去除率的变化进行了监测,对矿化产物的主要元素和矿物组成进行了分析.证实了真菌M5-1为Aspergillus tubingensis（MH978623）,其最适生长pH值范围为6~7,对铀（~0.84mmol/L）具有较强的耐受性;Aspergillus tubingensis介导植酸盐水解促进U（VI）-PO₄^3-矿化62d后,铀的去除率达95.2%;Aspergillus tubingensis介导U（VI）-PO₄^3-矿化过程中可能形成了难溶的氢铀云母和变钠铀云母矿物.结果表明,Aspergillus tubingensis能有效水解植酸盐释放可溶性正磷酸盐,从而促进U（VI）-PO₄^3-矿化.研究结果为采用Aspergillus tubingensis介导植酸盐水解原位修复铀污染地表水提供了试验依据.     

微生物溶解载铀赤铁矿及再固定铀的试验研究

将载铀赤铁矿、核黄素(RF)和Sphingomonas sanxanigenens(S. sanxanigenens)同时投加到培养基中,监测培养过程中溶液的总铁、亚铁以及U(VI)浓度的变化,表征载铀赤铁矿还原性溶解前后固相产物中铁和铀的化学形态与价态,分析温度、共存离子对RF介导S. sanxanigenens还原性溶解载铀赤铁矿及再固定铀的影响.结果表明:S. sanxanigenens能够还原性溶解载铀赤铁矿,从而导致铀的释放;RF能够促进S. sanxanigenens还原性溶解载铀赤铁矿,且RF浓度越高越有利于这种还原性溶解;在30℃下RF能显著促进载铀赤铁矿的还原性溶解,且产物中稳定态铀的比例较高;添加2mmol/L Ca²⁺或CO₃^2-对RF介导S. sanxanigenens还原性溶解载铀赤铁矿具有促进作用;添加2mmol/L PO₄^3-能提高残渣态铀的比例,促进铀的固定;RF能够促进S. sanxanigenens对Fe(III)和U(VI)的还原,且反应过程伴随着次生铁矿物的生成.这些研究结果为提出RF介导S. sanxanigenens释放及再固定铀的新方法奠定了基础.     

氨基修饰稻壳生物炭对水溶液中铀的吸附动力学特性

为了探究NBC（氨基修饰生物炭）对U（Ⅵ）的吸附性能,通过在BC（未修饰生物炭）上负载氨基的方法得到氨基修饰生物炭,研究BC、NBC对水溶液中U（Ⅵ）的吸附特征,分析生物炭添加量、溶液pH、溶液中阴离子、初始ρ〔U（Ⅵ）〕、吸附时间和吸附体系温度等因素对U（Ⅵ）吸附的影响,筛选最优的吸附条件,并利用SEM（扫描电镜）、FT-IR（傅里叶红外光谱）、XRD（X-射线衍射）、XPS（X-射线能谱）、BET比表面积、元素分析、零点电位（Zeta电势）测定等手段表征BC、NBC的结构特征,并进一步探讨其对U（Ⅵ）的吸附机理.结果表明:①NBC的比表面积和吸附位点显著增加,对U（Ⅵ）的吸附速率和吸附量明显增加,NBC的最大吸附量（69.63 mg/g）大于BC（53.95 mg/g）. ②NBC对U（Ⅵ）吸附的最佳条件为生物炭添加量0.4 g/L、pH 6、初始ρ〔U（Ⅵ）〕20 mg/L、吸附时间1 h、吸附体系温度328 K. ③BC、NBC对U（Ⅵ）的吸附动力学均符合伪二级动力学方程,R2均为0.999;等温吸附过程均符合Sips等温吸附模型,R2均大于0.914.研究显示,NBC的吸附能力强、环境耐受性好,具有很好的应用潜力.      

磁性生物炭对水体中对硝基苯酚的吸附特性

为了制备同时具备磁分离和优良吸附性能的环境友好吸附材料,以棉花秸秆为生物质原料制备生物炭（CSBC）,采用共沉淀法制得磁性棉花秸秆生物炭（MCSBC）.通过元素分析、SEM、XRD、XPS、FTIR和VSM等对MCSBC进行表征,研究了CSBC和MCSBC对水中对硝基苯酚（PNP）的吸附特性.结果表明,溶液pH值对CSBC和MCSBC吸附PNP的影响较大,在酸性条件下的吸附量更大.CSBC和MCSBC对PNP的吸附动力学过程可被准二级动力学模型很好地描述,吸附过程包括液膜扩散和颗粒内扩散两个阶段.Langmuir、Freundlich和Sips模型都可以很好地描述PNP在CSBC和MCSBC上的吸附行为,最大吸附量分别为44.54和48.94mg/g,MCSBC相较于CSBC对PNP的吸附具有更好的效果.热力学研究结果表明,CSBC和MCSBC对PNP的吸附过程为熵增加的自发吸热过程.再生试验结果表明,经6次吸附-解吸循环后,MCSBC对PNP的吸附容量仍能达到初始吸附量的82%.     

镧改性生物炭对砷、镉的吸附特征研究

为研究改性生物炭对砷镉复合污染水体中镉和砷的吸附特征。本研究以牛粪、污泥、竹屑三种不同原料制备生物炭,利用镧(La)对生物炭进行改性,并采用元素分析、扫描电镜、傅里叶变换红外光谱和X射线光电子能谱等分析手段对改性前后的生物炭进行表征,结合等温吸附实验及吸附动力学实验,对比各生物炭对As (V)、Cd (II)的吸附性能并探讨其内在机理。结果表明,竹屑炭(BB)的芳香性大于牛粪炭(CB)和污泥炭(SB)。La改性使三种生物炭在热解过程中形成了酮类、酯类、羰基等含氧官能团,并在表面引入羟基。X射线光电子能谱结果显示La以氢氧化物的形式负载在生物炭表面。各生物炭对Cd (II)、As (V)的吸附符合准二级吸附动力学和Langmuir等温吸附方程。La改性生物炭对As (V)的最大拟合吸附量达到3.47～4.51 mg/g,显著高于未改性生物炭(1.82～2.50 mg/g)(p<0.05)。在As (V)、Cd (II)吸附过程中,La改性生物炭表面的La与As (V)发生络合反应,同时Cd (II)与镧基氢氧化物发生配体交换,生成Cd (OH)₂沉淀。本研究证明了La改性有效提高了生物炭对As (V)、Cd (II)同时吸附的能力。     

TiO2/生物炭复合材料处理低浓度氨氮废水

为研究功能复合材料对低浓度氨氮〔ρ(NH₄+-N)≤50 mg/L〕废水的处理效果,采用水热法制备TiO₂/生物炭复合材料,并在自制光催化反应装置中对低浓度氨氮废水进行处理,考察TiO₂负载量、温度、pH等因素对NH₄+-N去除过程的影响以及催化的最终降解产物.结果表明,TiO₂/生物炭复合材料能有效催化去除废水中的NH₄+-N,其优化处理条件:ρ(NH₄+-N)为50 mg/L,TiO₂/生物炭复合材料投加量为1.5 g/L,254 nm紫外灯照射120 min,TiO₂负载量为20%,废水初始pH为11.0,曝气量为150 mL/min.在优化处理条件下,当温度为60 ℃时NH₄+-N去除率可达100%,常温(30 ℃)下可达67%.反应最终产物中ρ(NO₂--N)非常低,并且无NO₃--N生成.研究显示,TiO₂/生物炭复合材料具有将NH₄+-N转化为N₂的良好光催化氧化选择性.      

磁性膨润土材料吸附处理印染废水研究

针对目前膨润土在应用中的一些问题,对膨润土进行磁性能改性,通过共沉淀法制备磁性膨润土颗粒,并对其进行了X射线衍射和磁性能表征分析.以阴离子染料OrangeⅡ为目标化合物,研究了磁性膨润土材料对OrangeⅡ废水的吸附效果,并探讨了主要工艺参数如阳离子表面活性剂的质量浓度、pH、温度等对染料去除率的影响.结果表明:阳离子...     

磷酸改性生物炭负载硫化锰去除废水中重金属镉

采用磷酸作为活化剂对黍糠生物炭进行改性,得到富含活性官能团的功能性生物炭（fCBC）,并将其作为硫化锰（MnS）的载体,最终成功制备出硫化锰负载的磷酸改性生物炭（MnS-fCBC）,可用于水体中镉（Cd）的高效去除.系统评价了初始浓度、初始pH值以及MnS-fCBC投加量对于吸附反应的影响. MnS-fCBC表现出优越的吸附Cd的能力,在初始Cd浓度为200mg/L、pH=6和投加量1g/L的条件下,MnS-fCBC对于Cd的吸附容量最大,达145.15mg/g.吸附反应受pH值影响显著,在偏酸性条件下能取得较好的去除效果.通过X射线衍射仪（XRD）和拉曼光谱仪（Raman）对MnS-fCBC进行结构表征分析,结合批次试验探讨了Cd的去除机理.结果表明,表面络合和化学沉淀是Cd去除的主要机理.材料的回用性能试验显示,在5次循环使用后,材料依然有较高的Cd去除能力,表明其具有较高的可重用性.因此,MnS-fCBC可作为一种高效的Cd吸附剂,应用于含Cd废水处理.     

针铁矿改性生物炭的制备及对Cr (Ⅵ)的吸附性能研究

在不同热解温度及原料配比条件下,采用水解共沉淀方法制备针铁矿改性生物炭材料（GMB）,借助SEM-EDS、XRD、FTIR、XPS进行表征,并进行Cr （Ⅵ）吸附实验,探究吸附性能和机理。结果表明:1）经改性后生物炭表面生成了羟基氧化铁（FeOOH）,吸附能力有大幅提升;2）热解温度为600℃,生物炭与Fe （NO₃）₃·9H₂O的质量比为1:12时制备的GMB600-12表现出最佳吸附性能,最大吸附容量为20.67 mg/g;3）准二级动力学揭示Cr （Ⅵ）的吸附以化学吸附为主,Langmuir和Freundlich模型都能很好地描述GMB对Cr （Ⅵ）的吸附特征;4） XPS的结果进一步表明GMB去除水溶液中Cr （Ⅵ）是氧化还原和表面吸附协同作用的结果。     

改性多孔生物炭的制备及其对水中四环素的吸附性能研究

以常见的农业废弃物玉米秸秆为原料,以NaHCO_3和三聚氰胺为活化剂,一步碳化活化制备得到了一种改性多孔生物炭,研究了其对模拟四环素(TC)废水的吸附行为,同时采用SEM、XRD、Raman、FTIR、BET和元素分析对材料进行表征分析.探究了热解温度、三聚氰胺添加量、吸附剂投加量、反应时间、初始浓度、环境温度和pH对改性多孔生物炭去除水溶液中TC的影响.相比于原始生物炭(C800),改性后的秸秆生物炭(MPC800-10)对TC拥有更优异的吸附能力,能在短时间内快速高效地去除TC.由表征结果可知,同时添加NaHCO_3和三聚氰胺得到的改性多孔生物炭(MPC800-10)相对于原始生物炭(C800)比表面积更大,孔结构更丰富,芳香性增强,且亲水性和极性也有所增大,表面官能团更丰富,含氧官能团增加.MPC800-10对TC的吸附更符合Pseudo-second-order动力学模型和Freundlich等温吸附模型,且最大吸附量达到347 mg·g~(-1).热力学分析表明MPC800-10对TC的吸附是一个自发、吸热的过程.在酸性和中性条件下MPC800-10对TC都有较好的吸附能力,且具有一定的抗离子干扰能力和良好的再生性能.本研究将为农田废弃物的资源化利用及废水中抗生素的污染治理奠定坚实的基础.     

造纸污泥生物炭对四环素的吸附特性及机理

以造纸污泥为原料,在限氧条件下,通过控制热解温度（300,500和700℃）,制备生物炭（SBC300、SBC500和SBC700）,比较了3种生物炭的基本理化性质;以四环素（TC）为目标污染物,研究了造纸污泥生物炭（SBC）对TC的吸附特性及机理.结果表明,SBC对TC的吸附以化学吸附为主,吸附平衡时,SBC300对TC的去除率最低,为38.8%,SBC700的去除率最高,为54.1%;同时Langmuir模型能更好地描述此吸附过程,且最大吸附量依次为SBC700（63.8mg/g） > SBC500（50.6mg/g） > SBC300（40.0mg/g）.热力学分析表明,SBC对TC的吸附为自发且吸热的过程.pH值影响TC的存在形态及SBC的表面带电情况,对吸附过程有较大影响.通过吸附等温线分解法定量描述了表面吸附作用及分配作用的贡献率,结合FTIR分析,表明SBC对TC的吸附可能是分配作用、静电作用、氢键作用、π-π EDA作用及离子交换作用等共同作用的结果.     

磷酸改性水生植物生物炭吸附微囊藻毒素-LR及其影响因素

将水生植物制成生物炭是水生植物资源化利用的新方式,本研究将两种水生植物苦草和狐尾藻在不同温度下热解制备生物炭并用磷酸进行改性,探究了生物炭对水中微囊藻毒素（以MC-LR为例）去除的影响,并研究了其对MC-LR的吸附动力学及影响因素.同时,采用扫描电镜、元素分析、比表面及孔径分析、FTIR和XPS对生物炭进行表征.结果表明,生物炭表面含有丰富的含氧官能团,更高热解温度制备的生物炭具有更丰富的孔隙,对MC-LR的去除率也更高.生物炭对MC-LR的吸附符合准一级动力学、准二级动力学和颗粒内扩散模型.离子强度对生物炭吸附的影响较小,而较高的pH、较大分子量的DOM会抑制吸附.磷酸改性能提高生物炭的吸附性能,并且减弱pH和DOM对生物炭吸附效果的影响.综上,利用水生植物制备的改性生物炭可用于吸附MC-LR,为控制水体中的微囊藻毒素污染提供了新的思路和理论依据.     

香榧壳生物炭/g-C3N4活化过硫酸盐的光催化性能

采用简便一步热聚合法制备高催化活性的生物炭/g-C₃N₄复合光催化剂,并在可见光下活化过硫酸盐（PS）应用于对-乙酰氨基酚（AAP）废水的降解研究.通过紫外-可见漫反射吸收光谱（UV-vis DRS）、光致发光光谱（PL）对该复合催化剂的光学性质进行了研究.结果表明,生物炭的引入使g-C₃N₄的可见光吸收边界从483nm增强至553nm,并且提高了光致电子-空穴对的分离效率.扫描电子显微镜（SEM）、X射线衍射光谱（XRD）、傅里叶变换红外光谱（FT-IR）及X射线光电子能谱（XPS）的表征结果显示生物炭的引入改善了g-C₃N₄的微结构.在反应体系中引入PS强化了AAP的去除效率,在可见光照射下其降解速率是未添加PS的8.9倍,表明该催化体系可有效活化PS产生更多高活性氧化物质.自由基捕获实验表明该催化系统可能存在·O₂^-、h⁺、·OH和·SO₄^-活性物种,复合材料性能的提升主要归因于生物炭作为电子受体,有效抑制了电子-空穴的复合.     

Mg/Al双金属氧化物对As(V)吸附性能的研究

研究了以镁铝水滑石为原料制备的Mg/Al双金属氧化物对溶液中As(V)的吸附作用及其影响因素.结果表明：Mg/Al双金属氧化物对As(V)具有较强的吸附能力,吸附规律符合Langmuir等温吸附方程,根据计算所得的理论最大吸附量为51.02 mg·g-1,与实验得出的最大吸附量50.53 mg·g-1基本一致;运用3种...     

La-EDTA coated Fe3O4 nanomaterial: Preparation and application in removal of phosphate from water

La-EDTA-Fe3O4 was prepared by a chemical co-precipitation method. The magnetic composite was characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). Furthermore, the adsorption properties of La-EDTA-Fe3O4 toward phosphate in water were investigated. The uptake rate of phosphate in water by La-EDTA-Fe3O4 was 3-1000 times than that of EDTA-Fe3O4 , and reached 97.8% at 7 hr. The adsorption process agreed well with the Freundlich model and kinetics studies showed that the adsorption of phosphate proceeds according to pseudo second-order adsorption kinetics. The maximum removal rate was achieved at pH 6.0-7.0. The La-EDTA-Fe3O4 had good adsorption properties and could be separated well from aqueous solution by a permanent magnet. Therefore, this nanomaterial has potential application for the removal of phosphate from large water bodies.     

Enhanced removal of Cr(VI) by biochar with Fe as electron shuttles

Biochar is extensively used as an effective soil amendment for environmental remediation. In addition to its strong contaminant sorption capability, biochar also plays an important role in chemical transformation of contaminant due to its inherent redox-active moieties. However, the transformation efficiency of inorganic contaminants is generally very limited when the direct adsorption of contaminants on biochar is inefficient. The present study demonstrates the role of Fe ion as an electron shuttle to enhance Cr(VI) reduction by biochars. Batch experiments were conducted to examine the effects of Fe(III) levels, pyrolysis temperature of biochar, initial solution pH, and biochar dosage on the efficiency of Cr(VI) removal. Results showed a significant enhancement in Cr(VI) reduction with an increase in Fe(III) concentration and a decrease of initial pH. Biochar produced at higher pyrolysis temperatures (e.g., 700°C) favored Cr(VI) removal, especially in the presence of Fe(III), while a higher biochar dosage proved unfavorable likely due to the agglomeration or precipitation of biochar. Speciation analysis of Fe and Cr elements on the surface of biochar and in the solution further confirmed the role of Fe ion as an electron shuttle between biochar and Cr(VI). The present findings provide a potential strategy for the advanced treatment of Cr(VI) at low concentrations as well as an insight into the environmental fate of Cr(VI) and other micro-pollutants in soil or aqueous compartments containing Fe and natural or engineered carbonaceous materials.