Simultaneous Determination of Cd, Pb, Cu, Zn, and Se in Human Blood of Jordanian Smokers by ICP-OES

A total of 73 blood samples (56 from smokers and 17 from nonsmokers) were collected to determine the concentrations of selected heavy metal in the whole blood of smokers and nonsmokers living in and around the city of Amman, Jordan. Analysis of heavy metals in the whole blood samples of various groups took in consideration the number of cigarettes smoked per day. The analysis of blood samples was carried out using inductively coupled plasma optical emission spectrometry. This study aimed to evaluate the blood metal levels in smokers and nonsmokers and to assess the influence of smoking cigarettes on blood metal levels. The results were compared with those from a control group. The results indicated that the average concentrations of cadmium (Cd), lead (Pb), copper (Cu), zinc (Zn), and selenium (Se) were 0.0313, 0.344, 2.328, 3.214, and 0.332 mg/L, respectively. Statistical analysis of results indicated that these average concentrations were significantly higher compared with the average concentrations in nonsmokers (P < 0.05). Moreover, the correlations between blood metal and other blood metal levels in smokers, the correlations between blood metal and other blood metal levels in nonsmokers, and the correlations between blood metal concentration in smokers and its concentration in nonsmokers were calculated. The standard reference material (blood serum National Institute of Standards and Technology 1598) and the quality control were used to validate the reliability of the method used for the estimation of heavy metals in blood samples. Results revealed that there was an agreement between the certified values and the measured values.     

Litter accumulation in woodlands contaminated by Pb,Zn, Cd and Cu

Summary Close to a primary lead-zinc-cadmium smelter the standing crop of litter in woodlands was found to be elevated relative to more distant sites. The total litter accumulation is similar to that from contaminated sites reported by other authors but in this case the concentrations of heavy metals are considerably lower than those reported for other sites. Evidence is provided to support the hypothesis that within the woodlands studied, litter accumulation is not closely pH dependent, but is clearly related to both cadmium and zinc concentrations in litter. Litter accumulation occurs in certain particle size ranges and fractionation shows that the weight of accumulated litter in these size ranges is highly correlated to cadmium concentrations. These results are discussed in relation to the reported possible long term effects of metal contamination on decomposition processes and the possibility of adaptation to these adverse effects.     

Serum levels of Cd, Pb, Cu and Zn in cigarette smokers

In order to show the accumulation of Cd, Pb, Cu and Zn in smokers, levels of these metals in serum were determined in 108 subjects: 32 non-smokers, 37 average cigarette smokers and 39 heavy cigarette smokers. The analysis was carried out by potentiometric stripping analysis (PSA) with the Tecator "Striptec System". Backward oxidation time of the amalgamated metals, by means of electrolysis, in a thin "film" of mercury in an electrode, gives their concentration measure. Our data showed an increase in average values of Cd and Pb in the serum of heavy smokers compared with average and non-smokers. Instead, as regards Cu and Zn, no differences were found in the two groups of smokers compared with the non-smokers used as controls. Results obtained of the Cd and Pb levels in serum are compatible with the presence of these metals in cigarette tobacco and inhaling them could contribute to disease connected with their accumulation in the human organism. For these subjects the increase in Cd values is of particular importance as it could predispose pulmonary emphysema.     

Simultaneous determination of Zn,Cd, Pb,and Cu in urine of patients with blackfoot disease using anodic stripping voltammetry

Blackfoot disease (BFD) is an endemic peripheral vascular disorder resulting in gangrene of the lower extremities, especially the feet, among residents in a limited area on the southwest coast of Taiwan. In the present study, the concentrations of zinc, cadmium, lead, and copper in urine of BFD patients with matched normal controls are investigated by differential pulse anodic stripping voltammetry (DPASV) on a hanging mercury drop electrode (HMDE). The analytical results indicate that urinary copper, cadmium, and lead of the BFD patients are significantly higher than those of the controls. In addition, the patients showed a significantly lower concentration of zinc in the urine than the normal controls. The possible connection of these elements with the etiology of the disease is discussed.     

Determination of Cd, Cu, Pb and Zn in neoplastic kidneys and in renal tissue of fetuses, newborns and corpses

The incidence of kidney tumors in USA and Europe (in particular, Central Europe and Italy) has been dramatically increasing since the 1970s, possibly as a consequence of ongoing environmental pollution. Environmental factors have been considered responsible for at least 80% of the incidence of neoplastic diseases. To shed some light on this issue, the amounts of Cd and Pb were measured in neoplastic tissue and adjacent normal part of kidney excised for carcinoma and compared with those in renal tissues of fetuses, newborns and subjects that died of non-neoplastic diseases. Cd and Pb were determined by Inductively Coupled Plasma Atomic Emission Spectrometry and Atomic Absorption Spectrometry with Electrothermal Atomization. Metallothionein immunoperoxidase staining technique was used to localize the accumulation of Cd and Zn in the nephrons. Content of Cd and Pb in kidneys of fetuses and newborns was extremely low. However, it was significantly increased in adjacent-normal tissues of kidneys with carcinomas, and significantly higher compared to kidneys of individuals that died of non-neoplastic diseases. In tumoral tissues of the excised kidneys, Cd content was very low, while that of Pb significantly elevated. High amounts of Cd and Pb in the adjacent-normal parts of kidneys with carcinomas are suggestive of possible, individual or synergistic, effects of these pollutants on enzymatic systems, priming an oncogenic pathway. Detection of metallothioneins, primary ligands of Cd, exclusively in the cells of proximal tubuli, i.e. wherein renal carcinoma develops in over 80% of cases, strongly supports the assumption that Cd exerts a carcinogenic effect.     

Sorption behavior of Cd, Cu, Pb, and Zn and their interactions in phytoremediated soil

The aim of our study was to compare the sorption properties of a contaminated soil before and after two types of phytoremediation (natural phytoextraction vs. phytostabilization with dolomite limestone (DL) application). Soil from a pot experiment in controlled greenhouse conditions performed for two vegetation periods was used for the study. Lead, as the main contaminant in the studied soil, was easily desorbed by Cu, especially due to the increased affinity of Cu for soil organic matter; hence input of Cu to the studied soil can present another environmental risk in soils contaminated with other metals (such as Pb). In addition, the sorption behavior of chosen metals from single-element solutions differed from multielement solutions. The obtained results proved the different sorption behavior of metals in the single-element solution compared to the multi-element ones. Soil sorption behavior of Cd, Cu, and Zn decreased with the presence of the competitive metals; nevertheless, Pb sorption potential was not influenced by other competitive metals. Natural phytoextraction showed no significant effect on the sorption of Cd, Cu, Pb, and Zn onto the soil On the other hand, phytostabilization associated with DL application improved the soil sorption efficiency of all chosen metals, especially of Cu.     

污染条件下VAM玉米元素积累和分布与根际重金属形态变化的关系

为了了解重金属Cu、Zn、Pb、Cd在土壤－根际－植物系统中的行为,揭示VAM植物减弱土壤中过量重金属对植物生理毒的抗性机理,采用原子吸收光谱测定Cu、Zn、Pb、Cd在污灌土壤中生长的VA菌根玉米和无菌根玉米中的积累和分布,并用连接形态分析技术分析了菌根际中Cu、Zn、Pb、Cd的形态分布和变化趋势,结果表明,Cu、Zn、Pb、Cd在菌根玉米中的积累量比非攻根中积累量分别减少10％、18％和29％,Cd积累量没有改变,生长7周后,菌根玉米是非菌根玉米生物量的1．5倍,与对照土壤相比,根际中除Cu交换态显著增加外,Zn、Pb、Cd各形态相对改变量显著大于非菌根,且菌根根际上中Cu、Zn、Pb有机结合态增加量显著大于非根际土,说明菌根际金属向稳定状态转移的程度显著大于非菌根际,同时,讨论了根际金属形态对金属有效性的影响,及其与菌根植物金属抗性机理的关系。     

重金属Cd、Zn、Cu、Pb对土壤微生物和酶活性的影响

采用室内培养实验(25℃),研究了不同培养时间下重金属Cd、Zn、Cu、Pb(浓度分别为50,800,400,800mg.kg-1)污染对土壤微生物和酶活性的影响。结果表明,土壤蔗糖酶、过氧化氢酶和脱氢酶活性随着培养时间的增加而显著下降,在培养20d的时候达到最小值,然后酶活性缓慢升高。Cu对脲酶活性以及Cd对酸性磷酸酶和脲酶活性的抑制作用随时间增加而增加。土壤微生物生物量碳、细菌、真菌和放线菌数量随培养时间的增加均表现出先降低后升高的变化趋势。Cd和Cu对微生物生物量氮的抑制作用则随着培养时间的增加而增强,在培养30d时微生物生物量氮到达最低值,分别较培养10天减少了12.6%和16.5%。     

芜湖钢铁厂周边土壤及油菜籽中镉、铜、锌、铅含量和形态分布研究

研究了污染土壤、油菜籽中Cd、Cu、Zn、Pb含量、形态分布特征和重金属富集状况及可能存在的生物毒性.结果表明,土壤中Cd、Zn、Pb以铁锰氧化物结合态、Cu以残留态占5种形态最高比例,分别为31.1%、39.3%、53.79%、46.24%;Cd、Pb交换态比例较高,为23.47%、16.32%,Cu、Zn的交换态比例较小,为3.14%、0.54%;土壤中不同重金属与各重金属形态相关关系有差别,5种重金属形态转化为有效态重金属难易程度不同;油菜籽和油菜籽壳中不同重金属累积趋势有差异,Cu易在油菜籽壳中累积,Cd、Zn、Pb易在油菜籽中累积;油菜籽中不同重金属累积率不同,Cd累积率最高,为0.56.油菜籽中重金属累积率与土壤中重金属总量呈显著负相关关系(P＜0.05),土壤中重金属的形态、转化差异是此种负相关关系的主要原因;油菜籽中Cd、Cu、Pb以氯化钠态为主,分别为32.50%、22.94%、34.69%,Zn以EDTA态为主,为45.97%.油菜籽中重金属形态可能影响其毒性,但其毒性的人类膳食风险还需进一步研究证实.油菜籽中重金属形态与油菜中重金属总量相关性不好.     

Distribution of Toxic Trace Metals Zn,Cd, Pb,and Cu in Tirupati Soils,India

The concentrations of toxic trace metals in the soil samples collected from Tirupati, India, have been determined using differential pulse anodic stripping voltammetry (DPASV). The total metal concentrations of the soils in the study area were in the following ranges: 19.5 to 23.6 mg of Zn, 0.032 to 0.036 mg of Cd, 15.8 to 18.9 mg of Pb, and 19.0 to 23.4 mg of Cu per kg soil. Analysis of standard reference material IAEA-SOIL-5 indicates good accuracy. Recoveries were nearly quantitative for all elements studied. Comparison of the average metal concentration levels with world averages indicates an elevated value for Pb. The applicability of this method was crosschecked with AAS and the results were in good agreement.     

Phytoremediation of Cd,Ni, Pb and Zn by Salvinia minima

Most metals disperse easily in environments and can be bioconcentrated in tissues of many organisms causing risks to the health and stability of aquatic ecosystems even at low concentrations. The use of plants to phytoremediation has been evaluated to mitigate the environmental contamination by metals since they have large capacity to adsorb or accumulate these elements. In this study we evaluate Salvinia minima growth and its ability to accumulate metals. The plants were cultivated for about 60 days in different concentrations of Cd, Ni, Pb and Zn (tested alone) in controlled environmental conditions and availability of nutrients. The results indicated that S. minima was able to grow in low concentrations of selected metals (0.03 mg L^?1 Cd, 0.40 mg L^?1 Ni, 1.00 mg L^?1 Pb and 1.00 mg L^?1 Zn) and still able to adsorb or accumulate metals in their tissues when cultivated in higher concentrations of selected metals without necessarily grow. The maximum values of removal metal rates (mg m² day^?1) for each metal (Cd = 0.0045, Ni = 0.0595, Pb = 0.1423 e Zn = 0.4046) are listed. We concluded that S. minima may be used as an additional tool for metals removal from effluent.     

Molecular fractionation of Zn, Cu, Cd and Pb in the midgut gland of Helix pomatia L

Specimens of Helix pomatia were fed lettuce enriched with Zn, Cu, Cd and Pb for 30-35 days, after which time the distribution of the four metals in the midgut gland was studied by centrifugation, ion exchange and gel chromatography. In control snails the distribution between the soluble and particulate fraction of the midgut gland is relatively uniform, with a ratio of approximately 3:1 for Cu, Cd and Pb, and of 1:1 for Zn. However, after metal-loading about two-thirds of total Zn and Pb appears in the particulate fraction whereas little change in relative distribution is observed with Cu and Cd. After ion exchange chromatography of the supernatant both Cd and Zn eluted in one distinct peak, Cu in two peaks, whereas Pb seemed to be distributed unspecifically throughout the elution volume. If ion exchange is followed by gel chromatography, Zn, Cu and Cd are found associated with from one to four molecular species, ranging in mol. wt from 1000 to greater than 20,000, whereas no complex was found for Pb. The molecular patterns are specific for each of the three metals and there are some specific shifts in abundance, usually involving one molecular fraction, if control snails are compared with metal-loaded snails.     

Development of a Rapid and Simple Digestion Method of Freshwater Sediments for As,Cd, Cr,Cu, Pb,Fe, and Zn Determination by Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES): An Evaluation of Dilute Nitric Acid

In this study, a simple and rapid methodology based on the hot-plate digestion method using dilute nitric acid solution was used to extract trace metals (such as As, Cd, Cr, Cu, Pb, Fe, and Zn) from freshwater sediments. The concentrations of the elements were determined using inductively coupled plasma-optical emission spectrometry (ICP-OES). The factors (temperature, nitric acid concentration, and volume) affecting the digestion method were optimized using one-factor-at-a-time (OFAT) or univariate methodology, and the optimization process was carried out using freshwater sediment certified reference material (CRM015). The optimal conditions for temperature, nitric acid concentration, and time in the method were 180°C, 10 mL of 5 mol L^?1 HNO₃, and 45 min, respectively. Under optimum conditions, the limit of detection (LOD) ranged between 0.02 and 0.08 µg L^?1 and the limit of quantification (LOQ) ranged from 0.07 and 0.27 µg L^?1. In addition, the method detection limits (MDLs) and method quantification limits (MQLs) were 0.10–0.17 and 0.30?0.57 µg g^?1, respectively. The overall accuracy of the method determined by recovery of the trace elements in the CRMs ranged from 98 to 111% with the precision ranging from 1.4 to 5.8%. The method was successfully applied for the determination of target metals from real freshwater sediment samples.     

Biochemical responses of the aquatic moss Fontinalis antipyretica to Cd,Cu, Pb and Zn determined by chlorophyll fluorescence and protein levels

Biochemical reactions to Cu, Cd, Zn and Pb in the aquatic moss Fontinalis antipyretica were studied in order to characterize the physiological background of the metal response. Chlorophyll fluorescence and intracellular metal localization and stress protein levels were measured. Exposure to 25 or 100 μM Cu over a 7-day period resulted in a decline of chlorophyll fluorescence to about 70% and 52%, respectively. Up to 100 μM Cd caused a decrease in chlorophyll fluorescence to 75%. With all metals used at 25–100 μM concentrations, the intracellular uptake increased. For all metals investigated at 25–100 μM, the intracellular uptake increased. Maximum values were reached at 100 μM Cu, Pb, Zn or Cd exposure. As shown by analytical electron microscopy (EDX, EELS) moss material treated with 50 μM Cu exhibited reduced sulphur levels in the cytoplasm and an increase in phosphate in vacuolar dense particles. EEL-spectra indicated that Cu is chelated in the cytoplasm by SH-groups and coprecipitated with orthophosphate in vacuoles. To monitor the stress response at the protein level, heavy metal induced heat shock protein 70 (hsp70) was measured. An antibody was raised against conserved plant metallothionein p2 motifs derived from Brassica juncea. In all metal-treated samples the antibody bound to proteins of about 8 kDa. However, sequencing failed to reveal significant homologies to known proteins. These experiments provide for the first time results on protein level after heavy metal stress in the aquatic bioindicator moss.     

农作物体内铅,镉,铜的化学形态研究

本文报道了农作物体内重金属存在的化学形态。用逐步提取法分析了生长在污染土壤上的水稻、小麦的根与叶。结果表明,在两种作物中,根部的铅以活性较低的醋酸可提取态与盐酸可提取态占优势,而叶中的铅以盐酸可提取态占优势。不论根部或叶部,在各种形态镉中,以氯化钠可提取镉所占比例较高,作用较重要。作物体内的铜活性较强,根部以乙醇可提取态占优势,叶中以水提取态占优势。各种结合形态的重金属迁移能力、毒性效应有显著差异。作物体内重金属化学形态特征与其表观毒性效应有密切联系。     

Distribution patterns of Cd,Cu, Mn,Pb and Zn in wood fly ash emitted from domestic boilers

Abstract

Wood fuels being a renewable source of primary energy have been considered environmentally friendly. However, wood combustion in domestic boilers is a source of air pollution. The lack of a dust collection device is the reason why flue gases emit a significant load of particulate pollutants into the air, including heavy metals. The aim of this research was to assess the environmental hazard caused by both emissions of heavy metals during wood combustion in domestic boilers and their chemical forms present in fly ash.

From the various wood fuels burnt in domestic boilers, the fly ash selected for this study came from the combustion of briquettes of softwood from non-polluted areas, and from burning hardwood fuel from trees exposed to pollutants from heavy traffic. The wood fuels satisfy the quality demands determined in the EN 14961 Solid Biofuels - Fuel quality assurances. However, the concentrations of Cd, Cu, Pb and Zn in the fly ash are considerably higher than the appropriate limit values determined for soil improvers. Sequential extraction shows that Cd and Zn are associated mainly with the water leaching and carbonate fractions, regarded as mobile and bioavailable, and pose the potentially greatest hazard to the environment and human health. Cu, Mn and Pb associated with less mobile fractions may not pose a direct air quality hazard but, due to their high concentrations, medium-term and long-term effects on soils and surface and subsurface waters should be considered.     

Epidermal uptake of Pb,Cd, and Zn in tubificid worms

Summary The epidermal uptake of Pb, Cd, and the essential element Zn by tubificid worms was investigated. The animals were starved and contaminated via the water column at 4°C and 25°C. Atomic absorption spectroscopy (AAS), energy-dispersive X-ray microanalysis (EDX), laser induced mass analysis (LAMMA), electron microscopy, and the sulfide-silver method at the electron microscopical level were used. The sulfidesilver method revealed many reaction products indicating heavy metals in membrane-limited lysosomal structures in epidermal cells of contaminated Limnodrilus udekemianus. In these lysosomes, which were particularly abundant in the epidermis of the hind end, Pb, Cd, and Zn were detected by LAMMA and EDX analysis. Beside this distinct occurrence of the three elements a uniform pattern of reaction products was found in epidermal cells after contamination with Cd and Zn, but not after treatment with Pb. As shown by atomic absorption spectroscopy, Cd was the most enriched element at 25°C, followed by Pb and Zn. Simultaneous application of Zn reduced the uptake of Cd, whereas the uptake of Pb was increased. At 4° C uptake of Pb and Cd was slower than at 25° C, while Zn uptake was blocked completely. This shows that heavy metal uptake can be strongly dependent on environmental conditions, which has to be taken into account if animals are used as monitor organisms for heavy metal pollution in the environment.     

Accumulation properties of As,Cd, Cu,Pb and Zn by four wetland plant species growing on submerged mine tailings

Plants may reduce element leakage from submerged mine tailings by phytostabilisation. However, high shoot concentrations of elements might disperse them and could be harmful to grazing animals. The aim of this investigation was to find out which of the three properties; low-accumulation, root accumulation or shoot accumulation of elements, occur in four of the most common wetland species growing on an old submerged mine tailings and if their properties can be determined by a hydroponic experiment. Above- and below-ground parts of Salix (mixed tissue from S. phylicifolia and S. borealis), Carex rostrata, Eriophorum angustifolium, and Phragmites australis were sampled and analysed for Cd, Cu, Zn, Pb and As. Differences in uptake and translocation properties of the same plant species were observed between field-grown plants and plants grown in hydroponics. These differences were probably due to processes in the soil–root interface. Thus, hydroponic screening studies should not be used to find suitable species for vegetation of wet-covered mine tailings. Most species were found to have restricted translocation of elements to the shoot, i.e. they were root accumulators, and only the shoot concentrations of Salix for Cd and Zn and E. angustifolium for Pb might be toxic to grazing animals. Thus, plant establishment on submerged tailings can be a safe method to stabilise the metals.     

Interspecific differences in Zn,Cd and Pb accumulation by freshwater algae and bryophytes

The relationships between the concentrations of zinc, cadmium and lead in aquatic plants and the concentrations of these metals in the ambient water have been compared for three algae (Lemanea fluviatilis, Cladophora glomerata, Stigeoclonium tenue), one liverwort (Scapania undulata) and three mosses (Amblystegium riparium, Fontinalis antipyretica, Rhynchostegium riparioides). The data to establish these relationships are all based on our own studies, some published already, some here for the first time. They come from a wide range of streams and rivers in Belgium, France, Germany, Ireland, Italy and the U.K. There were significant bivariate positive relationships between concentrations of Zn, Cd and Pb in water and plant for all species except Cd and Pb in Stigeoclonium tenue. When relationships were compared using datasets with total or filtrable metals in water, most differences were slight. However there were marked differences both between species and between metals. Comparison for the seven species of Zn in the plant when aqueous Zn is 0.01 mg l^–1, a concentration at which all seven were found, shows that the four bryophytes had the highest concentrations; however the two green algae had steeper slopes (representing change in concentration in plant in response to change in aqueous concentration). Lemanea fluviatilis had a slope closer to that of the bryophytes, but the concentration was about one order of magnitude lower. All seven species were found at a concentration of 0.01 mg l^–1 Pb, and at this concentration there were almost two orders of magnitude difference between the species which accumulated the most (Scapania undulata) and the one which accumulated the least (Cladophora glomerata). The steepest slope was however shown by C. glomerata.When multiple stepwise regression was applied, the aqueous metal under consideration was the first variable extracted in only nine of the 21 regressions. However one of the other heavy metals (aqueous or accumulated) was extracted first in all but one of the other regressions, presumably because the occurrences of Zn, Cd and Pb were strongly cross-correlated. The principal non-heavy metal factor extracted for Zn and Cd, but not Pb, was aqueous Ca. The relevance of these results to the use of aquatic plants for monitoring heavy metals is discussed.     

Partitioning of Zn,Cd, Pb,and Cu in organic-rich soil profiles in the vicinity of a zinc smelter

Abstract

A five-step sequential extraction procedure was applied to organic-rich soil samples from five soil profiles situated 1–8 km from a zinc smelter. The partitioning of Zn, Cd, Pb, and Cu into five operationally defined fractions (exchangeable, “carbonate’’-bound, reducible, oxidizable, and residual) was studied at different soil depths down to 35cm. In the surface soil (0–1 cm) a major part of Pb and Cu was extracted in the oxidizable fraction, whereas for Zn and Cd slightly more was extracted in the ‘‘carbonate”-fraction than in the other four fractions. Extracted metal proportions in the oxidizable fraction were respectively of the order of 30%, 20%, 50%, and 80% for Zn, Cd, Pb, and Cu in the surface soil for all sites, but these proportions decreased with soil depth. In the surface soil less than 20% of all the elements were extracted in the residual fraction, but the proportions associated with this fraction generally increased with soil depth. In the C-horizon, differences in extracted proportions of Pb and Cu in the residual fraction were probably due to geochemical factors, whereas for Zn the low extracted proportion at a highly contaminated site (20%) may be due to Zn migration to the C-horizon at this site. For Cd the extracted proportions in the C-horizon were lower than for the other elements, generally below 20%, presumably because Cd is weaker in terms of its adsorption to the soil than the other elements studied. Total concentrations of the metals decreased strongly with increasing distance from the smelter, but less systematic differences were observed for their distributions among fractions. Potentially bioavailable metal proportions (exchangeable + “carbonate”-bound fraction) in the surface soil were about 50%, 60%, 20%, and 10% for Zn, Cd, Pb, and Cu, respectively. In C-horizon soil the mobility sequence Cd>Zn>Pb = Cu was generally observed. The present results indicate that the concentrations and chemical fractionation of Zn, Pb, and Cd in these soils represent a considerable risk to natural terrestrial food chains.