壳-核结构Fe3O4/MnO2磁性吸附剂的制备、表征及铅吸附去除研究

采用共沉淀法制备了具有壳-核结构的磁性吸附剂Fe₃O₄/MnO₂,对其性质进行了系统表征,并对其铅吸附行为进行了初步研究.透射电镜(TEM)结果表明,Fe₃O₄/MnO₂为大小不规则的纳米级细小颗粒.X-射线衍射仪(XRD)表征结果表明,Fe₃O₄/MnO₂具有尖晶石的结构.振动样品磁强计(VSM)测得比饱和磁化强度为54.7 A·m²·kg^-1, 吸附剂磁性较强,易于磁分离;BET比表面积为76.5 m²·g^-1.吸附试验结果表明,Fe₃O₄/MnO₂对铅具有良好的去除效果(特别是在低平衡浓度情况下),最大吸附量为142.0 mg·g^-1(pH=5.0);Langmuir等温线能更好地拟合Fe₃O₄/MnO₂对溶液中铅的吸附(R²=0.852);吸附速率较快,在初始30 min内可达到平衡吸附量的80%,准二级动力学模型(R²=0.959)能较好地描述吸附过程;溶液pH对Fe₃O₄/MnO₂吸附铅的影响较为明显,随pH升高,吸附量增大,但离子强度变化对吸附影响不大.     

不同离子桥键的有机矿质复合体对菲的吸附-解吸研究

从自然土壤中有机质与矿物的结合方式出发,研究了Ca²⁺、Fe³⁺和Al³⁺桥键的有机矿质复合体对菲的吸附-解吸行为.结果表明,不同离子饱和的蒙脱石及其相应的胡敏酸-矿物复合体对菲的吸附-解吸数据都能用Freundlich模型较好地拟合,吸附容量（K_f）大小的顺序分别为Ca-Mont（0.184）>Fe-Mont（0.028）>Al-Mont（0.015）和Fe-Mont-HA（2.341）>Ca-Mont-HA（1.557）>Al-Mont-HA（1.136）.有机矿质复合体的K_f值远远高于相应的矿物,表明了复合体中的胡敏酸对菲的吸附容量贡献较大.但不同离子桥键的复合体K_f值的大小与它们有机质的含量高低次序不一致,表明了复合体中有机质的含量以及有机质与矿物结合方式的不同,都可能会影响它们对菲的吸附.Ca²⁺和Al³⁺桥键的有机矿质复合体对菲的解吸都有滞后现象,滞后现象主要来自有机质对菲的吸附,而矿物对菲的解吸滞后现象影响不明显.     

MnO2/Al2O3催化剂-微气泡臭氧体系催化降解喹啉及其机理

制备了纳米MnO₂,并以Al₂O₃为载体制备了掺杂型MnO₂/Al₂O₃颗粒催化剂.催化剂焙烧温度和时间分别为500℃和4 h、MnO₂质量分数为8%时,催化剂具有最高的臭氧催化氧化活性.SEM分析表明,纳米MnO₂均匀分布于Al₂O₃载体表面.MnO₂/Al₂O₃催化剂的比表面积（BET）为183.22 m²·g^-1,平均孔容为0.27 cm³·g^-1,平均孔径为4.87 nm.建立了MnO₂/Al₂O₃催化剂-微气泡臭氧催化反应体系,研究了该体系对喹啉的降解去除效果及其机理.臭氧微气泡的平均粒径为61.7 μm.微气泡臭氧投量为30 mg·L^-1时,反应60 min后喹啉去除率能达到95%以上;反应20 min后,MnO₂/Al₂O₃催化剂-微气泡臭氧体系对实际煤化工废水二级出水的TOC去除率可达到55%以上.以叔丁醇作为分子探针,证明了羟基自由基（·OH）氧化作用在臭氧微气泡催化氧化体系中对喹啉的降解起到主导作用.     

沉积物中氧化物结合态镉对芦苇的生物有效性研究：氧化物种类、结合形式、老化的影响

沉积物中重金属的生物有效性在很大程度上取决于其赋存形态.选用沉积物中2种典型氢氧化物矿物:氢氧化铁和氢氧化铝,以水培法和矿物结合态Cd为培养介质,以芦苇为受试植物,研究环境中吸附和共沉淀态Cd生物有效性差别,并探究老化过程对生物有效性的影响.经过13 d的培养,发现2种结合形式的Cd均可被芦苇富集,不同处理体系中富集强度不同,根中富集量为9.1~37.8 mg.kg-1;地上部分富集量为0~10.0 mg.kg-1.其中,结合在Fe0.5Al0.5(OH)3矿物上的Cd的生物有效性最大,其次是Fe(OH)3和老化的Fe0.5Al0.5(OH)3,富集量最少的是老化的Fe(OH)3的处理.采用2种低分子量有机酸对Cd进行解吸实验,Cd的解吸规律与芦苇对Cd的富集规律一致.因此,共沉淀处理降低了Cd的富集,矿物的理化性质决定了含铝矿物对Cd的结合较差,老化作用抑制了吸附态Cd的富集,有机酸解吸实验也验证了不同形态Cd生物有效性的差异.     

不同铁源对剩余污泥厌氧系统中蓝铁石生成的影响

以污水处理厂剩余污泥为研究对象,污泥经酸/碱预处理（pH=3.0/pH=10.0）后,分别以FeOOH、FeCl₃及Fe₂O₃为外加铁源,进行厌氧发酵,探究铁源对厌氧系统中蓝铁石晶体生成的影响.结果表明：FeCl₃和FeOOH可以高效地被还原为Fe²⁺,其铁还原效率（E_Fe）最高为56.24%~80.10%,且酸处理效果优于碱处理（3.00%~13.31%）,而Fe₂O₃的E_Fe相对较低,最高分别为31.94%（pH=3.0）和50.1%（pH=10.0）.FeOOH和Fe₂O₃的投加,可促进胞外聚合物（EPS）中蛋白质含量的提升,增强胞外电子传递能力,但Fe₂O₃因其结晶度高,阻碍了铁还原微生物对铁源的利用,导致铁还原效率低.上清液PO₄^3-浓度、污泥Fe-P比例与E_Fe呈负相关,E_Fe越高则PO₄^3-浓度、Fe-P比例越低.FeOOH组上清液PO₄^3-浓度下降幅度最大,反应第9 d PO₄^3-浓度最低,仅为对照组的10.30%（pH=3.0）和17.20%（pH=10.0）,其次是FeCl₃组（22.83%/27.87%）,Fe₂O₃组最终剩余较多PO₄^3-（65.02%/56.33%）;FeOOH、FeCl₃和Fe₂O₃酸/碱组的Fe-P比例分别为32.19%/21.20%、34.41%/23.09%和20.92%/11.99%.铁源的添加提高了污泥的磷回收率（R_p）,并且酸预处理效果优于碱处理,其中FeCl₃组R_p最高,是对照组的2.91倍,其次是FeOOH组（2.63倍）和Fe₂O₃组（2.12倍）.XRD分析表明,FeOOH和FeCl₃酸/碱预处理组均生成了蓝铁石晶体.     

AMD污泥复合材料吸附As (Ⅴ)的机制及其影响因素

污泥基吸附剂被广泛用于水和土壤中各种污染物的治理,是资源化利用的有效途径.以酸性矿山废水（AMD）污泥为骨料,玉米秸秆为还原剂,膨润土为载体,采用固相还原法制备污泥复合材料,并比较了不同原料配比和不同煅烧温度制备的复合材料吸附As （Ⅴ）的性能,探究了溶液pH、吸附剂投加量和竞争离子等对材料吸附As （Ⅴ）的影响,使用SEM-EDS、XRD、FT-IR、BET和XPS等分析技术对材料性能进行表征,探讨其吸附机制.结果表明,在900℃时AMD污泥：玉米秸秆：膨润土=2 ：1 ：1制备出的材料吸附As （Ⅴ）效果最好,材料表面生成大量Fe₃O₄、Fe₂ O₃和Fe⁰颗粒.该材料对As （Ⅴ）的吸附符合准二级动力学模型和Freundlich吸附等温模型,最大吸附容量为164.5mg ·g^-1,比原始AMD污泥提高了4.4倍.静电吸附、含氧官能团络合作用、铁氧化层的吸附和Fe⁰释放出Fe²⁺/Fe³⁺形成Fe （OH）₂/Fe （OH）₃,与砷酸盐的共沉淀等是复合材料吸附As （Ⅴ）的主要作用机制.     

垃圾焚烧中吸附剂对Cd、Pb迁移分布的影响

利用管式炉和模拟垃圾,研究了焚烧过程中SiO₂、Al₂O₃、CaO等吸附剂对重金属Cd、Pb迁移分布的影响规律,考察了不同吸附剂添加量、管式炉反应温度和停留时间的影响.结果表明,在各反应温度下,SiO₂、Al₂O₃、CaO均有利于Cd停留在底渣中;对于Pb,SiO₂、Al₂O₃亦使其易于停留在底渣中,而CaO在高温时表现为使Pb更易于向飞灰迁移.上述影响的程度均随着吸附剂添加量的增加而增加.当反应炉温度为850℃时,各吸附剂对于Cd的吸附效果顺序为CaO>Al₂O₃>SiO₂,对Pb的顺序为Al₂O₃>SiO₂>CaO.反应炉温度和停留时间的增加,也都易于使Cd、Pb向飞灰迁移.     

纳米Fe3O4负载的浮游球衣菌去除重金属离子的工艺研究

以纳米Fe₃O₄负载浮游球衣菌（Sphaerotilus natans）制备复合生物吸附剂,对此吸附剂进行表征并考察了其吸附水中重金属离子的性能.红外光谱分析表明,此复合生物吸附剂表面的主要活性基团为酰胺基（—CONH—）和羟基（—OH）.吸附性能研究表明,菌含量和流量是影响复合生物吸附剂吸附重金属离子的主要因素,在Cu²⁺初始浓度c₀<20 mg/L,菌含量1.5 g/L（菌/ Fe₃O₄＝3∶2）,流量0.96 L/h 时吸附剂对Cu²⁺的吸附效果最好;用稀盐酸对复合生物吸附剂进行再生,吸附剂可重复使用10次以上,再生液可重复使用3次; 吸附选择性为：Pb²⁺ > Cu²⁺ > Zn²⁺>Cd²⁺.     

生物质型煤固硫添加剂的固硫增强作用

在管式炉中进行了生物质型煤的燃烧固硫试验,考察了Al₂O₃、Fe₂O₃和MnO₂共3种添加剂对钙基固硫剂的固硫增强作用.结果表明,只有Al₂O₃增强了型煤的固硫作用.通过TGA试验进一步证实,在还原性气氛下Al₂O₃可有效地抑制固硫产物CaSO₄的高温分解.XPS和XRD分析表明,Al₂O₃通过与CaSO₄和CaO作用,形成了热稳定性高的复盐CaSO₄·3CaO·3Al₂O₃,并包裹在CaSO₄晶体的表面,从而抑制了CaSO₄的分解.     

不同铁氧化物对小麦幼苗镉积累的影响

小麦富镉（Cd）问题受到广泛关注,铁氧化物具备降镉潜力.通过盆栽小麦幼苗实验,分析了三氧化二铁（Fe₂O₃）、氢氧化铁[Fe（OH）₃]及拜耳法赤泥（B-RM）3种铁氧化物的降镉能力.结果显示3种铁氧化物中,Fe（OH）₃可显著降低小麦幼苗茎叶Cd含量,与对照相比降幅为16.3%~27.7%,投加量为0.5%时降Cd效果最优.Fe（OH）₃能够显著降低小麦幼苗根部向茎叶的Cd转运,投加量为10%时富集系数及转运系数最低.小麦幼苗根际土壤Fe/Cd、Cu/Cd及Zn/Cd是影响小麦幼苗茎叶Cd积累的关键因子,当Fe/Cd>25000、Cu/Cd > 50或Zn/Cd > 100时,根际土壤元素比与茎叶镉含量呈显著负相关.该比值的确定对于大田应用中钝化剂材料投加量的确定具有指导意义.     

Adsorption of Pb, Cd to Fe, Mn oxides in natural freshwater surface coatings developed in different seasons

Metal oxides( Fe, Mn oxides) in natural surface coatings(biofilms and associated minerals) are believed to play a significant role n the fate and transport of trace metal in aquatic environments. Seasonal variation of Fe, Mn oxides and organic materials in surface oatings, which were developed periodically on glass slides in Nanhu Lake, Jilin Province, China over the time frame of three seasons,was investigated in order to understand the influence of metal oxides on Pb and Cd adsorption to heterogeneous surface coating materials(biofilm). Pb and Cd adsorption was measured under controlled laboratory conditions( mineral salts solution with defined speciation, ionic trength 0.05 mol/L, 25~C and pH 6.0). The classical Langmuir adsorption isotherm was applied to estimate equilibrium coefficients of Pb nd Cd adsorption to the surface coatings. In general, components in the surface coatings varied greatly with seasons altering and btained higher concentrations in summer while the content of iron oxides always exceeded that of manganese oxides. Correlation nalyses between the maximum adsorption of Pb and Cd and components in the surface coatings developed periodically indicated that Pb hase association with Mn oxides and Cd phase association with Fe oxides as well as Mn oxides were statistically significant. Effect of Mn xides on Cd adsorption was confirmed in view of its higher content in the surface coatings. The importance of ferromanganese oxides for b and Cd adsorption to the natural surface coatings developed in different seasons was evidenced.     

负载磷酸盐生物质炭材料对重金属复合污染土壤的稳定化机制研究

为探讨负载磷酸盐生物质炭材料对重金属复合污染土壤中共存重金属的稳定化效果和迁移转化特征,以玉米秸秆和小麦秸秆为原材料,负载磷酸盐后在600 °C下无氧热解制备两种生物质炭材料,并将其用于重金属复合污染土壤中进行稳定化批处理试验. 结果表明:负载磷酸盐的玉米秸秆和小麦秸秆生物质炭材料可通过增加土壤中无定形铁、铝氧化物的含量而促进其对Cd的吸附,且负载磷酸盐后玉米秸秆生物质炭材料对土壤中无定形氧化物含量的增幅和游离态氧化物含量的降幅高于小麦秸秆生物质炭;同时,两种生物质炭材料均显著提高了土壤铁的活化度,进而有效控制了土壤重金属的生物有效性. 添加不同比例(如5%、10%和15%)的负载磷酸盐生物质炭均可降低土壤中Pb、Cd、Zn和Cu的迁移风险,并促进Pb的酸可提取态、铁锰结合态向有机结合态和残渣态转化,以及Cd、Zn和Cu的酸可提取态向残渣态转化. 两种负载磷酸盐生物质炭材料均可有效降低重金属的浸出浓度,10%及以上的添加量均可使Pb的浸出浓度降低98%以上. 15%的负载磷酸盐玉米秸秆生物质炭可使Cd和Zn的浸出浓度分别降低89%和47%,而15%的负载磷酸盐小麦秸秆生物质炭可使Cu的浸出浓度降低56%. 研究显示,施用10%~15%的负载磷酸盐生物质炭材料可显著降低重金属复合污染土壤中Pb和Cd的潜在环境风险,对矿区重金属污染土壤的安全利用具有参考和指导意义.      

Bioaccumulation of heavy metals by Phragmites australis cultivated in synthesized substrates

Accumulation of heavy metals from various oxides with adsorbed cadmium by wetland plant Phragmites australis was studied to evaluate the fate of heavy metals in the sediment of constructed wetlands. Hoagland solution was used as nutrition supply, and single metal oxide with adsorbed cadmium was applied as contaminant to study the accumulation characteristics of cadmium and the substrate metals by P. australis. After 45-d treatment, the bioaccumulation degree in root followed the order: Al(OH)3 > Al2O3 > Fe3O4 > MnO2 > FeOOH. Heavy metals absorbed by P. australis were largely immobilized by the roots with little translocation to aboveground parts.     

影响土壤重金属生物毒性的若干因子

本文应用发光细菌法探讨了土壤类型、粘土矿物、无定形金属氧化物、吸附剂对重金属纯溶液以及重金属污染土壤的降毒效应.红壤、砖红壤对Cu、Cd、Pb呈现负的降毒效应,而对As具有明显的降毒作用.黑土、黄棕壤对供试阳离子金属具有明显的降毒效应,对As降毒却不明显.试验证明粘土矿物及其组成是影响土壤重金属毒性的最基本因素.无定形氧化锰对供试阳离子金属的降毒能力大于无定形氧化铁,对As的效应二者则相反.不同吸附剂对Cu、Cd、Pb呈现基本相同的降毒顺序,即炉烟灰>活性炭>泥炭>干活性污泥,不同配比吸附剂对红壤添加性阳离子和东乡铜矿污染土壤均具有明显的降毒作用.添加吸附剂的东乡铜矿污染土壤随着土壤溶液毒性的消除,随之也消除或减轻了其对水稻种芽的急性毒害.     

沉积物中颗粒态镉的赋存形态对文蛤富集效性的影响

利用颗粒物悬浮系统研究了沉积物中Cd的特定赋存形态(如氢氧化铁结合态、氢氧化铝结合态、二氧化锰结合态)对其在文蛤体内富集速率的影响.结果表明,结合于沉积物中不同组分Cd的生物有效性存在明显差异.在Cd浓度为70 mg/kg时,22 d富集实验中氢氧化铁结合态和氢氧化铝结合态Cd在文蛤体内均没有明显的积累,而二氧化锰结合态Cd在文蛤体内有明显的富集,其富集速率为(0.009 4±0.001 0)μg/(g.d)(r2=0.853 9,p0.000 1).在Cd浓度为140 mg/kg时,氢氧化铁结合态Cd仍然无法被文蛤吸收,氢氧化铝和二氧化锰结合态Cd则可以被文蛤富集,其富集速率分别为(0.016 6±0.001 7)μg/(g.d)和(0.024 8±0.001 7)μg/(g.d).不同赋存形态Cd的生物有效性表现为:Cd-MnO2Cd-Al(OH)3Cd-Fe(OH)3.对于不同赋存形态的Cd,吸收效率(AE)和摄食率(IR)的差异导致了其生物有效性的不同.     

Comparison of Pb and Cd adsorption to the surface coatings and surficial sediments collected in Xianghai Wetland

Surface coatings and surficial sediments were obtained in four natural waters in Xianghai Wetland in China to study the role of surface coatings and surficial sediments in controlling the transporting and cycling of heavy metals in aquatic environments. Pb and Cd adsorption to the surface coatings and surficial sediments were measured under controlled laboratory conditions(mineral salts solution with defined speciation, ionic strength 0.0.5 mol/L, 25℃ and pH 6.0 for surface coatings: and 0.00.5 mol/L CaCl2 solution, 25℃ and pH 6.0 for surficial sediments). The Langmuir adsorption isotherm was applied to estimate equilibrium coefficients of Pb and Cd adsorption to the surface coatings and surficial sediments, and the component analyses of surface coatings and surficial sediments were also carried out.Correlation analyses between the maximum adsorption of Pb and Cd (Гmax) and the components in the surface coatings and surficial sediments suggested that there was a statistically significant trend for Pb and Cd adsorption(Гmax) to the surface coatings to increase with increasing in contents of Fe and Mn oxides in the surface coatings and surficial sediments. And the metal adsorption abilities of surface coatings were much stronger than those of surficial sediments, highlighting that in the same water, i.e. at the same pH and initial metal concentrations, the metals(such as lead and cadmium) in supernatant were feasible to be adsorbed by surface coatings than surficial sediments. The more importance of surface coatings than surficial sediments for adsorbing and cycling of heavy metals in aquatic environments was evidenced.     

矿业废弃地重金属形态分布特征与迁移转化影响机制分析

为探究矿业废弃地重金属形态分布特征和迁移转化的影响机制,在广东大宝山矿区矿业废弃地采集土壤和尾砂样品,分析重金属形态特征;采用Pb稳定同位素分析进行矿区污染源解析,并结合矿区典型矿物的X射线衍射分析(XRD)、透射电镜-能谱分析(TEM-EDS)和拉曼分析,以及室内模拟浸出实验,阐明矿区重金属迁移转化的特征和影响因素.结果表明,矿区土壤和沉积物样品中Cd、 Pb和As的赋存形态以残渣态为主,占总量的比例范围为85%～95%;其次为铁锰氧化物结合态(1%～15%).矿区土壤和尾砂中的主要矿物类型为黄铁矿(FeS₂)、黄铜矿(CuFeS₂)和金属氧化物,同时也存在少量的闪锌矿(ZnS)和方铅矿(PbS).酸性条件(pH=3.0)有利于Cd和Pb从土壤、尾砂和矿物(黄铁矿和黄铜矿)中释放迁移,并从残渣态向非残渣态转化.铅同位素分析显示土壤和尾砂中的重金属(Pb)主要来自采矿区金属矿物的释放,矿区柴油的贡献率在30%以内.多元统计分析表明矿区土壤和尾砂重金属主要来源于3种类型的矿物污染源,即黄铁矿、黄铜矿和闪锌矿+金属氧化物,其中Cd、 As和Pb主...     

几种水合金属氧化物的磷酸根吸附性能

利用简单的碱沉淀法制备不同的水合金属氧化物,并对所得七种水合金属氧化物的磷酸根吸附等温线进行了系统的探讨比较.研究表明,25℃条件下,Al、Fe、Ni、Cu和Ce的水合金属氧化物对磷酸根的吸附最符合Langmuir线性吸附方程,而水合氧化锌和水合氧化钴吸附剂最符合线性等温线模型.所有这七种水合金属氧化物对磷酸根的吸附都...     

Speciation and fractionation of heavy metals in soil experimentally contaminated with Pb,Cd, Cu and Zn together and effects on soil negative surface charge

Speciation and fractionation of heavy metals in soil subsamples experimentally loaded with Pb, Cd, Cu and Zn in orthogonal design was investigated by sequential extraction, and operationally defined as water-soluble and exchangeable(SE), weakly specific adsorbed( WSA),Fe and Mn oxides-bound(OX) and organic-bound( ORG). The results showed that fractions of heavy metals in the soil subsamples depended on their speciation. About 90% of Cd and 75% of Zn existed in soil subsamples in the SE fraction. Lead and Cu existed in soil subsamples as SE, WSA and OX fractions simultaneously, although SE was still the major fraction. Organic-bound heavy metals were not clearly apparent in all the soil subsamples. The concentration of some heavy metal fractions in soil subsamples showed the good correlation with ionic impulsion of soil, especially for the SE fraction. Continuous saturation of soil subsamples with 0.20 mol/L NH4CI, which is the first step for determination of the negative surface charge of soil by the ion retention method, resulted in desorption of certain heavy metals from the soil. It was found that the percentage desorption of heavy metals from soil subsamples depended greatly on pH, the composition and original heavy metal content of the soil subsamples. However, most of the heavy metals in the soil subsamples were still be retained after multiple saturation. Compared with the parent soil, the negative surface charge of soil subsamples loaded with heavy metals did not show difference significantly from that of the parent one by statistical analysis. Heavy metals existed in the soil subsamples mainly as exchangeable and precipitated simultaneously.