Accumulation of heavy metals by aquatic mosses. 2: Rhynchostegium riparioides

A study was made of general ecology and metal accumulation in the widespread aquatic moss Rhynchostegium riparioides, (Hedw.) C. Jens. with a view to developing the use of this species as a monitor of heavy metal pollution. In order to establish a data bank for statistical analysis, samples of water and moss were taken within a 6-week period from 105 sites (10-m reaches) in Northern England from streams and rivers of diverse physical and chemical types. Analyses were made of 14 metals (Na, Mg, K, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Ba, Pb) in both 2-cm tips and whole plants. The same 14 metals were also measured in both total and filtrable water, together with 12 other variables. Samples of tips were easier to prepare for analysis, but had significantly (p < 0.001) lower concentrations of all metals except Na and K. Significant correlations (p < 0.001) between metal in moss and aqueous metal were found for ten metals (Na, K, Mg, Ca, Mn, Cu, Zn, Cd, Ba, Pb). Correlations between metals in moss and in water were in general similar for tips and whole plants, but much higher for tips with Na, Zn and Cd; the relationship was quite similar whether total or filtrable water was considered, with the exception of Ba where the correlation was much higher with the latter. A multiple regression was used to suggest which variables in water and/ or moss may influence accumulation of Co, Ni, Cu, Zn, Cd, Ba and Pb in the moss. For instance, the variables which had a very highly significant effect on Pb in tips were Pb, filtrable reactive phosphate and Zn in the water. A discussion is included of how the data may be used for monitoring purposes.     

Comparative Evaluation of Trace Metal Distribution and Correlation in Human Malignant and Benign Breast Tissues

Selected trace metals were analyzed in human malignant and nonmalignant (benign) breast tissue samples by the flame atomic absorption spectrophotometric method. In malignant tissues, dominant mean concentrations were revealed by Na, K, Ca, Mg, Fe, Zn, and Al at 927, 552, 231, 61.7, 36.5, 18.3, and 8.94 microg/g, respectively, while the mean metal levels in benign tissues were 903, 435, 183, 63.3, 24.7, 14.5, and 10.1 microg/g, respectively. Average concentrations of Cd, Co, Cr, Cu, Fe, Mn, K, Ca, and Zn were noted to be significantly higher in the malignant tissues compared with the benign tissues. Significantly strong correlations (r > 0.50) in malignant tissues were observed between Mn and Co, Mn and Cd, Cd and Cr, Fe and Mn, Cd and Co, Fe and Co, Mg and Pb, Cd and Fe, Mg and Ni, Pb and Ni, Ni and Sr, and Fe and Pb, whereas, Cd and Co, Cd and Mn, Co and Mg, Co and Mn, Cu and Mn, Co and Ni, Mg and Ni, Cd and Cu, Cd and Ni, Ca and Mg, Mn and Pb, Cu and Ni, Fe and Ni, Cd and Mg, Co and Cu, Cr and Na, and Cd and Cr revealed strong and significant relationships in benign tissues at p < 0.001. Principal component analysis of the metals data yielded six principal components for malignant tissues and five principal components for benign tissues, with considerably different loadings, duly supported by cluster analysis. The study revealed a considerably different pattern of distribution and mutual correlations of trace metals in the breast tissues of benign and cancerous patients.     

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.     

Copper,Lead, Cadmium,and Zinc Sorption By Waterlogged and Air-Dry Soil

Competitive sorption of copper (Cu), lead (Pb), cadmium (Cd), and zinc (Zn) was studied in three soils of contrasting chemical and physical properties under air-dry and waterlogged conditions. Competitive sorption was determined using the standard batch technique using six solutions, each with Cu, Pb, Cd, and Zn concentrations of approximately 0, 2.5, 5, 10, 20, and 50?mg L^?1Waterlogged soils tended to sorb higher amounts of added Cu, Pb, Zn and Cd relative to soils in the air-dry condition; however, this increase in sorption was generally not statistically (p<0.05) significant. The magnitude of sorption under both waterlogged and air-dry conditions was affected by the type and amount of soil materials involved in metal sorption processes, and competition between other metals for the sorption sites. Metal sorption was closely correlated with soil properties such as cation exchange capacity, organic carbon, and Fe and Mn hydrous oxides. Exchangeable Al may have markedly reduced metal sorption due to its strong affinity for the sorption sites, while increases in exchangeable Mn may have enhanced Zn and Cd sorption. Heavy metal sorption was best described as a combination of both specific and nonspecific interactions. The extractability of Cu, Pb, Cd, and Zn under waterlogged and air-dry conditions was also studied. Three solutions containing these metals were mixed with each soil to achieve a final concentration of 0, 50, and 500?mg kg^?1. Each soil was extracted every 7 days using 1?M MgCl₂ (pH 7) to determine metal extractability. Metal extractability initially decreased then increased due to waterlogging. The increased extractability of added metals was closely related to increased solubility of Fe and Mn suggesting that dissolution of Fe and Mn, oxides under reducing conditions caused a release of previously sorbed Cu, Pb, Cd, and Zn.     

Screening of Trace Metals in the Plasma of Breast Cancer Patients in Comparison with a Healthy Population

The plasmas of breast cancer patients and healthy donors were analyzed for selected trace metals by a flame atomic absorption spectrophotometric method. In the plasma of breast cancer patients, mean concentrations of macronutrients/essential metals, Na, K, Ca, Mg, Fe, and Zn were 3584, 197.0, 30.80, 6.740, 5.266, and 6.170 ppm, respectively, while the mean metal levels in the plasma of healthy donors were 3908, 151.0, 72.40, 17.70, 6.613, and 2.461 ppm, respectively. Average concentrations of Cd, Cr, Cu, Mn, Ni, Pb, Sb, Sr, and Zn were noted to be significantly higher in the plasma of breast cancer patients compared with healthy donors. Very strong mutual correlations (r > 0.70) in the plasma of breast cancer patients were observed between Cd–Pb, Cr–Li, Li–K, Li–Cd, K–Cr, Li–Pb, Cr–Co, Cu–Ni, Co–K, Cd–K, and K–Pb, whereas, Al–Cr, Ca–Zn, Cd–Sb, Cd–Zn, Ca–Mg, Fe–Zn, and Na–Mn exhibited strong relationships (r > 0.60) in the plasma of healthy donors. The cluster analysis revealed considerably different apportionment of trace metals in the two groups of donors. The average metal concentrations of different age groups of the two donor categories were also evaluated, which showed the build-up of Al, Cd, Co, Cr, Mn, Li, Pb, Sb, and Zn in the plasma of breast cancer patients. The role of some trace metals in carcinogenesis is also discussed. The study indicated appreciably different patterns of metal distribution and correlation in the plasma of breast cancer patients in comparison with the healthy population.     

Co-ordination of transition metal ions by galactaric acid: a potentiometric and spectroscopic study

A solution study on the ability of galactaric acid [GalaH(2), HOOC(CH)(4)COOH] in the complexation of biological metal ions such as Co(II) and Ni(II) and toxic metal ions such as Cd(II), Pb(II) and Hg(II), is reported. The stability constants of the complex species are determined by means of potentiometric measurements. Galactaric acid behaves as chelate ligand through carboxylic oxygen and alpha-hydroxy group towards Co(II) and Ni(II), while in the Pb(II) and Cd(II) containing system it co-ordinates the metal ion with carboxylic oxygen and two alcoholic hydroxy groups. The prevailing species at acidic or neutral pH is [MGala] which is also isolated in the solid state and characterized by means of IR spectroscopy. On increasing pH, the [MGalaH(-1)](-) species is also formed where the co-ordinated OH group undergoes deprotonation in all metal ion complexes except those with Hg(II), where the co-ordination of hydroxide ion is suggested as the precipitation of the metal hydroxide occurs at pH 7.     

Comparative Assessment of Essential and Toxic Metals in the Blood of Rheumatoid Arthritis Patients and Healthy Subjects

The present study deals with the comparative evaluation of essential and toxic metals in rheumatoid arthritis and healthy donors. Blood samples collected from rheumatoid arthritis patients and healthy subjects were analysed for selected essential and toxic metals (Ca, Mg, Fe, Zn, Cu, Co, Mn, Cr, Cd and Pb). The samples were digested in nitric acid and perchloric acid mixture, followed by quantification of the metals using atomic absorption spectrometry. Mean levels of Ca, Mg, Fe and Zn were significantly higher in the blood of healthy donors; however, elevated levels of Cd, Co, Cr, Cu and Pb were observed in blood of the patients. The correlation coefficients among the selected metals in the blood of arthritis patients were significantly different compared with the healthy counterparts. Multivariate cluster analysis revealed mutual apportionment of the essential and toxic metals in blood of the patients, whereas, in controls, the essential and toxic metals revealed diverse apportionment. Variations in the metal levels with gender, residence and smoking habits were also evaluated in both donor groups. Relative distribution, correlation and apportionment of the essential and toxic metals in the blood of the patients were significantly different than of controls.     

The distribution of cadmium,copper, lead,zinc and calcium in the tissues of the earthworm Lumbricus rubellus sampled from one uncontaminated and four polluted soils

Summary The tissue distribution of Cu, Cd, Pb, Zn, and Ca in the earthworm Lumbricus rubellus living in non-polluted and heavy-metal polluted soils was investigated. Cd, Pb and Zn were primarily accumulated within the posterior alimentary canal. As the whole-worm Pb burden increased, the proportion of the metal accumulated within this tissue fraction increased. A similar pattern was found for Zn. By contrast, 70%–76% of the Cd burden was found in the posterior alimentary canal, irrespective of the whole-worm Cd content. The accumulation of Cd, Pb and Zn primarily in the posterior alimentary canal prevents dissemination of large concentrations of these metals into other earthworm tissues, and may thus represent a dextoxification strategy based on accumulative immobilisation. Cu was distributed fairly evenly in the tissue fractions investigated. There was no evidence of sequestration of this metal. The apparent lack of a detoxification strategy may contribute to the well-known susceptibility of earthworms to low environmental Cu concentrations. Indeed, earthworms from the site of highest soil Cu (Ecton) were markedly smaller than those from the other sites sampled. The highest Ca concentrations were found in the anterior alimentary canal, and were related to calciferous gland activity. A large proportion of Ca was also stored as a physiologically available pool in the posterior alimentary canal. Despite huge variations in soil Ca concentrations, the body wall Ca levels were fairly similar in L. rubellus from all the study sites. Thus, L. rubellus may become physiologically adapted to soils of exceptionally low Ca concentration. The observations are discussed in the context of the merits of analysing specific tissues, rather than whole organisms, for the purpose of monitoring metal bioaccumulation.     

Spectrophotometric study of the relative affinities of teichoic acid for different metal ions.

Spectrophotometric study of the relative affinities of teichoic acid (TA) for Na+, Ca2+, Mg2+, Cd2+, Hg2+, Cu2+ and Pb2+ described on the basis of the disruption of metachromasia of dye 1,9-dimethyl methylene blue (DMMB)-polyanion (TA) system has revealed the following sequence of relative affinities of TA for these metals: Na+ < Ca2+ < or = Mg2+ < Cd2+ < Hg2+ < Cu2+ < Pb2+. Some of the metal ions particularly Pb2+ and Hg2+ have specific interactions with the dye, and induce distinct metachromatic band of the dye even in the absence of the polyanion.     

Spectral and thermodynamic properties of Ag(I), Au(III), Cd(II), Co(II), Fe(III), Hg(II), Mn(II), Ni(II), Pb(II), U(IV), and Zn(II) binding by methanobactin from Methylosinus trichosporium OB3b

Methanobactin (mb) is a novel chromopeptide that appears to function as the extracellular component of a copper acquisition system in methanotrophic bacteria. To examine this potential physiological role, and to distinguish it from iron binding siderophores, the spectral (UV–visible absorption, circular dichroism, fluorescence, and X-ray photoelectron) and thermodynamic properties of metal binding by mb were examined. In the absence of Cu(II) or Cu(I), mb will bind Ag(I), Au(III), Co(II), Cd(II), Fe(III), Hg(II), Mn(II), Ni(II), Pb(II), U(VI), or Zn(II), but not Ba(II), Ca(II), La(II), Mg(II), and Sr(II). The results suggest metals such as Ag(I), Au(III), Hg(II), Pb(II) and possibly U(VI) are bound by a mechanism similar to Cu, whereas the coordination of Co(II), Cd(II), Fe(III), Mn(II), Ni(II) and Zn(II) by mb differs from Cu(II). Consistent with its role as a copper-binding compound or chalkophore, the binding constants of all the metals examined were less than those observed with Cu(II) and copper displaced other metals except Ag(I) and Au(III) bound to mb. However, the binding of different metals by mb suggests that methanotrophic activity also may play a role in either the solubilization or immobilization of many metals in situ.     

Comparative Evaluation of Trace Metals in the Blood of Hepatitis C Patients and Healthy Donors

Hepatitis C is one of the common types of chronic liver disease, and its plausible association with trace metal imbalance has been investigated in the present study. The blood samples of hepatitis C patients and healthy donors were analysed for trace metals (Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Pb, and Zn) by flame atomic absorption spectrophotometry after wet acid digestion. In the blood of the hepatitis patients, mean concentrations of essential metals, Na, K, Fe, Ca, Mg, and Zn, were 918.7, 361.0, 102.5, 20.00, 24.66, and 9.429 ppm, respectively, while the mean metal levels in the blood of healthy donors were 1509, 406.8, 232.5, 28.35, 24.59, and 8.799 ppm, respectively. On the average, Cr was significantly higher, while Na, Fe, Ca, Cu, Mn, Pb, and Cd were comparatively lower in the blood of the patients. The correlation study manifested significantly divergent mutual relationships of trace metals in the blood of the patients and healthy donors. Multivariate statistical methods revealed considerably diverse distribution of trace metals in the two groups. Dissimilarity in the trace metal distribution was also noted with the gender and residential location of the donors in both groups.     

Distinct metal ion binding sites on Ca(2+)-activated K+ channels in inside-out patches of human erythrocytes.

Effects of Cd2+, Co2+, Pb2+, Fe2+ and Mg2+ (1-100 microM) on single-channel properties of the intermediate conductance Ca(2+)-activated K+ (CaK) channels were investigated in inside-out patches of human erythrocytes in a physiological K+ gradient. Cd2+, Co2+ and Pb2+, but not Fe2+ and Mg2+, were able to induce CaK channel openings. The potency of the metals to open CaK channels in human erythrocytes follows the sequence Pb2+, Cd2+ > Ca2+ > or = Co2+ > Mg2+, Fe2+. At higher concentrations Pb2+, Cd2+ and Co2+ block the CaK channel by reducing the opening frequency and the single-channel current amplitude. The potency of the metals to reduce CaK channel opening frequency follows the sequence Pb2+ > Cd2+, Co2+ > Ca2+, which differs from the potency sequence Cd2+ > Pb2+, Co2+ > Ca2+ to reduce the unitary single-channel current amplitude. Fe2+ reduced the channel opening frequency and enhanced the two open times of CaK channels activated by Ca2+, whereas up to 100 microM Mg2+ had no effect on any of the measured single-channel parameters. It is concluded that the activation of CaK channels of human erythrocytes by various metal ions occurs through an interaction with the same regulatory site at which Ca2+ activates these channels. The different potency orders for the activating and blocking effects suggest the presence of at least one activation and two blocking sites. A modulatory binding site for Fe2+ exists as well. In addition, the CaK channels in human erythrocytes are distinct from other subtypes of Ca(2+)-activated K+ channels in their sensitivity to the metal ions.     

A method for controlling the activities of free metal,hydrogen, and phosphate ions in hydroponic solutions using ion exchange and chelating resins

Summary An ion exchange and chelating resin system was developed to buffer the activities of selected free cations and phosphate in hydroponic solutions at concentrations similar to those that occur naturally in soil solutions. Free-ion activities of Cd, Cu, Ni, Zn, Mn, H, Ca, Mg, and K were maintained by ion exchange and chelating resins in a controlled ionic strength system. Iron was controlled by EDDHA and chelating resin, and P by a cation-exchange resin containing adsorbed polynuclear hydroxyaluminum. This mixed-resin hydroponic system was used to establish a range of ionic Cd activities similar to that found in soil solutions of soils amended with sewage sludge. Activities of other nutrients were maintained at realistic soil-solution levels. A metal complexing agent (EDTA) was used to increase total metal concentration in the hydroponic solutions without significantly altering the ionic activities of the metals maintained in solution. This allowed differentiation of the effects of free ions and complexed metals on metal uptake. Concentrations of metal complexes in solution were controlled by the ion activities of the metals maintained and the concentrations and selectivities of the complexing agent. The mixed-resin system supplied sufficient nutrients for the growth of tomato plants (Lycopersicon esculentum, cv. Wisconsin-55) in hydroponic culture. Research supported by the College of Agricultural and Life Sciences, University of Wisonsin-Madison and by United States Environmental Protection Agency through Grant CR807270010.     

Effects of atmospheric deposition,soil pH and acidification on heavy metal contents in soils and vegetation of semi-natural ecosystems at Rothamsted Experimental Station,UK

The effects of acidification on the soil chemistry and plant availability of the metals Pb, Cd, Zn, Cu, Mn and Ni in new and archived soil and plant samples taken from the >100-year-old experiments on natural woodland regeneration (Geescroft and Broadbalk Wildernesses) and a hay meadow (Park Grass) at Rothamsted Experimental Station are examined. We measured a significant input of metals from atmospheric deposition, enhanced under woodland by 33% (Ni) to 259% (Zn); Pb deposition was greatly influenced by vehicle emissions and the introduction of Pb in petrol. The build up of metals by long-term deposition was influenced by acidification, mobilization and leaching, but leaching, generally, only occurred in soils at pH<4. Mn and Cd were most sensitive to soil acidity with effective mobilization occurring at pH 6.0–5.5 (0.01 M CaCl₂), followed by Zn, Ni and Cu at pH 5.5–5.0. Pb was not mobilized until pH<4.5. Acidification to pH 4 mobilized 60–90% of total soil Cd but this was adsorbed onto ion exchange surfaces and/or complexed with soil organic matter. This buffering effect of ion exchange surfaces and organic matter in soils down to pH 4 was generally reflected by all the metals investigated. For grassland the maximum accumulation of metals in herbage generally corresponded to a soil pH of 4.0. For woodland the concentration of Pb, Mn and Cd in oak saplings (Quercus robur) was 3-, 4- and 6-fold larger at pH 4 than at pH 7. Mature Oak trees contained 10 times more Mn, 4 times more Ni and 3 times more Cd in their leaves at pH 4 than at pH 7. At pH values <4.0 on grassland the metal content in herbage declined. Only for Mn and Zn did this reflect a decline in the plant available soil content attributed to long-term acid weathering and leaching. The chief cause was a long-term decline in plant species richness and the increased dominance of two acid-tolerant, metal-excluder species     

Influence of Ca/mg ratio on phytoextraction properties of Salix viminalis I. The effectiveness of Cd, Cu, Pb, and Zn bioaccumulation and plant growth

Phytoremediation and its efficiency--influenced by several factors-is prime concern in reduction of environment contamination with heavy metals. The aim of the study was to estimate in controlled conditions--in relation to the natural Ca/Mg ratio 4:1--the influence of different Ca/Mg ratios (1:1/4, 20:1, 1:10) on selected heavy metals (Cd, Cu, Pb, and Zn) accumulation efficiency shown by three morphological parts of Salix viminalis 'Cinamomea' (cane bark, shoots and roots). Accumulation of heavy metals in experimental conditions was significantly Ca/Mg ratio dependent, and occurred in the following order: 1:10 > 4:1 > 20:1 > 1:1/4. The highest accumulation under 0.5 mM solutions (as compared to 0.1 mM) was noted for copper and zinc, and the lowest for cadmium. Biometric parameters of Salix viminalis cuttings revealed the highest biomass productivity under 20:1 and 4:1 Ca/Mg ratios. In the case of shoot length increase, both metal concentration and kind of metal present in the solution were important. The results indicate that higher calcium ion concentration in solution (Ca/Mg 20:1) stimulates Salix viminalis growth by 3 fold when compared to other Ca/Mg ratio. It can be an important factor in remediation of the environment with this plant.     

Biosorption of lead(II), cadmium(II), copper(II) and nickel(II) by anaerobic granular biomass

Biosorption is potentially an attractive technology for treatment of wastewater for retaining heavy metals from dilute solutions. This study investigated the feasibility of anaerobic granules as a novel type of biosorbent, for lead, copper, cadmium, and nickel removal from aqueous solutions. Anaerobic sludge supplied from a wastewater treatment plant in the province of Quebec was used. Anaerobic granules are microbial aggregates with a strong, compact and porous structure and excellent settling ability. After treatment of the biomass with Ca ions, the cation exchange capacity of the biomass was approximately 111 meq/100 g of biomass dry weight which is comparable to the metal binding capacities of commercial ion exchange resins. This work investigated the equilibrium, batch dynamics for the biosorption process. Binding capacity experiments using viable biomass revealed a higher value than those for nonviable biomass. Binding capacity experiments using non-viable biomass treated with Ca revealed a high value of metals uptake. The solution initial pH value affected metal sorption. Over the pH range of 4.0-5.5, pH-related effects were not significant. Meanwhile, at lower pH values the uptake capacity decreased. Time dependency experiments for the metal ions uptake showed that adsorption equilibrium was reached almost 30 min after metal addition. It was found that the q(max) for Pb2+, Cd2+, Cu2+, and Ni2+ ions, were 255, 60, 55, and 26 mg/g respectively (1.23, 0.53, 0.87, and 0.44 mmol/g respectively). The data pertaining to the sorption dependence upon metal ion concentration could be fitted to a Langmiur isotherm model. Based on the results, the anaerobic granules treated with Ca appear to be a promising biosorbent for removal of heavy metals from wastewater due to its optimal uptake of heavy metals, its particulate shape, compact porous structure, excellent settling ability, and its high mechanical strength.     

Ion exchange during heavy metal bio-sorption from aqueous solution by dried biomass of macrophytes

In this study, potentials of oven dried biomass of Eichhornia crassipes, Valisneria spiralis and Pistia stratiotes, were examined in terms of their heavy metal (Cd, Ni, Zn, Cu, Cr and Pb) sorption capacity, from individual-metal and multi-metal aqueous solutions at pH 6.0+/-0.1 (a popular pH of industrial effluent). V. spiralis was the most and E. crassipes was the least efficient for removal of all the metals. Cd, Pb and Zn were efficiently removed by all the three biomass. Cd was removed up to 98% by V. spiralis. Sorption data for Cr, Ni and Cd fitted better to Langmuir isotherm equation, while, the sorption data for Pb, Zn and Cu fitted better to Freundlich isotherm equation. In general, the presence of other metal ions did not influence significantly the targeted metal sorption capacity of the test plant biomasses. Ion exchange was proven the main mechanism involved in bio-sorption and there was a strong ionic balance between adsorbed (H(+) and M(2+)) to the released ions (Na(+) and K(+)) to and from the biomass. No significant difference was observed in the metal exchanged amount, by doubling of metal concentration (15-30 mg/l) in the solution and employing individual-metal and multi-metal solutions.     

Use of the green alga Ulva rigida C. Agardh as an indicator species to reassess metal pollution in the Thermaikos Gulf, Greece, after 13 years

The concentrations of metals (Mn, Pb, Fe, Zn, Cu, Cd,Co, Ni, Cr, Na, K, Ca, Mg) were determined in thegreen alga Ulva rigida, in the sediment andseawater of Thermaikos Gulf (Greece) during monthlysamplings in 1994–1995. This Gulf is the recipientof domestic and industrial effluents. Pb, Fe, Cu, Coand Cr concentrations in U. rigida at the studyarea were higher than those 13 years earlier andapparently came from different sources than those forZn, Cd and Ni. The relative abundance of metals inthe alga decreased in the order: Mg > Na > K >Ca > Pb > Fe > Mn > Zn > Cr, Cu > Ni >Co > Cd. Only Cu concentrations in the alga fromKalochori and Cd ones from Viamyl showed significantseasonal changes. Cu and Cd concentrations ingeneral followed the same pattern of variation, withminimum values in winter-spring. This pattern isdiscussed in relation to growth dynamics and tissueage. Only Pb concentrations in the alga showed asignificant positive correlation with concentrationsin the seawater. There were both positive andnegative correlations among some metals in the alga. It is concluded that U. rigida can be used as anindicator species, especially for Pb.     

Comparative Assessment of Selected Metals in the Scalp Hair and Nails of Lung Cancer Patients and Controls

Lung cancer is seriously threatening human health and exposure to trace metals is the most important aetiology for lung cancer. Selected essential/toxic metals (Ca, Mg, Na, K, Fe, Zn, Cu, Sr, Li, Co, Mn, Ni, Cr, Cd and Pb) are measured in the scalp hair and nails of lung cancer patients and controls by atomic absorption spectrophotometric method employing nitric acid-perchloric acid-based wet digestion. Average concentrations of Pb, Cd, Mn, Co and Cu are found to be significantly higher (p?<?0.05) in the scalp hair and nails of lung cancer patients compared with the controls, however, appreciably higher concentrations of Zn, Ca, Na, Mg and Cr are noted in the scalp hair of the controls. Most of the metal levels reveal higher dispersion and asymmetry in the scalp hair/nails of the patients compared with the controls. Average metal levels are also compared to investigate probable differences based on sex, abode, food and smoking habits. The correlation study shows significantly diverse mutual variations of the metals in the scalp hair and nails of the patients and controls. Considerable variations in the metal levels are also noted for various stages and types of lung cancer (adenocarcinoma, squamous cell carcinoma, large cell carcinoma and small cell lung cancer). Multivariate apportionment of the metals in the scalp hair and nails of the patients and controls are also significantly diverse. The study reveals considerably divergent variations in the metal levels in lung cancer patients in comparison with healthy subjects.     

Spectral and thermodynamic properties of Ag(I), Au(III), Cd(II), Co(II), Fe(III), Hg(II), Mn(II), Ni(II), Pb(II), U(IV), and Zn(II) binding by methanobactin from Methylosinus trichosporium OB3b

Methanobactin (mb) is a novel chromopeptide that appears to function as the extracellular component of a copper acquisition system in methanotrophic bacteria. To examine this potential physiological role, and to distinguish it from iron binding siderophores, the spectral (UV–visible absorption, circular dichroism, fluorescence, and X-ray photoelectron) and thermodynamic properties of metal binding by mb were examined. In the absence of Cu(II) or Cu(I), mb will bind Ag(I), Au(III), Co(II), Cd(II), Fe(III), Hg(II), Mn(II), Ni(II), Pb(II), U(VI), or Zn(II), but not Ba(II), Ca(II), La(II), Mg(II), and Sr(II). The results suggest metals such as Ag(I), Au(III), Hg(II), Pb(II) and possibly U(VI) are bound by a mechanism similar to Cu, whereas the coordination of Co(II), Cd(II), Fe(III), Mn(II), Ni(II) and Zn(II) by mb differs from Cu(II). Consistent with its role as a copper-binding compound or chalkophore, the binding constants of all the metals examined were less than those observed with Cu(II) and copper displaced other metals except Ag(I) and Au(III) bound to mb. However, the binding of different metals by mb suggests that methanotrophic activity also may play a role in either the solubilization or immobilization of many metals in situ.