17O-NMR研究Al(Ⅲ),Fe(Ⅲ)盐对水缔合的影响

测试了AlCl3,Al2(SO4)3,FeCl3,Fe2(SO4)3等对水的^17O-NMR化学位移和半峰宽的影响。并利用水^17O-NMR化学位移和半峰宽的变化与氢键的关系，分析了AlCl3,Al2(SO4)3。FeCl3,Fe2(SO4)3等对水缔合的影响，研究表明，AlCl3,Al2(SO4)3。FeCl3,Fe2(SO4)3等对水缔合有促进作用。且Fe^3 对水缔合的作用大于Al^3 。     

水体酸化条件下Cu(II)对斑马鱼胚胎的毒性效应

为评价由酸雨、酸性矿山排水等环境污染导致的水体酸化及水体重金属联合作用对水生生物的生态毒性效应,研究了不同pH值(pH=3、4、5、6、7和7.8)条件下Cu2+对斑马鱼胚胎发育的影响。结果表明,酸性水体及Cu2+单一存在时,酸对斑马鱼胚胎24h半数效应浓度值EC50为pH=3.65,Cu2+(pH=7.8)对斑马鱼胚胎24h-EC50为0.267mg·L-1;当水体酸化及水体中的Cu2+共存时,较低的pH对Cu2+的生物毒性起协同作用,表现为随溶液pH的降低,各浓度Cu2+对斑马鱼胚胎的24h凝结率显著增高(P24h致死率=0.001),而斑马鱼胚胎96h孵化率显著降低(P96h孵化率=0.002),且不同浓度的Cu2+之间的生物毒性效应存在显著性差异(P24h致死率=0.0321;P96h孵化率=0.0028)。这说明酸性水体和Cu2+都显著影响斑马鱼胚胎的发育,且Cu2+在酸性水体中对斑马鱼胚胎的毒性显著增强。因此,在受重金属Cu2+污染的地区,如同时受到酸雨或酸性矿山排水等较低pH值和Cu2+的双重胁迫,较低浓度的Cu2+就能够对水生生物的生殖发育及水生生态系统产生严重的影响和危害。     

有机酸对潮褐土和红壤吸附Cu(II)的影响及其机制

采用吸附平衡法,研究了有机酸(草酸、柠檬酸)对潮褐土和红壤吸附Cu2+的影响及机制。结果表明,潮褐土、红壤对Cu2+吸附明显有异,潮褐土对Cu2+吸附量是红壤对Cu2+吸附量的5倍多。潮褐土对Cu2+的竞争吸附率随有机酸浓度升高而降低,当草酸、柠檬酸浓度为10 mmolL-1时,Cu2+吸附率均分别比对照的降低40%和70%以上。在低浓度条件下,红壤对Cu2+的竞争吸附率随有机酸浓度的提高而增加,当草酸、柠檬酸浓度分别超过1 mmolL-1和0.05 mmolL-1时,又随有机酸浓度的升高而降低。两种土壤对Cu2+次级吸附率随有机酸浓度升高而变化的规律与竞争吸附的一致。在相同有机酸浓度下,土壤对Cu2+的次级吸附率均比竞争吸附率的高。     

Mutagenic activity of transition‐metal complexes: Relation structure‐mutagenic and antibacterial activity for some Pd(II), Pt(II) and Rh(I) complexes†

The inhibitory and mutagenic action of some Pd(II), Pt(II) and Rh(I) complexes towards various bacterial strains has been evaluated, and some correlations have been found between the chemical behaviour of the complexes and their selective biological activity: most of the complexes cause only a DNA damage repaired by the excision repair system. Particularly, the Rh(I) complexes used in this work show selective antibacterial effects on defective but no effect on wild‐type strains.     

Cu(Ⅱ)、Fe(Ⅲ)和Cr(Ⅲ)在弱酸性条件下对大肠杆菌的毒性和致毒机制

比较了弱酸性条件下Cu(Ⅱ)、Fe(Ⅲ)和Cr(Ⅲ)单独或加入抗坏血酸(L-AscA)对大肠杆菌(E.coli)的毒性,深入分析了Cu(Ⅱ)/L-AscA体系的特性;通过电子自旋共振(ESR)定量分析羟基自由基(.OH)浓度以分析其毒性机理.结果表明,pH 4.0下L-AscA促进了Cu(Ⅱ)、Fe(Ⅲ)而非Cr(Ⅲ)的毒性,三者毒性Cu(Ⅱ)>Cr(Ⅲ)>Fe(Ⅲ).通常被认为无毒的Cr(Ⅲ)却在0.2 mmol.L-1,pH 4.0时表现出了很高的杀菌率.与0.01%L-AscA共存时,Cu(Ⅱ)为200、20μmol.L-1和2、0.2μmol.L-1下,E.coli的存活率分别在30 min和2 h内迅速降至零,且该体系对自然水体中分离所得的其它7种菌株同样具有明显的制御作用.ESR结果表明L-AscA的加入使200μmol.L-1Cu(Ⅱ)反应体系的.OH浓度约提高两倍,.OH浓度呈Cu(Ⅱ)浓度依赖.但在Fe(Ⅲ)、Cr(Ⅲ)/L-AscA体系中未检测到.OH,表明三者对细胞的致毒机制存在明显差异.     

Approaching the binding between Cu(II) and aerobic granules by a modified titration and µ-XRF

Interactions between metals and activated sludge can substantially affect the fate and transport of heavy metals in wastewater treatment plants. Therefore, it is important to develop a simple, fast and efficient method to elucidate the interaction. In this study, a modified titration method with a dynamic mode was developed to investigate the binding of Cu(II), a typical heavy metal, onto aerobic granules. The titration results indicated that pH and ionic strength both had a positive effect on the biosorption capacity of the granular sludge. The µ-XRF results demonstrated that the distribution of metals on the granular surface was heterogeneous, and Cu showed strong correlations and had the same “hot spots” positions with other metal ions (e.g., Ca, Mg, Fe etc.). Ion exchange and complexing were the main mechanisms for the biosorption of Cu(II) by aerobic granules. These results would be beneficial for better understanding of Cu(II) migration and its fate in wastewater treatment plants.     

Al(Ⅲ)与Fe(Ⅲ)溶液共聚合研究

以AlCl_3·6H_2O和FeCl_3·6H_2O混合溶液通过滴加NaOH溶液的方法制备了不同Al/Fe(摩尔比,下同)和不同[OH]_b/[Al+Fe]值的共聚物.测定了聚合过程和熟化过程中的pH值变化,并对不同碱化度和熟化时间下的聚合物进行了混凝效能实验.结果表明,在共聚过程中,Fe(Ⅲ)与 OH~-的络合速度比Ai(Ⅲ)快,即 Fe(Ⅲ)具有较强的共聚合活性.Al/Fe,[OH」_b/[Al+Fe]值对铝铁共聚物形态分布有明显影响.不同条件下共聚物混凝对比实验表明,在Al/Fe为5:5,[OH]_b/[Al+Fe]为 1.6,熟化时间为24h时,显示出了较优异的混凝效能.     

Potentiometric studies of mixed complexes of cobalt(II) and copper(II) with l‐Asparagine and adenine

A potentiometric titration technique has been used to determine the stability constants for the various complexes of Co(II) and Cu(II) with L‐asparagine and from DNA base, e.g. adenine. Stability constants of ternary systems have been evaluated by the method suggested by Irwing‐Rossotti. In addition, the conditional constants were calculated as a function of pH. The maximum values of the conditional formation constants were found to be in accordance with the mixed‐ligand complex formation constants in a determined pH region. Furthermore, the molar fractions of different species from mixed complexes were calculated by means of formation constants. The values of stability constants of mixed‐ligand complexes at 25°C are as follows: log K= 5.25 for Co(II)‐L‐asparagine‐adenine; log K= 9.30 for Cu(II)‐L‐asparagine‐adenine. The ionic strength was kept constant at I = 0.20 with NaClO₄.     

外源可溶性有机物(DOM)活化土壤Cu(Ⅱ)模型研究

研究了底泥水溶性有机质(DOM)活化处理土壤Cu(Ⅱ)的可行性,以寻求最优实验条件.在单因素实验基础上,采用二次回归正交旋转组合设计对DOM活化土壤铜进行了优化,建立了土壤铜潜在去除率(y)与DOM投加量(X1)、振荡速度(X2)、振荡时间(X3)和反应温度(X4)四个因素间的正交回归模型: y=47.73671+55176X3-2.63327X21-3.46235X22-1.09187X1X2+1.40813X1X2+1.40813X2X4-1.09187X3X4.从模型推知,最佳实验条件为:DOM投加量为31.1 m1、振荡速度159r·min-1、振荡时间为1.7h和反应温度为24.3℃.在此条件下,根据数学模型推知土壤铜潜在去除率可达53.4%,验证实验结果与模型值基本一致.     

南黄海沉积物间隙水中重金属(Fe,Mn,Cu,Co,Ni)的地球化学特征

本文主要研究了南黄海(32°N)沉积物间隙水中的Fe,Mn,Cu,Co,Ni与其硫化物及粘土矿物间的关系,结果表明:间隙水中的Mn~(2+),Cu~(2+)硫化物趋向于沉淀,Co~(2+),Ni~(2+)硫化物趋向于溶解,Fe~(2+)则有其硫化物的溶解-沉淀控制,Mn~(2+),Cu~(2+)还有其他体系和硫化物体系共同控制其浓度,间隙水中的Fe~(2+)可被蒙脱石吸附,Mn~(2+)被绿泥石吸附,Ca~(2+),Ni~(2+)被蒙脱石、绿泥石吸附,Co~(2+)被绿泥石、蒙脱石吸附,Fe~(2+),Mn~(2+)对粘土矿物吸附剂的专属性要求远比Cu~(2+),Co~(2地+),Ni~(2+)高,蒙脱石是南黄海沉积物中最重要的阳离子吸附剂,绿泥石次之。     

Fe(Ⅲ)改性生物质炭对水相Cr(Ⅵ)的吸附试验

为考察Fe(Ⅲ)改性对生物质炭吸附水相中Cr(Ⅵ)的影响,采用吸附平衡试验结合Zeta电位、傅里叶变换红外光谱(FTIR)、X射线衍射法(XRD)等方法研究了Fe(Ⅲ)改性秸秆生物质炭对Cr(Ⅵ)的吸附作用及机制。结果表明,Fe(Ⅲ)通过与生物质炭表面官能团形成络合物及氢氧化铁表面沉淀的物理覆盖作用降低生物质炭表面负电荷,增加表面正电荷,从而促进生物质炭对Cr(Ⅵ)的吸附。Fe(Ⅲ)改性对花生秸秆炭吸附Cr(Ⅵ)的促进作用大于稻草炭,pH值为5.0时Fe(Ⅲ)改性分别使花生秸秆炭和稻草炭对Cr(Ⅵ)的最大吸附量提高79%和26%。在pH值为4.0~6.5范围内,生物质炭和改性生物质炭对Cr(Ⅵ)的吸附量均随悬液pH值升高而降低,Fe(Ⅲ)改性对生物质炭吸附Cr(Ⅵ)的促进作用也呈相似的变化趋势。改性生物质炭的表面负电荷随pH值升高而增加是Cr(Ⅵ)吸附量减小的主要原因。Cr(Ⅵ)可在改性生物质炭表面的同时发生静电吸附和专性吸附,Cr(Ⅵ)的专性吸附量也随pH值升高而减小。因此,改性秸秆生物质炭在酸性条件下对Cr(Ⅵ)有较高的吸附容量,可用于酸性废水中Cr(Ⅵ)的吸附和去除。     

2种水稻土中Cu(Ⅱ)和Pb(Ⅱ)的解吸动力学

用一次平衡法研究了2种水稻土表面吸附态Cu(Ⅱ)和Pb(Ⅱ)的解吸动力学行为及柠檬酸和酒石酸对2种重金属离子解吸的影响。结果表明,虽然2种土壤对Pb(Ⅱ)的吸附量比Cu(Ⅱ)高得多,但无论在单一重金属体系还是Cu(Ⅱ)和Pb(Ⅱ)共存体系中,Cu(Ⅱ)的解吸量均大于Pb(Ⅱ),湖州水稻土Cu(Ⅱ)的解吸量大于嘉兴水稻土,说明土壤对重金属离子的吸附亲和力越大,吸附的重金属离子越不易解吸。用E lovich方程拟合动力学数据可以获得比较满意的结果。解吸速率与时间的关系曲线表明,Cu(Ⅱ)和Pb(Ⅱ)的解吸速率随时间的增加迅速减小。Cu(Ⅱ)的解吸速率大于Pb(Ⅱ),柠檬酸和酒石酸不仅使重金属的解吸量增加,而且使Cu(Ⅱ)和Pb(Ⅱ)的解吸速率大大提高。2种有机酸对Cu(Ⅱ)解吸的促进作用大于Pb(Ⅱ),柠檬酸的促进作用大于酒石酸。     

CuO和Cu(Ⅱ)催化臭氧氧化的研究

以乙二酸为实验对象,研究了CuO/Al_2O_3和Cu(II)对臭氧的催化作用实验结果表明,在低pH条件下,CuO/Al2O3有较强的催化臭氧氧化能力,可以将乙二酸的去除率提高约15%而在中性条件下,20g·l-1CuO/Al2O3的催化效果有限磷酸盐缓冲液可以强烈抑制臭氧氧化乙二酸以及CuO/Al2O3的催化作用与CuO/Al2O3相比,Cu(II)离子有更强的催化臭氧氧化乙二酸的能力     

三峡库区消落带土壤对Cu(Ⅱ)、Zn(Ⅱ)的吸附特征

以三峡库区消落带紫色土为对象,采用平衡吸附法研究了Cu(Ⅱ)、Zn(Ⅱ)在紫色土中的吸附特征,分析了紫色土对重金属的吸附能力.结果表明:(1)随着加入Cu(Ⅱ)、Zn(Ⅱ)浓度增高,紫色土对Cu(Ⅱ)、Zn(Ⅱ)的吸附量增大,碱性紫色土对Cu(Ⅱ)、Zn(Ⅱ)的吸附量最高分别为1499.5 mg.kg-1、2845.4 mg.kg-1;(2)土壤中有Cu(Ⅱ)、Zn(Ⅱ)的专性吸附位点,在两者共存的条件下存在竞争吸附,Cu(Ⅱ)的竞争吸附能力大于Zn(Ⅱ),其各自的最大吸附量小于单一离子条件下的吸附量,碱性、中性、酸性紫色土Cu(Ⅱ)最大吸附量的下降幅度分别是14.5%、15.2%、15.9%,Zn(Ⅱ)的最大吸附量下降幅度分别为31.7%、28.1%、25.7%;(3)共存阳离子类型及浓度影响紫色土有效Cu(Ⅱ)、Zn(Ⅱ)含量,随着阳离子的加入,碱性紫色土的有效Cu(Ⅱ)含量增加,酸性紫色土减少,而3种紫色土的有效Zn(Ⅱ)含量均增加.消落带土壤淹水后,水体中Cu(Ⅱ)及其他阳离子的存在使土壤对Zn(Ⅱ)的吸附力降低,造成Zn(Ⅱ)污染的环境风险增加.     

Fe(Mn)OOH催化臭氧氧化水中扑米酮和溶解性有机物(DOMs)

使用碱式共沉淀法成功制备Fe(Mn)OOH催化剂,并且证实Fe(Mn)OOH可以高效催化臭氧降解水中扑米酮(PMD)和溶解性有机物(DOMs).表征分析表明,Fe(Mn)OOH表现出α-FeOOH和MnFe_2O_4两相的特征晶相结构.在相同条件下,Fe(Mn)OOH催化臭氧体系比单独臭氧、MnFe_2O_4和FeOOH催化臭氧体系表现出更好的扑米酮降解效能.在20 min时,Fe(Mn)OOH催化臭氧体系可以降解去离子水中97.5%的扑米酮,并且在快速和慢速反应阶段的反应速率常数分别可达0.46044 min~(-1)和0.10723 min~(-1).结果还表明,初始扑米酮和臭氧浓度以及催化剂投量之间的配比关系可能对扑米酮的降解有重要影响.Fe(Mn)OOH催化体系遵循羟基自由基的反应机制,可能是通过促进臭氧快速分解产生大量的羟基自由基,进而提高了水中有机物的降解效能.此外,Fe(Mn)OOH还具有结构稳定,可重复利用性好的优势.     

Cr(Ⅵ)和Cu(Ⅱ)在胡麻和油菜生物质炭上吸附的交互作用

以胡麻、油菜的秸秆和油渣热解制得的4种生物炭为吸附剂,以批平衡吸附实验研究了Cr(Ⅵ)-Cu(Ⅱ)混合溶液体系中两种金属的吸附作用,考察吸附时间和初始金属浓度对吸附作用的影响,并与单一吸附体系对比,分析了可能的交互作用机制.发现混合体系中生物炭对Cr(Ⅵ)和Cu(Ⅱ)的吸附动力学和热力学规律与单一金属体系下相似,但生物炭对Cr(Ⅵ)的吸附量较单一Cr(Ⅵ)体系略有增加但不显著,而Cu(Ⅱ)的吸附量较单一Cu(Ⅱ)体系明显增大.表明两种金属在4种生物炭上的吸附存在交互作用,为协同吸附作用.交互作用的主要机制是两种金属离子间正负电荷的静电引力作用.     

Voltammetric study on the interaction of the heavy metals Cd(II) and Mn(II) with transfer‐RNA,DNA and other polynucleotides

Small amounts of bivalent cations, usually provided by Mg²⁺, are in the living cell necessary for the biological activity of t‐RNA as these bivalent cations influence the tertiary and secondary structure of this globular polynucleotide.

In context with the discussed possibility of carcinogenic actions of ingested Cd it is of particular interest to check whether there exist specific strong interactions of this toxic heavy metal with nucleic acids.

Therefore, the binding of the toxic heavy metal ion Cd²⁺ and the essential heavy metal ion Mn²⁺ to t‐RNA and for comparison to DNA and the polynucleotides poly‐U, poly‐A and poly‐A‐poly‐U has been studied. Free metal ion concentrations have been determined by differential pulse polararography. Association constants and the number of binding sites have been evaluated by the Scatchard method and alternatively according to a simple electrostatic model of the polyelectrolytes. With the Scatchard method for t‐RNA and all polynucleotides with helical structure two different binding sites of different strength are observed. Those with higher association constants are assigned to the helical parts of t‐RNA. Interaction sites with low association constants correspond to the parts with no ordered tertiary structure, as their exclusive occurrence for poly‐U, having a completely stochastic coil structure, reflects. The values of the association constants for the stronger and weaker association sites are in the respective polynucleotides for both investigated bivalent metal ions of comparable magnitude. This emphasizes that the interaction is essentially of electrostatic nature and depends primarily on the charge of the interacting species.

Thus the specific strong interaction of Cd by the intercalation into the tertiary structure of nucleic acids or by chelation of their base units can be ruled out as one possibility for carcinogenity of Cd.

Moreover, under physiological conditions the high excess of competitive Mg²⁺ will suppress the interaction of Cd based on electrostatic forces.     

磺酸基改性磁性吸附剂去除水中的Cu(Ⅱ)

利用水热法制备出Fe_3O_4磁性粒子,通过正硅酸乙酯水解使Fe_3O_4外面包覆SiO_2(Fe_3O_4@SiO_2),最后利用3-氨丙基三甲氧基硅烷和氯磺酸进行改性,合成了磺酸基改性磁性吸附剂.采用FT-IR、BET和XRD等方法对合成吸附剂进行表征,并探讨接触时间、初始浓度、溶液pH值等因素对吸附性能的影响.表征结果显示,成功合成了磺酸基改性磁性Fe_3O_4@SiO_2粒子;Fe_3O_4@SO_3Na比表面积为20.4587 m~(-2)·g~(-1).吸附实验结果显示,在25℃条件下,Fe_3O_4@SO_3Na对Cu~(2+)的吸附等温线符合Freundlich吸附等温方程,实验条件下最大吸附量为16.13 mg·g~(-1).Fe_3O_4@SO_3Na吸附Cu~(2+)可在1 h内达到吸附平衡且吸附动力学遵循拟二级动力学模型.溶液中存在盐离子时,发现盐离子的存在对吸附效果几乎没有影响;溶液中含有柠檬酸时对吸附效果产生抑制.吸附剂经3次循环使用后仍有吸附性能,表明吸附剂具有良好的再生性和经济性.