Kinetic studies on the adsorption of Cd2+, Cu2+ and Zn2+ ions from aqueous solutions by cassava (Manihot sculenta Cranz) tuber bark waste

The kinetics of Cd2+, Cu2+ and Zn2+ adsorption onto pure and thioglycolic acid treated cassava tuber bark wastes (CTBW) were investigated using a batch sorption technique at 30 degrees C. Kinetic data suggested that the adsorption process was exothermic, the rate limiting sorption step was physisorption and adsorption rates could be best described by a pseudo-second order model. Rate coefficients were determined to range between 1.39x10(-2)min(-1) and 5.94x10(-2)min(-1), 1.46x10(-3)min(-1) and 5.76x10(-3)min(-1) and 0.69x10(-3)min(-1) and 5.8x10(-3)min(-1) for Cd2+, Cu2+ and Zn2+, respectively. The results from these studies indicated that the sorption process is fast and stable. The adsorption equilibria were evaluated using the Langmuir equation and the monolayer sorption capacity was found to range between 5.88-26.3mg/g, 33.3-90.9 mg/g and 22.2-83.3mg/g for Cd2+, Cu2+ and Zn2+, respectively. Negative values of DeltaG(ads)(0) indicated that the adsorption process was spontaneous and exothermic in nature.     

Impact of Cell Wall Structure on the Behavior of Bacterial Cells as Sorbents of Cadmium and Lead

Batch metal sorption studies were conducted to compare the behavior of Gram-positive Bacillus subtilis and Gram-negative Escherichia coli as sorbents of Cd 2+ and Pb 2+ . A pH range from 3.0 to 6.5 was investigated at total metal concentrations of 1 2 10 -4.0 and 3.2 2 10 -5 M. Concentration apparent equilibrium sorption constants (K s n M ) and sorption capacity (S max n ) values were determined for the bacteria by fitting experimental data to one- ( n = 1) and two-site ( n = 2) Langmuir sorption isotherms. The sorption data for each of the bacteria were described well by a one-site model (r 2 > 0.9), Cd 2+ exhibited somewhat lower sorption affinities (log K s M =- 1.5 for B. subtilis , and -0.7 for E. coli ) than Pb 2+ (log K s M =-0.6 for B. subtilis and -0.8 for E. coli ). Corresponding S max values for Cd 2+ and Pb 2+ on B. subtilis were 0.36 mmole/g and 0.27 mmole/g, respectively. For E. coli Cd 2+ and Pb 2+ S max values were lower at 0.10 mmole/g and 0.21 mmole/g. A two-site sorption model yielded an improved fit for only the E. coli data with several orders of magnitude difference evident between high (Cd 2+ log K s1 M = 0.9; Pb 2+ log K s1 M = 1.5) and low (Cd 2+ log K s2 M =- 1.1; Pb 2+ log K s2 M = -1.6) affinity sorption sites. In addition, allowing for the presence of low affinity sorption (i.e., S max2 ) sites further increased the total E. coli metal sorption capacity closer to that of B. subtilis . As expected, the sorption of Cd 2+ and Pb 2+ by the bacteria exhibited a strong dependence on pH with sorption edges in the range of pH 4.2 to 5.6. The results of this study show that, despite differences in cell wall structure and composition, B. subtilis and E. coli exhibit remarkably similar sorption behavior toward Cd 2+ and Pb 2+ , respectively. These similarities can be attributed to the specific chemical reactivity of acidic functional groups (e.g., carboxyl, phosphoryl) that occur in the cell walls of both bacteria.     

Interactions between different selenium compounds and zinc, cadmium and mercury

In this paper, we present a polarographic study of systems containing different inorganic and organic selenium compounds (sodium selenite, sodium selenate, seleno-methionine and seleno-urea) and metal ions (Zn2+, Cd2+ Hg2+) of the 12th group of elements in the periodic table. While zinc is a trace element known to be essential for plants and animals, cadmium and mercury are exogenous elements and are harmful pollutants that accumulate during aging; selenium is also recognized as an important micronutrient and is sometimes added to the diet. Experiments investigating the interactions were carried out using polarographic techniques in unbuffered systems. The three metal cations originated complexes with different strength and solubility in the presence of selenite anions; in the presence of selenate, polarography was not able to detect formation of complexes with these metal ions, at least under the experimental conditions used: a decrease of Hg2+ ion concentration was observed. Seleno-methionine did not react with Cd2+; in the presence of Zn2+, a soluble complex with a co-ordination number 1 was formed, while, again, the concentration of Hg2+ decreased in the presence of increasing concentrations of the selenium derivative. Seleno-urea did not react with Zn2+, but formed a complex with Cd2+ with limited solubility. Finally, this ligand could not be studied with Hg2+ because of the overlapping of the reduction potentials of both the ligand and the metal cation. Overall equilibrium constants for complex formation (Kf) and the solubility product (Ksp) for poorly soluble species are also reported.     

Selective metal binding to a membrane-embedded aspartate in the Escherichia coli metal transporter YiiP (FieF)

The cation diffusion facilitators (CDF) are a ubiquitous family of metal transporters that play important roles in homeostasis of a wide range of divalent metal cations. Molecular identities of substrate-binding sites and their metal selectivity in the CDF family are thus far unknown. By using isothermal titration calorimetry and stopped-flow spectrofluorometry, we directly examined metal binding to a highly conserved aspartate in the Escherichia coli CDF transporter YiiP (FieF). A D157A mutation abolished a Cd2+-binding site and impaired the corresponding Cd2+ transport. In contrast, substitution of Asp-157 with a cysteinyl coordination residue resulted in intact Cd2+ binding as well as full transport activity. A similar correlation was found for Zn2+ binding and transport, suggesting that Asp-157 is a metal coordination residue required for binding and transport of Cd2+ and Zn2+. The location of Asp-157 was mapped topologically to the hydrophobic core of transmembrane segment 5 (TM-5) where D157C was found partially accessible to thiol-specific labeling of maleimide polyethylene-oxide biotin. Binding of Zn2+ and Cd2+, but not Fe2+, Hg2+, Co2+, Ni2+, Mn2+, Ca2+, and Mg2+, protected D157C from maleimide polyethylene-oxide biotin labeling in a concentration-dependent manner. Furthermore, isothermal titration calorimetry analysis of YiiP(D157A) showed no detectable change in Fe2+ and Hg2+ calorimetric titrations, indicating that Asp-157 is not a coordination residue for Fe2+ and Hg2+ binding. Our results provided direct evidence for selective binding of Zn2+ and Cd2+ for to the highly conserved Asp-157 and defined its functional role in metal transport.     

胁迫时间与非毒性离子对重金属抑制拟南芥种子发芽及幼苗生长的影响

测定了Hg²⁺、Cd²⁺、Cu²⁺、Pb²⁺单一重金属胁迫对拟南芥种子发芽和幼苗生长的影响.结果表明,重金属对幼苗生长的毒性大于对种子发芽的毒性,以抑制种子发芽的IC₅₀为指标,4种重金属的毒性顺序为Hg²⁺＞Cd²⁺＞Pb²⁺/Cu²⁺,以幼苗生长为指标,则毒性顺序为:Cu²⁺＞Hg²⁺＞Cd²⁺/Pb²⁺,并随着胁迫时间延长,种子萌发率下降.此外,不同重金属在不同发芽时段对种子的毒性也不尽相同,Cd²⁺的毒性在种子吸水后的0～12 h大于12～24 h,而Hg²⁺毒性在12～24 h大于0～12 h,其中,种皮对减轻重金属毒性起着十分重要的作用.通过非毒性离子(Ca²⁺、Mg²⁺、K⁺、Na⁺)与重金属离子(Hg²⁺、Cd²⁺、Cu²⁺、Pb²⁺)交互作用对拟南芥种子发芽及幼苗生长效应的研究发现, mmol·L^-1的Ca²⁺、Mg²⁺、K⁺、Na⁺可以增强Hg²⁺对种子发芽的毒性,但对Cd²⁺的毒性却没有影响.对于幼苗来说,Ca²⁺、Mg²⁺、K⁺、Na⁺可以显著增强Hg²⁺的毒性,Ca²⁺可以缓解Cd²⁺的毒性,但却增加Cu²⁺的毒性,K⁺可以缓解Pb²⁺对幼苗的毒害作用.最后,本文对重金属的毒害机理进行了探讨.     

Hg2+和Cd2+胁迫对满江红生理和细胞超微结构的影响

研究了在梯度浓度Hg2+和Cd2+胁迫下,满江红(Azolla imbricata (Roxb.) Nakai)的叶绿素含量、叶绿素a/b比值、光合放氧速率、呼吸速率、抗氧化酶系(超氧化物歧化酶(SOD)、过氧化氢酶(CAT)、过氧化物酶(POD))和细胞超微结构受Hg2+和Cd2+的毒害影响.结果显示:随着胁迫程度的增大,叶绿素含量、叶绿素a/b比值、光合放氧速率明显下降,呼吸速率均在2 mg/L浓度下达到峰值,尔后下降; SOD、CAT、POD的活性均出现不同程度的应激性升高(除POD在Cd2+处理时下降),尔后下降.电镜观察发现,随着污染物浓度的增加和胁迫时间的延长,叶绿体出现膨大、破损和解体;线粒体嵴突膨胀和线粒体变形及空泡化;核染色质凝集,核仁消失,核膜破裂.实验结果表明: Hg2+和Cd2+污染不仅损害植物的生理活性,而且也破坏细胞的超微结构,最终导致植物死亡;随着Hg2+和Cd2+胁迫的增大,细胞超微结构的损伤程度和植物的生理变化是同步的;植物受毒害的程度表现出明显的剂量效应关系;在同一处理时间和浓度下,Cd2+对满江红的毒性大于Hg2+.Hg2+对满江红的致死浓度为3.5～4.0 mg/L,Cd2+为3.0～3.5 mg/L.对满江红鱼腥藻(Anabaena azollae Strasburger)细胞的超微结构变化观察表明,满江红鱼腥藻对Hg2+和Cd2+的耐受性明显高于满江红.     

Activation of three types of membrane currents by various divalent cations in identified molluscan pacemaker neurons

We investigated membrane currents activated by intracellular divalent cations in two types of molluscan pacemaker neurons. A fast and quantitative pressure injection technique was used to apply Ca2+ and other divalent cations. Ca2+ was most effective in activating a nonspecific cation current and two types of K+ currents found in these cells. One type of outward current was quickly activated following injections with increasing effectiveness for divalent cations of ionic radii that were closer to the radius of Ca2+ (Ca2+ greater than Cd2+ greater than Hg2+ greater than Mn2+ greater than Zn2+ greater than Co2+ greater than Ni2+ greater than Pb2+ greater than Sr2+ greater than Mg2+ greater than Ba2+). The other type of outward current was activated with a delay by Ca2+ greater than Sr2+ greater than Hg2+ greater than Pb2+. Mg2+, Ba2+, Zn2+, Cd2+, Mn2+, Co2+, and Ni2+ were ineffective in concentrations up to 5 mM. Comparison with properties of Ca2(+)-sensitive proteins related to the binding of divalent cations suggests that a Ca2(+)-binding protein of the calmodulin/troponin C type is involved in Ca2(+)-dependent activation of the fast-activated type of K+ current. Th sequence obtained for the slowly activated type is compatible with the effectiveness of different divalent cations in activating protein kinase C. The nonspecific cation current was activated by Ca2+ greater than Hg2+ greater than Ba2+ greater than Pb2+ greater than Sr2+, a sequence unlike sequences for known Ca2(+)-binding proteins.     

镉、汞暴露在中华绒螯蟹卵巢中的富集及其氧化应激反应

研究以中华绒螯蟹(Eriocheir sinensis)为实验对象, 用不同浓度的Cd2+ 溶液(0、0.63、1.26、2.52、5.04和10.07 mg/L)或Hg2+ 溶液(0、0.06、0.11、0.23、0.46和0.91 mg/L)对其分别进行染毒, 6d后解剖取其卵巢, 检测卵巢中Cd和Hg的富集量以及氧化应激相关指标的变化情况。结果显示, 随着Cd2+或Hg2+染毒浓度的升高, 卵巢中Cd和Hg的富集量显著增加; H₂O₂、MDA和NO含量、MT mRNA表达量及NOS活性均随着Cd2+和Hg2+浓度的增加出现上升的趋势, 但SOD、CAT和GPx活性呈先升后降的趋势。这说明镉、汞均可引起卵巢组织产生过量的自由基和脂质过氧化, 并诱导氧化应激酶及MT mRNA的表达以抵抗不良的环境。总之, MT对中华绒螯蟹卵巢中重金属的解毒发挥着重要作用, 抗氧化酶能有效地消除活性氧自由基(ROS), 维持机体的氧化还原处于平衡状态, 共同保护膜脂免受氧化损伤。     

Maleate induced change in the kidney binding of mercury in rats pretreated with cadmium

The kidney uptake of Hg2+ was increased by Cd2+-pretreatment when Hg2+ was given intraperitoneally but not subcutaneously. Subsequent s.c. administration of maleate increased Hg2+ release from the kidneys only if Hg2+ was given subcutaneously. Neither the effect of Cd2+, nor that of maleate, on the distribution of Hg2+ among the renal soluble protein fractions was affected by the route of Hg2+ administration. The protective effect of Cd2+-pretreatment against the nephrotoxic effect of Hg2+ was also independent of the route of Hg2+ administration. Maleate given in nephrotoxic doses removed Hg2+ and copper, but not Cd2+ from the renal metallothionein fraction. Mercury in the urine, however, was not complexed by proteins with the molecular weight of thionein, but was bound to high molecular weight proteins and diffusible molecules. These findings are discussed in relation to the role of metallothionein in the interaction between Cd2+ and Hg2+.     

Hg^2＋和Cd^2＋胁迫对满江红生理和细胞超微结构的影响

研究了在梯度浓度Hg^2 和Cd^2 胁迫下,满江红（Azolla imbricata(Roxb.)Nakai)的叶绿素含量,叶绿素a/b比值,光合放氧速率,呼吸速率,抗氧化酶系（超氧化物歧化酶（SOD）,过氧化氢酶（CAT）,过氧化物酶（POD）和细胞超微结构受He^2 和Cd^2 的毒害影响。结果显示：随着胁迫程度的增大,叶绿素含量,叶绿素a/b比值,光合放氧速率明显下降,呼吸速率均在2mg/L浓度下达到峰值,尔后下降;SOD,CAT,POD的活性均出现不同程度的应激性升高（除POD在Cd^2 处理时下降）,尔后下降,电镜观察发现,随着污染物浓度的增加和胁迫时间的延长,叶绿体出现膨大,破损和解体;线粒体嵴突膨胀和线粒体变形及空泡化;核染色质凝集,核仁消失。核膜破裂,实验结果表明：Hg^2 和Cd^2 污染不仅损害植物的生理活性,而且也破坏细胞的超微结构,最终导致植物死亡,随着Hg^2 和Cd^2 为3.0-3.5mg/L。对满江红鱼腥藻（Anabaena azollae Strasburger)细胞的超微结构变化观察表明,满江红鱼腥藻对Hg^2 和Cd^2 的耐受性明显高于满江红。     

汞、镉复合污染对金鱼藻的影响及其抗性机制的探讨

研究了金鱼藻在不同浓度 Hg2 +、Cd2 +以及 Hg2 +、Cd2 +共同胁迫下叶绿素含量、叶绿素 a/b值、可溶性蛋白含量、SOD活性和游离脯氨酸含量等的变化。结果表明 :低浓度 Cd2 + (≤ 2 mg.L- 1)对上述指标有激应性反应 ,低浓度 Hg2 + (≤ 0 .5mg.L- 1)对叶绿素含量、叶绿素 a/b值、可溶性蛋白含量、SOD活性也有激应性反应 ;可以认为这是植物的一种保护性机制。但随着 H2 +、Cd2 +处理浓度增大 ,上述生理指标呈下降趋势 ,表明植物细胞遭受伤害。Hg2 + 、Cd2 + 共同胁迫下上述生理指标下降幅度明显增大 ,表现为协同作用。     

Immunotoxicological investigation of subacute combined exposure with low doses of Pb, Hg and Cd in rats

Detectable interactions between NOEL (No Observed Effect Level) doses of Pb, Hg and Cd in general toxicological, hematological, and immune function parameters were investigated. The metals (Pb-acetate, 20 mg/kg; HgCl2, 0.40 mg/kg; CdCl2, 1.61 mg/kg) were combined. First, the rats received the combination Pb + Hg + Cd for 4 weeks per os. Significant difference vs. control was found only in the weight of lung and popliteal lymph node (PLN). The Pb + Hg and Pb + Cd combinations significantly decreased the PLN to 100 g body weight and PLN to brain weight ratio, and Pb+Hg also decreased the relative adrenal weight. After 12 weeks treatment with the same doses, effects on the thymus, kidney, and adrenal weights in the Pb + Hg, and thymus weight in the Pb + Cd, combination were seen. Pb + Cd also affected the white and red blood cell count and hematocrit. Combined with Hg or Cd, NOEL dose Pb showed toxicity, indicating that exposure limits may be inefficient in combined exposure situations.     

Adsorption of Cd(II) by rhizosphere and non-rhizosphere soil originating from mulberry field under laboratory condition

In this study, the adsorption behavior of Cd ions by rhizosphere soil (RS) and non-rhizosphere soil (NS) originated from mulberry field was investigated. The Langmuir, Freundlich and the Dubinin–Radushkevich (D-R) equations were used to evaluate the type and efficiency of Cd adsorption. The RS was characterized by lower pH but the higher content of soil organic matter and cation exchange capacity (CEC) as compared to NS. Also, the maximum adsorption of Cd²⁺ for RS (5.87 mg/g) was slightly bigger than that for NS (5.36 mg/g). In Freundlich isotherm, the K_f of the adsorption of Cd²⁺ to surface of the RS components was higher than that of the NS, indicating stronger attraction between Cd²⁺ and components of the RS. According to the D-R model, the adsorption of Cd²⁺ by both soils was dominated by ion exchange phenomena. These results indicated that mulberry roots modified physical and chemical properties of the RS under field conditions, which also affected the Cd sorption efficiency by soil components during laboratory experiments. Current knowledge of the Cd²⁺ sorption processes in the rhizosphere of mulberry may be important if these trees are planted for use in phytoremediation of Cd contaminated soils.     

重金属对水稻和小麦DNA甲基化水平的影响

和对照相比,0．025（或0.05)-0.1mmol/L的Cu^2 （或0．05）－1．0mmol/L的Cd^2 或Hg^2 导致水稻（或小麦）叶DNA中的5－甲基胞嘧啶百分含量大幅度上升;当Cu^2 浓度＞0.1mmol/L时,小麦和水稻叶DNA中5－甲基胞嘧啶的百分含量随Cu^2 浓度的增高略有下降,但仍高于对照。0.1-1.0mmol/L的Cu^2 ,Cd^2 和Hg^2 也导致小麦穗DNA为5－甲基胞嘧啶的百分含量随Cu^2 ,Cd^ 和Cd^2 能使小麦和水稻根系DNA中5－甲基胞嘧啶的百分含量显著高于对照,而0.1-1.0mmol/L的Hg^2 以及1．0mmol/L的Cu^2 和Cd^2 则造成小麦和水稻根系DNA中5－甲基胞嘧啶的百分含量显著低于对照。     

Biosorption of Cu2+, Cd2+, Pb2+, and Zn2+ using dried marine green macroalga Caulerpa lentillifera

The sorption of Cu2+, Cd2+, Pb2+, and Zn2+ by a dried green macroalga Caulerpa lentillifera was investigated. The removal efficiency increased with pH. The analysis with FT-IR indicated that possible functional groups involved in metal sorption by this alga were O-H bending, N-H bending, N-H stretching, C-N stretching, C-O, SO stretching, and S-O stretching. The sorption of all metal ions rapidly reached equilibrium within 20min. The sorption kinetics of these metals were governed by external mass transfer and intraparticle diffusion processes. The sorption isotherm followed the Langmuir isotherm where the maximum sorption capacities was Pb2+>Cu2+>Cd2+>Zn2+.     

Queuine-containing isoacceptor of tyrosine tRNA in Drosophila melanogaster. Alteration of levels by divalent cations

Dietary cadmium causes the queuine-containing, Q(+), isoacceptors to increase relative to the guanine-containing, Q(-), ones of tRNATyr, tRNAHis and tRNAAsp of Drosophila melanogaster. Of the other divalent cations examined, Sr2+, Ni2+, Cu2+, Zn2+ and Hg2+, only Hg2+ failed to cause an increase in Q(+)tRNATyr. For these results, all pre-adult stages of the organism were spent on media containing the divalent ions. Adult flies that had developed on a normal diet also responded to divalent ions; Hg2+ as well as Cd2+, Sr2+ and Zn2+ caused an increase in Q(+)tRNATyr in 4 days. Using adult flies, the rate of the response was measured; when placed on a Cd2+-containing diet, they formed significantly more Q(+)tRNATyr within 24 h as compared to adults on a normal diet. Whether the queuine is derived from the diet or from de novo synthesis is yet to be determined. Since the metal ions represent a range of values in the 'hard-soft' classification, different sites of reaction are expected, yet for Drosophila a common result is an alteration in the ratio of Q(+) and Q(-) isoacceptors of these tRNAs. The transition to Q(+)tRNA may be an early indication of the metabolic imbalances resulting from the presence of the divalent cation.     

Effect of some metal ions on blood and liver delta-aminolevulinate dehydratase of Pimelodus maculatus (Pisces, Pimelodidae)

1. delta-ALA-D from Pimelodus maculatus was inhibited in vitro by Cd2+ greater than Pb2+ greater than Hg2+ greater than Cu2+ greater than Zn2+ in blood and by Pb2+ greater than Cd2+ greater than Hg2+ greater than Cu2+ = Zn2+ in the liver. 2. Kinetic analysis of the inhibition by the metal ions showed that Cd2+ and Hg2+ act as non-competitive inhibitors on both sources. 3. Pb2+ showed a mixed type of inhibition in blood and a non-competitive type in the liver. 4. Zn2+ acted as a competitive or mixed inhibitor, on both sources, depending on concentration.     

Inhibition of sarcoplasmic reticulum Ca(2+)-ATPase activity by cadmium, lead and mercury.

The effect of Cd2+, Pb2+ and Hg2+ on the Ca(2+)-ATPase activity of sarcoplasmic reticulum from rabbit muscle was studied. The concentration of relevant free and complex species for the assay conditions have been computed. As a result, ATP hydrolysis was found to be inhibited with an IC50 value of 950 nmol/l free Cd2+ or 95 nmol/l free Pb2+. Although calculation of the free Hg2+ was not possible, the comparison of the IC50 values for total metal ions show that Hg2+ is the strongest inhibitor of enzyme activity. The inhibition by Cd2+ seems to be independent of substrate concentration, whereas the inhibitory effect of Pb2+ is lowered in the presence of higher MgATP concentrations. Our data illustrate that the three heavy metals are potent inhibitors of the Ca2+ pump. Therefore low concentrations of these metal ions may disturb intracellular Ca2+ homeostasis and act on Ca(2+)-mediated cell functions.     

Changes in 45Ca and 109Cd uptake, membrane potential and cell pH in Saccharomyces cerevisiae provoked by Cd2+

The effect of Cd2+ poisoning of Saccharomyces cerevisiae on 45Ca, 109Cd and [14C]tetraphenylphosphonium (TPP) uptake and cell pH was examined. At Cd2+ concentrations that produced substantial K+ efflux the rates of uptake of 45Ca, 109Cd and [14C]TPP increased progressively during incubation of the cells with Cd2+, and the cell pH was lowered concomitantly. The initial rates of uptake of the divalent cations and of TPP were increased in cells pre-loaded with Cd2+, which shows that stimulation of the ion fluxes was exerted by the Cd2+ that accumulated in the cells. The distribution ratio of TPP between cells and medium, however, was decreased by Cd2+. Although hyperpolarization of the cell membrane by Cd2+ cannot be excluded, it is argued that Cd2+ primarily stimulated divalent cation uptake by increasing the cation permeability of the cell membrane allowing the cations to enter the cells more easily.