Separation of heavy metals from water solutions at the laboratory scale

Separation of heavy metals from water may be done by sulphide precipitation. In order to make the metal sulphides more valuable for reuse, they should be as pure as possible. To separate the metals from each other during the precipitation process different parameters as pH, sulphide concentration and redox potential may be controlled. Adjustment of the redox potential to specific values results in separation of copper from cadmium even at the same pH. In the copper precipitation step 98.7 +/- 0.5% was precipitated and the remaining part was transferred to the cadmium precipitation step where 0.7 +/- 0.5% of the copper precipitated. The main part of cadmium (95.6 +/- 1.3%) was precipitated in the second step. These results show that it is possible to separate copper from cadmium by the use of redox potential control.     

乐安河—鄱阳湖湿地植物群落特征及其优势植物对重金属Cu、Pb、Cd的富集

选择乐安河—鄱阳湖湿地典型植物群落,采用重要值方法评价各样点植物群落特征并筛选出典型优势植物,通过室内理化测试分析不同生境中优势植物植株及其根区土壤中重金属Cu、Pb、Cd的含量;采用生物富集系数(BCF)方法评价不同优势植物对重金属Cu、Pb、Cd的富集特性。结果表明:研究区湿地植物以草本为主,在各样点共发现124种物种,包括蕨类植物2科2属2种,种子植物40科97属122种,并从中筛选出羊蹄、红蓼、鼠曲草、紫云英、苎麻等5种富集能力较强的优势植物;植物根区土壤中的Cu、Cd含量均超过土壤环境质量三级标准,而且Cu、Cd的最高含量分别为824.03、5.03 mg·kg-1;不同优势植物对Cu、Pb、Cd等3种重金属元素中的1种或2种表现出较强的富集能力,其中优势物种红蓼对Cu具有较强的富集能力,含Cu量最高为148.80 mg·kg-1,另一种优势物种鼠曲草对三种元素的生物富集系数均较高,且对Cd的最高富集含量为15.17 mg·kg-1,对Cd的生物富集系数最高值为19.14,高于其他植物10倍以上,鼠曲草对重金属Cd具有富集植物的基本特征,且对Cu和Cd具有共富集特征并具有较高的耐性,紫云英、羊蹄等对Cd的富集能力也较强。上述5种优势植物种群对鄱阳湖湿地Cu、Pb、Cd等重金属污染物的生态修复具有一定参考价值,可作为鄱阳湖湿地重金属污染修复植物的选择对象。     

Influence of dietary cadmium on the distribution of the essential metals copper,zinc and iron in tissues of the rat

The effect of long-term dietary cadmium treatment upon the distribution of the metals copper, iron and zinc has been compared in various organs of male and female rats. The renal accumulation of cadmium was similar in both sexes without a plateau being reached. In contrast, the hepatic accumulation of cadmium was higher in the female than in the male rat and a plateau was observed after 30–35 weeks of dietary cadmium treatment. Most of the cadmium which accumulated in these organs was recovered in the metallothionein fraction and the concentration of hepatic cadmiumthionein in the female rat was correspondingly higher than in the male rat. Accumulation of cadmium was associated with an increased zinc concentration in the liver and an increased copper concentration in the kidney; these increases were correlated with increases in liver and kidney metallothioneins induced by cadmium. Uptake of cadmium into organs other than liver and kidney occurred to a small extent but was not associated with changes in the concentration of copper and zinc. Cadmium also accumulated in the intestinal mucosa where it could be recovered in a fraction corresponding to metallothionein. A loss of iron from the liver and kidney was also observed following dietary cadmium treatment and involved mainly a loss of iron from ferritin.     

Heavy metal stress. Activation of distinct mitogen-activated protein kinase pathways by copper and cadmium

Excessive amounts of heavy metals adversely affect plant growth and development. Whereas some regions naturally contain high levels of heavy metals, anthropogenic release of heavy metals into the environment continuously increases soil contamination. The presence of elevated levels of heavy metal ions triggers a wide range of cellular responses including changes in gene expression and synthesis of metal-detoxifying peptides. To elucidate signal transduction events leading to the cellular response to heavy metal stress we analyzed protein phosphorylation induced by elevated levels of copper and cadmium ions as examples for heavy metals with different physiochemical properties and functions. Exposure of alfalfa (Medicago sativa) seedlings to excess copper or cadmium ions activated four distinct mitogen-activated protein kinases (MAPKs): SIMK, MMK2, MMK3, and SAMK. Comparison of the kinetics of MAPK activation revealed that SIMK, MMK2, MMK3, and SAMK are very rapidly activated by copper ions, while cadmium ions induced delayed MAPK activation. In protoplasts, the MAPK kinase SIMKK specifically mediated activation of SIMK and SAMK but not of MMK2 and MMK3. Moreover, SIMKK only conveyed MAPK activation by CuCl(2) but not by CdCl(2). These results suggest that plants respond to heavy metal stress by induction of several distinct MAPK pathways and that excess amounts of copper and cadmium ions induce different cellular signaling mechanisms in roots.     

Uptake of six heavy metals by oat as influenced by soil type and additions of cadmium,lead, zinc and copper

Summary The influence of heavy metal additions on availability and uptake of cadmium, lead, zinc, copper, manganese and iron by oat was studied. The experiments were carried out as pot experiments using sandy loam, sandy soil and organic soil. Selective extractants were used to remove metals held in different soil fractions.Lead and copper were preferently bound by organics and oxides, zinc by oxides and inorganics, and cadmium by inorganics and organics.Addition of cadmium to the soils resulted in higher cadmium concentrations in all plant parts but lower concentrations of lead, zinc, copper, manganese and iron, and the accumulation indexes of these metals were also lower when cadmium was added to the soil.Addition of cadmium plus lead, zinc and copper resulted in higher cadmium concentrations in leaves and straw of plants grown in sandy loam and sandy soil, but lower concentrations when plants were grown in organic soil as compared with the results when cadmium was added separately. The transfer of cadmium, lead, zinc and copper from soil to plant was greatest from sandy soil, and zinc and cadmium were more mobile in the plant than were lead and copper.Cadmium concentrations in leaves correlated significantly with CaCl₂ and CH₃COOH extractions in sandy loam and sandy soil and with CH₃COOH extractions in organic soil.Generally, the total metal uptake was lowest from organic soil.     

大肠杆菌拓扑异构酶I结合重金属的特性及功能影响

【背景】大肠杆菌拓扑异构酶Ⅰ(Escherichia coli topoisomerase I,E.coli TopA)在DNA复制、转录、重组和基因表达调控等过程发挥关键作用。研究表明E.coli TopA只有结合锌离子才具有活性,然而E.coli TopA能否结合其他金属离子尤其是重金属离子,以及结合其他金属后是否具有活性,目前仍不清楚。【目的】探究大肠杆菌拓扑异构酶Ⅰ是否结合环境中常见重金属离子,研究重金属离子结合E.coli TopA蛋白后对其活性的影响。【方法】在分别添加有锌、钴、镍、镉、铁、汞、砷、铬、铅、铜离子的M9基础培养中表达、纯化出E.coli TopA蛋白,并对纯化得到的蛋白用电感耦合等离子体质谱仪进行相应金属离子含量的测定;利用表达E.coli TopA锌指结构的突变体蛋白鉴定重金属离子的结合位点;通过体外超螺旋DNA松弛实验测定不同金属结合E.coli TopA的拓扑异构酶活性;通过测定蛋白内源性荧光推测不同金属结合E.coli TopA的空间构象差异。【结果】E.coli TopA在体内除了能结合锌和铁之外,还能够结合钴、镍、镉3种离子,但是不能结合汞、砷、铬、铅、铜离子。钴、镍、镉结合形式的E.coli TopA,每个蛋白分子最多可以结合3个相应的金属离子,他们与TopA蛋白的结合位点也是位于3个锌指结构域,而且每个锌指结构域结合1个金属离子。此外,E.coli TopA结合钴、镍、镉离子后,其DNA拓扑异构酶活性并未受到影响,可能是由于钴、镍、镉离子结合形式的E.coli TopA蛋白,其空间构象与锌结合形式相比并未发生显著变化。【结论】由于DNA拓扑异构酶在维持细胞正常生理功能中发挥关键作用,研究表明E.coli TopA的功能不会受到常见重金属的干扰(不结合或者结合后活性无影响),这也有可能是大肠杆菌在进化过程中产生的对抗环境中重金属离子毒害作用的一种自我保护和耐受机制,具有重要的生理意义。     

The effect of physico-chemical parameters on speciation of trace metals insediments from inland and coastal waters of Ghana

The speciation of cadmium, lead, copper, zinc, manganese and iron into exchangeable, carbonate, reducible and organic bound fractions was studied in sediments from coastal and freshwater environments in Ghana. This was relevant as the species in which metals are stored within specific sediment components is important in determining their impact on the environment. For both coastal and inland sediments, a higher percentage of cadmium was associated with the more available exchangeable and carbonate fractions, while iron, zinc and manganese were mainly associated with the reducible and organic fractions. Lead and copper were found to have the greatest ability to form different species in the samples examined and were more evenly associated with all the fractions. The metals generally showed more ability to form different species in inland freshwaters than in coastal relatively saline waters. However, differences between inland and coastal waters were based more on whether the environments were oxidising or reducing than on whether they were fresh or saline. The metals may be divided into three groups of high mobility consisting of lead and copper; moderate mobility made up of cadmium, manganese and zinc; and low mobility, represented by iron.     

In vitro exposure of heavy metals on nucleotidase and cholinesterase activities from the digestive gland of Helix aspersa

Zinc, copper and cadmium are important environmental contaminants and differences in purinergic and cholinergic systems of invertebrates have been described when compared to characteristics of these signaling systems in vertebrates. Here we evaluate the effect in vitro of these metals on the ATPase, 5'-nucleotidase and cholinesterase (ChE) activities in the digestive gland of Helix aspersa. Zinc (500 and 1000 microM) promoted a significant decrease in 5'-nucleotidase activity. However, it did not induce changes in ATP hydrolysis. Copper (25 and 50 microM), inhibited significantly ATPase activity, but did not alter 5'-nucleotidase when compared to control (no metal added). In relation to effects of cadmium, an inhibitory effect on ATP hydrolysis has been observed at concentrations of 100, 500 and 1000 microM and a similar decrease of AMP hydrolysis was observed at 500 and 1000 microM. However, there were no significant changes in ChE activity from homogenates of the digestive gland of H. aspersa for all metals tested. This study demonstrated that zinc, cadmium and copper affect ATPase and 5'-nucleotidase in digestive gland, but not ChE, suggesting that the purinergic system may be a target related to toxicity induced by these metals and a possible indicator of biological impact of exposure to these contaminants.     

Heavy metals in relation to the biology of the mummichog, Fundulus heteroclitus

Heavy metal levels of cadmium, copper, mercury, manganese, and zinc were examined in the mummichog, Fundulus heteroditus from industrialized and non-industrialized environments. With one exception, the environment with the highest trace metal in its waters, had the fishes with the highest metal concentration. Except for mercury, the concentration factor varied inversely with the metal concentrations of the fish and water, suggesting a possible regulatory mechanism for metals in the tissues of mummichogs from environments with high metal concentrations. There was an inverse relationship between standard length and concentrations of zinc, manganese, copper and cadmium in whole male and female fishes. The viscera contained significantly greater concentrations of these metals than somatic muscle tissue. There were also significant differences between males and females with respect to whole-body zinc and copper concentrations, but no sex differences for manganese and cadmium.     

Accumulation of cadmium and copper by the terrestrial snail Arianta arbustorum L.: kinetics and budgets

Summary Specimens of the terrestrial gastropod Arianta arbustorum were fed on cadmium- or copper-enriched agar plates with the aim of performing an input/output analysis and of studying the distribution of these metals in several organs of the snails. After a feeding period of 20 days about 45% of cadmium were lost. 36% accumulated in the hepatopancreas, where a cadmium concentration of more than 500 g/g was measured. The efficiency of cadmium assimilation decreased from about 90% at the beginning to about 55% after 20 days. Copper was distributed more evenly than cadmium, but the main site of copper storage seemed to be the foot/mantle tissues, where 49% of the ingested copper were found. The efficiency of copper assimilation always exceeded 95%. The patterns of distribution and assimilation of copper and cadmium are discussed in relation to differences in the cytological and biochemical detoxification mechanisms which exist for these metals in molluscs.     

Trace metals in the benthic habitat of the Maarsseveen Lakes system,The Netherlands

The cadmium, zinc, lead and copper concentrations in benthic invertebrates and sediment were determined during two consecutive winters in the Maarsseveen Lakes system. A sequential extraction procedure was applied to estimate the bioavailability of the trace metals in the sediment. Based on the trace metal analyses of organisms and sediment, it is concluded that the Maarsseveen Lakes system has background levels of cadmium, zinc, lead and copper. As the majority of metals was present in geochemically more stable sediment phases, the sequential extractions provided limited additional information on trace metal bioavailability.     

Cadmium,copper, and zinc levels in the rice and rice field soil of Houston,Texas

Fifty-one pairs of hulled rice samples and the soil from which each rice sample was grown were analyzed for heavy metals in August, 1979, in order to estimate the background contamination of cadmium (Cd), copper (Cu), and zinc (Zn) in rice grown in the Houston, Texas area. Both samples were divided into three groups by soil types and colors. The cadmium concentration in Texas rice was only one-half to one-quarter lower than that of Asian rice. However, the levels of Cu and Zn in rice in Texas were similar to those reported. Soil heavy metals were lower than ever reported, but these values were consistent with the geochemical characteristics of the Texas Houston area. No particular relationship was found between the three metals in rice and the metals in soil where the sampled rice was grown.     

Influence of selenium on uptake and toxicity of copper and cadmium in pea (Pisum sativum) and wheat (Triticum aestivum)

The detoxifying effect of selenium on animals toxicated with heavy metals is well known. In this study we examine if there is a similar effect in plants. Wheat ( Triticum aestivum L. cv. Sunny) and pea ( Pisum sativum L. cv. Fenomen) were grown for 21 days on a nutrient solution based on the nutrient proportions in healthy plants. Nutrients along with cadmium, copper, selenite, selenate or selenite and selenate in combinations with copper or cadmium were supplied in small amounts with a daily incremental increase of 0.12 (wheat) and 0.20 (pea). The metal and selenium uptake and distribution in the plants as well as the effects on growth were investigated.
The results show that selenium does not reduce the toxicity of heavy metals to plants. Instead, selenium enhances metal uptake and toxicity, especially in peas grown in the presence of metal and selenate. Selenite increased cadmium concentrations of pea roots up to 300% and selenate that of wheat shoots up to 50%.     

Cadmium and copper inhibit both DNA repair activities of polynucleotide kinase

Human exposure to heavy metals is of increasing concern due to their well-documented toxicological and carcinogenic effects and rising environmental levels through industrial processes and pollution. It has been widely reported that such metals can be genotoxic by several modes of action including generation of reactive oxygen species and inhibition of DNA repair. However, although it has been observed that certain heavy metals can inhibit single strand break (SSB) rejoining, the effects of these metals on SSB end-processing enzymes has not previously been investigated. Accordingly, we have investigated the potential inhibition of polynucleotide kinase (PNK)-dependent single strand break repair by six metals: cadmium, cobalt, copper, nickel, lead and zinc. It was found that micromolar concentrations of cadmium and copper are able to inhibit the phosphatase and kinase activities of PNK in both human cell extracts and purified recombinant protein, while the other metals had no effect at the concentrations tested. The inhibition of PNK by environmentally and physiologically relevant concentrations of cadmium and copper suggests a novel means by which these toxic heavy metals may exert their carcinogenic and neurotoxic effects.     

Cadmium-copper interaction in intestinal mucosal cell cytosol of mice

In vivo as well as in vitro protein-metal interaction was studied in cytosolic fractions from intestinal mucosal cells. Female Swiss-Webster mice wre pretreated with cadmium (25 ppm) or copper (100 ppm) in drinking water for 3 weeks. Treatment groups were divided into subgroups receiving Cd or Cd+Cu for an additional 6 weeks. In the in vitro study, mucosal cytosol obtained from pretreated animals was incubated with Cd-109 or Cd-109+Cu. Proteins were separated by gel filtration chromatography and metals determined by furnace AAS or gamma-spectrometry. Cadmium-induced synthesis of metallothionein-like proteins (MTP) in cytosol was indicated by increased Cd in those eluted fractions corresponding to the molecular weight of purified equine renal metallothionein. This cadmium level reached a plateau after 3 weeks of cadmium treatment. In addition, an increased amount of cadmium bound to MTP was noted when copper was added to cadmium in drinking water of mice pretreated with copper. This was not the case for Cd-pretreated animals. The in vitro experiments produced similar results, in that MTP fractions retained a greater percentage of Cd when animals were pretreated with copper compared to controls. Cadmium pretreatment resulted in even higher amounts of cadmium bound to MTP. The existence of a Cd as well as a separate Cu MTP, each with specific metal-binding properties, is suggested.     

Hepatic metallothionein production and resistance to heavy metals by rainbow trout (Salmo gairdneri)--I. Exposed to an artificial mixture of zinc, copper and cadmium

Rainbow trout developed elevated hepatic metallothionein concentrations after 4 weeks in a solution containing zinc, copper and cadmium in a fixed ratio of 400:20:1. Resistance to a combination of these metals increased in proportion to the concentration to which they were exposed for 4 weeks. The concentration of copper but not zinc or cadmium in the low molecular weight proteins separated by gel filtration was related to the concentrations of metallothionein present. The combined toxicity of the metals in the mixture was additive.     

Biosorption of heavy metals by Fucus spiralis

The sorption uptake of cadmium, nickel, zinc, copper and lead by marine brown alga Fucus spiralis was investigated in bimetallic, trimetallic and multimetallic solutions. The experimental data fitted very well to Langmuir model. In bimetallic systems, the affinity of biomass for lead and copper increased and the sorption uptake of these metals was not affected by increasing concentrations of cadmium, nickel or zinc. However, in solutions with both metals there was a significant mutual decrease of their sorption levels at high concentrations of the other metal. The sorption uptake of cadmium, nickel and copper was investigated in trimetallic aqueous systems. Based on the kinetic parameter b, the affinity of F. spiralis for copper was considerably higher than for cadmium or nickel: bCd=6.39, bNi=1.82 and bCu=17.89. In all tests, the maximum sorption uptake remained practically constant around 1 mmol/g, indicating that the number of active sites on the biomass was limited. Tests with four and five metals showed that copper was preferentially adsorbed. The differences between the experimental sorption data and those given by the chemical speciation program PHREEQCI were negligible. In general, the software used provided satisfactory estimated data for each metal and hence can be a useful tool to predict or simulate the real process.     

Biomonitoring Survey of Trace Metal Pollution in Streams of a Catchment Draining a Zinc and Lead Mining Area of Upper Silesia,Poland Using the Amphipod Gammarus fossarum

We have used accumulated metal concentration data to investigate variability in the bioavailabilities of cadmium, copper, lead, zinc and iron to the amphipod Gammarus fossarum inhabiting the Biala Przemsza river system draining an area of lead and zinc mining. The highest bioavailabilities of most of the metals were found in a stream carrying water from mine drainage and flotation processes. Significant amounts of bioavailable cadmium entered via another stream receiving waters from ore processing. The bioavailabilities of copper varied little, indicating the lack of a local point source of entry. All metals other than copper showed seasonal variations with the highest concentrations recorded in October. Comparative data show the Biala Przemsza system to be contaminated with cadmium, lead, zinc and iron. The data presented exemplify metal concentration ranges in G. fossarum inhabiting industrial areas, and can be used as a reference for future surveys involving this species in Central Europe.     

Changes of Blue Mussels Mytilus edulis L. Lipid Composition Under Cadmium and Copper Toxic Effect

The lipid and fatty acid composition of the blue mussels Mytilus edulis L. gills and digestive glands was evaluated after 24 and 72 h of cadmium (Cd) and copper (Cu) exposure. Mussels were exposed to different cadmium (10, 100, and 500 μg/L) and copper (5, 50, and 250 μg/L) concentrations. Similar stress response of predominant membrane phospholipids level as well as polyenoic and non-methylene interrupted (NMI) fatty acids content was observed in mussel gills under both cadmium and copper effects. Increased NMI fatty acids level after 24 h, the metal ions treatment suggests that these acids contribute to the protective response to the membrane oxidative stress caused by accumulation of the metals. The content of cholesterol, some minor membrane phospholipids, and storage lipids (triacylglycerols, TAG) in the mussels’ organs alter significantly under the cadmium and copper effect. A two-step response at the digestive glands TAG level depends on the duration of the cadmium and copper treatments (24 and 72 h) on the mussels. The results demonstrate that Cd and Cu impact has adverse effects on gills and digestive glands lipid and fatty acids composition. The type of observed effects varies with the nature and concentration of the metal ions and depends on the role of the metals in the mussels’ life activity.     

Heavy metals in Antarctic organisms

 To evaluate levels of essential (zinc and copper) and non-essential (mercury and cadmium) heavy metals, 34 species of organisms from different areas close to the Antarctic Peninsula were analysed. These included algae, filter-feeders, omnivorous invertebrates and vertebrates. Mercury was not detected, while cadmium was found in the majority of organisms analysed (detection limit was 0.05 ppm for both metals). The highest cadmium concentration was observed in the starfish Odontaster validus. Anthozoans, sipunculids and nudibranchs showed maximum levels of zinc, while the highest copper level was found in the gastropod Trophon brevispira. Mercury and cadmium levels in fishes were below the detection limit. Concentrations of essential and non-essential metals in birds were highest in liver followed by muscle and eggs. Cadmium and mercury levels in muscle of southern elephant seals were above the detection limit, whereas in Antarctic fur seals they were below it. The objective of the study was to gather baseline information for metals in Antarctic Ocean biota that may be needed to detect, measure and monitor future environmental changes. Received: 17 July 1995/Accepted: 11 April 1996