Al3+离子掺杂对负载TiO2薄膜光催化活性的影响

以钛酸丁酯和Al2(SO4)3·18H2O为原料,采用溶胶凝胶法在钛片、玻璃、釉面瓷砖、陶瓷、不锈钢和铝片六种载体上制备了Al3+掺杂TiO2薄膜,讨论了不同Al3+掺杂浓度下,不同载体表面上制备的TiO2薄膜对甲基橙脱色率的影响。试验结果表明Al3+对TiO2薄膜的掺杂效果与载体的类型密切相关,并且不同载体其Al3+掺杂的最佳浓度也不同。Al3+掺杂后,TiO2薄膜光催化活性提高最大的是玻璃,其次是釉面瓷砖、铝片、钛片、陶瓷,最差的是负载不锈钢。     

Distribution, speciation and availability of antimony (Sb) in soils and terrestrial plants from an active Sb mining area

Here, we present one of the first studies investigating the mobility, solubility and the speciation-dependent in-situ bioaccumulation of antimony (Sb) in an active Sb mining area (Xikuangshan, China). Total Sb concentrations in soils are high (527-11,798 mg kg⁻¹), and all soils, including those taken from a paddy field and a vegetable garden, show a high bioavailable Sb fraction (6.3-748 mg kg⁻¹), dominated by Sb(V). Elevated concentrations in native plant species (109-4029 mg kg⁻¹) underpin this. Both chemical equilibrium studies and XANES data suggest the presence of Ca[Sb(OH)₆]₂, controlling Sb solubility. A very close relationship was found between the citric acid extractable Sb in plants and water or sulfate extractable Sb in soil, indicating that citric acid extractable Sb content in plants may be a better predictor for bioavailable Sb in soil than total acid digestible Sb plant content.     

铁锰复合氧化物同时吸附锑镉性能研究

以五价锑（Sb（V））和镉（Cd²⁺）为对象,考察了二者单独存在和共存体系下铁锰复合氧化物（FMBO）对其吸附性能,探讨了Sb（V）（或Cd²⁺）的吸附对Cd²⁺（或Sb（V））吸附的影响.研究发现,单独存在体系下Sb（V）和Cd²⁺的吸附常数K_F分别为0.48和1.13 L·mg^-1,而共存体系下则分别提高至1.88和1.51 L·mg^-1;Elovich动力学模型可较好地描述共存条件下Cd²⁺与Sb（V）在FMBO表面的吸附,表明该体系的吸附为多层吸附且为非均相扩散过程;吸附48 h后Sb（V）和Cd²⁺的最大吸附量分别达到0.32和1.43 mmol·g^-1;Sb（V）在偏酸性而Cd²⁺在偏碱性pH范围具有较好的吸附效果.Sb（V）（或Cd²⁺）通过改变FMBO表面ζ电位和反应平衡pH等机制影响Cd²⁺（或Sb（V））的吸附.此外,XPS和吸附后水相铁锰浓度结果显示,Cd²⁺可能与FMBO体相中Mn²⁺进行晶格置换并促进Mn²⁺的溶出,进而促进了Sb（V）的吸附.     

黔西南汞铊矿废弃物中污染物释放的联合调控研究

为评价植生改良与先锋植物联合调控作用对矿产采冶废弃物中污染物迁移的控制情况,以黔西南兴仁市滥木厂大量露天堆存的汞铊矿废弃物（采冶废渣、尾矿、废石等混合物）为研究对象,选择当地广泛存在的碳酸盐岩、腐熟牛粪作为植生改良剂,并种植三叶草和黑麦草作为先锋植物进行联合调控,通过淋滤实验评价其对废弃物中高毒性污染物Hg、Tl、As和Sb释放的抑制效果。结果表明：对照组废弃物淋滤3次所得淋滤液中Hg、Tl含量平均为14.8 μg/L和170.6 μg/L,As和Sb平均为22.1 μg/L和4.9 μg/L,在雨水淋溶下具有持续释放进入环境的风险;联合调控可对废弃物中Tl和Hg的释放有明显的抑制效果,其中淋滤液Tl含量降为对照的12.2%～54.1%,10%碳酸盐岩梯度的混种组淋滤液Tl含量为19.6 μg/L,效果最好;5%、10%碳酸盐岩梯度的三叶组和混种组淋滤液中Hg含量显著低于对照水平（p<0.05）,较对照降低34.5%～47.9%;而联合调控则致使废弃物中As、Sb释放,相关性分析表明,植生改良剂添加引起的废弃物基质中溶解性有机质含量增加与植物诱导下游离氧化铁的溶解可能是导致As、Sb释放的关键因素。形态分析结果表明,联合调控促使汞铊矿废弃物中Hg、Tl向残渣态转变,而促使残渣态As、Sb占比下降导致其活化。综上,对汞铊矿废弃物采用植生改良剂-先锋植物联合调控可显著抑制Hg、Tl的释放,但需考虑所加植生改良剂中溶解性有机质增加及废弃物基质中游离氧化铁溶解引起的As、Sb活化与释放带来的环境风险。     

改性水稻生物炭对水体中Sb(Ⅲ)的吸附

采用铁、锰对水稻秸秆生物质碳（BC）进行改性,将制备所得的锰改性生物碳（Mn-BC）和铁锰改性生物碳（Fe-Mn-BC）作为吸附剂,用于对水中Sb （Ⅲ）的吸附实验.通过全自动比表面积及孔隙度分析仪（BET）、扫描电子显微镜（SEM）对吸附剂的表面性质进行研究,在吸附最佳pH值和投加量条件下开展等温吸附、动力学吸附及体系共存阴离子影响实验,探究改性生物炭的再生吸附能力,最后利用傅里叶红外光谱仪（FT-IR）、X射线光电子能谱仪（XPS）探究Mn-BC和Fe-Mn-BC对Sb （Ⅲ）的吸附机理.结果表明：改性生物炭具有更大的比表面积及总孔容积.BC在pH值为2,Mn-BC和Fe-Mn-BC在pH值为4,投加量为2.5g/L,25℃条件下,BC、Mn-BC和Fe-Mn-BC的最大吸附量分别为5.08,11.45,29.45mg/g.BC对Sb （Ⅲ）的吸附主要为物理吸附,Mn-BC和Fe-Mn-BC对Sb （Ⅲ）的吸附为化学兼具物理吸附.Mn-BC吸附Sb （Ⅲ）受F^-、HCO₃^-和H₂PO₄^-的影响较大,Fe-Mn-BC对Sb （Ⅲ）的吸附基本不受离子类型和离子强度的干扰.Fe-Mn-BC较Mn-BC具有更突出的吸附再生能力和重复利用性.Mn-BC和Fe-Mn-BC对Sb （Ⅲ）的吸附过程,先是氧化反应将大部分的Sb （Ⅲ）氧化为Sb （Ⅴ）,再通过酸性条件下明显的静电作用,Sb （Ⅴ）与负载于Mn-BC上的Mn和Fe-Mn-BC上的Fe/Mn分别形成较为稳定的内层络合物Mn-O-Sb和Fe-O-Sb-Mn.此外,改性生物炭的官能基团-OH、C=O、N-H在吸附作用中也发挥着重要作用.     

都柳江水系沉积物锑等重金属空间分布特征及生态风险

以都柳江沉积物为研究对象,通过系统采集表层沉积物样品,测定其重金属含量,查明了流域沉积物中重金属空间分布特征,结合主成分分析和相关性分析等统计学方法探讨了都柳江表层水系沉积物中重金属的来源,并利用地累积指数法、富集因子法和生态风险指数法评估了沉积物中重金属污染状况及其潜在生态风险.结果表明:(1)都柳江表层沉积物中Sb含量极高,可达7 080 mg·kg~(-1),且从上游到下游呈现逐渐降低的趋势,As、Cd、Co、Cr、Cu、Mo、Ni、Pb、Tl和Zn等含量变化不大;(2)主成分分析提取的两个因子的累积贡献率达到77.67%,表明沉积物中重金属来源主要包括:矿业活动和自然源等;(3)地累积指数和富集因子表明,都柳江水系沉积物中Sb污染最为严重,其次是As和Cd,Co、Cu、Mo、Ni、Pb、Tl和Zn的污染较轻,未受Cr污染;(4)各金属Hakanson潜在生态风险指数(Eir)依次为SbCdAsCoNiPbCuZnCr,而重金属综合潜在生态风险指数(RI)结果表明,中度生态风险及以上等级的样品约占58.1%,严重生态风险等级的样点主要集中在受锑矿采选冶活动影响和支流八洛河汇入后等周边采样点位;都柳江流域各重金属生态风险指数在综合指数中占主导地位的是Sb,表明Sb在都柳江流域水系沉积物中具有极强的生态风险性.     

典型城市土壤中重金属锑(Sb)的含量分布特征及风险评价

为探讨重金属锑（Sb）在城市土壤中的分布特征和潜在风险,基于上海市102个地块1670个不同深度剖面土壤样品数据,分析4种典型土地利用类型土壤重金属Sb的含量分布特征,并通过潜在生态风险指数法和健康风险评价模型进行风险评价.结果表明,研究区域土壤ω（Sb）的平均值为0.52 mg·kg^-1,并呈现明显的聚集分布特性;土壤Sb含量随着土壤深度的增加逐渐降低,表层土壤Sb存在一定程度的富集,人类活动影响了土壤中Sb的分布.工业用地表层土壤Sb含量相较于其它3种类型土壤差异显著,其累积程度高于住宅用地和商服用地,农用地Sb含量水平最低.区域整体上处于清洁至尚清洁水平,但工业用地的单项污染指数相对最高,达到轻度污染水平,住宅用地、商服用地和农用地分别为尚清洁或清洁水平;潜在生态风险指数范围为4.23~7.61,区域整体表现为轻微潜在生态风险.工业用地潜在生态风险等级为中等,需引起重视.健康风险评价结果显示土壤Sb非致癌风险较小或可忽略.     

Effect of heavy metal contaminated shooting range soils on mycorrhizal colonization of roots and metal uptake by leek

We grew leek (Allium porrum) in soils of two shooting ranges heavily contaminated with heavy metals in the towns of Zuchwil and Oberuzwil in Switzerland as a bioassay to test theactivity of arbuscular mycorrhizal (AM) fungi in these soils.Soil samples were taken from (1) front of the shooting house(HOUSE), (2) the area between house and target (FIELD) and (3) the berm (BACKSTOP). Samples of Ribwort plantain (Plantagolanceolata) growing naturally within the shooting ranges werealso collected and the colonization of its roots by mycorrhizalfungi was measured. The number of AM spores in the soils wassignificantly reduced concomitant with the increase in thedegree of soil contamination with metals. In Zuchwil,mycorrhizal fungi equally colonized roots of Ribwort plantainsampled from BACKSTOP and HOUSE. In Oberuzwil, however, plantsfrom BACKSTOP had lower colonization when compared with thosesampled from HOUSE. Colonization of leek was strongly reducedin the BACKSTOP soil of Zuchwil and slightly reduced in theBACKSTOP soil of Oberuzwil when compared with plants grown inrespective HOUSE soil. Concentrations of Cd, Cr, Cu, Ni, Pb andZn in the leaves of leek grown in the BACKSTOP soil was withinthe range considered toxic for human consumption. This pointsto the high degree of bio-availability of these metal in thesesoils. Significant decrease in the number of mycorrhizal sporesin the BACKSTOP soils in Zuchwil and the low colonization ofleek roots grown in these soils point to possible changes inthe species diversity of mycorrhizal fungi in these soils.     

广西大厂多金属矿区河流中Sb和As的迁移及环境影响

以广西大厂多金属矿山为例,对其矿山尾矿堆及地表河流进行采样,研究矿山开采中释放的毒害元素Sb和As对河流水环境的影响. 结果表明,矿渣堆中的w(Sb)和w(As)分别为175～7 119和309～24 233 mg/kg;选厂排水中ρ(Sb)和ρ(As)最高值分别为5 475和179 μg/L;受矿山影响的河流中的ρ(Sb)和ρ(As)平均值在枯水期为630和100 μg/L,在丰水期为497和65 μg/L. 该矿山的开采致使选厂排水和矿山尾渣均对矿区河流中重金属含量做出显著贡献,已对周边河流产生严重影响,造成了刁江上游河水的污染. Sb与As虽然化学性质相似,但二者在河水中的迁移特性仍有明显的差别,As在河水中的衰减强于Sb. 河水中Sb和As的影响范围都很大,模拟计算表明,Sb和As的影响范围分别离矿山区约120和60 km.      

Effect of Sb dopant amount on the structure and electrocatalytic capability of Ti/Sb-SnO2 electrodes in the oxidation of 4-chlorophenol

Ti/Sb-SnO_2 anodes were prepared by thermal decomposition to examine the influence',of the amount of Sb dopant on the structure and electrocatalytic capability of the electrodes in the oxidation of 4-chlorophenol.The physicochemical properties of the Sb-SnO_2 coating were markedly influenced by different amounts of Sb dopant.The electrodes,which contained 5% Sb dopant in the coating, presented a much more homogenous surface and much smaller mud-cracks,compared with Ti/Sb-SnO_2 electrodes containing 10% or 15% Sb dopant,which exibited larger mud cracks and pores on the surface.However,the main microstructure remained unchanged with the addition of the Sb dopant.No new crystal phase was observed by X-ray diffraction(XRD).The electrochemical oxidation of 4-chlorophenol on the Ti/SnO_2 electrode with 5% Sb dopant was inclined to electrochemical combustion;while for those containing more Sb dopant,intermediate species were accumulated.The electrodes with 5% Sb dopant showed the highest efficiency in the bulk electrolysis of 4-chlorophenol at a current density of 20 mA/cm~2 for 180 min;and the removal rates of 4-chlorophenol and COD were 51.0% and 48.9%,respectively.