Cumulative Title Index

Abstract

Metal fractionation is a powerful tool for studying the mobility, bioavailability and toxicity of metals in sediments and soils. A seven-step sequential extraction technique was used to determine the potential mobility of selected heavy metals (Fe, Mn, Zn, Cu, Pb, Cd and Ni) in the sediments of Lake Naivasha. Results indicate that residual fraction was the most important phase for the elements Fe, Mn, Cu and Zn. However, Pb and Cd are highly enriched in the non-residual phases. Nickel on the other hand was distributed evenly between the non-residual and the residual fractions.

The total concentrations of the heavy metals suggested a decreasing order of iron ?> manganese ? zinc > nickel > copper ? lead > cadmium. However, the detailed sequential extraction data indicated an order of release or mobility of cadmium > lead ? nickel ? zinc > manganese > copper > iron. The high percentage of Cd and Pb in the mobile fractions suggests high bioavailability of these two elements in the study area and maybe a pointer to anthropogenic input of the two elements in the study area.     

Aspects of trace element interactions during development

The origins of nutritional trace element deficiencies are summarized. Inadequate intake results in primary deficiency, whereas secondary or conditioned deficiencies can arise in several ways including trace element interactions. Evidence is presented and discussed for interactions of essential trace elements during prenatal and early postnatal development. Diets of widely different zinc and copper concentrations and ratios were fed to pregnant rats. Analysis of fetal outcome and copper and zinc concentrations of maternal and fetal livers showed that although there is an interaction between these metals it occurs only at levels of dietary copper deficiency. Iron and manganese interact so that high levels of one depress absorption of the other. Mice fed iron-supplemented diets had liver manganese concentrations lower than those of unsupplemented mice. Iron supplements at high but not low levels also depressed absorption of zinc. Conversely, zinc deficiency in pregnant rats caused higher than normal concentrations of iron in maternal and fetal liver. Trace element analyses of proprietary infant formulas indicate that in some, concentrations and ratios of these trace elements may be incorrect. The effects of essential trace element interactions during development should be further investigated. Caution is urged in considering levels of trace element supplements during pregnancy, lactation, or early childhood.     

Interaction of Lead with Calcium,Iron, and Zinc in the Biological Samples of Malnourished Children

There have been few investigations of trace elements in the urine and hair of populations exposed to high levels of arsenic (As) in drinking water. Therefore, concentrations of selected metals in urine and hair samples from a population in a study area where arsenism was endemic and a control area were determined. It was found that the median concentrations of barium (Ba), cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), manganese (Mn), molybdenum (Mo), nickel (Ni), lead (Pb), zinc (Zn), and As in the urine samples from the population in the study area were 3.87, 0.47, 0.50, 61.84, 26.82, 1.33, 128.45, 7.05, 1.10, 233.75, and 339.63 μg/L, respectively. The corresponding values in the urine samples from a population in the control area were 29.08, 0.19, 0.21, 27.77, 10.32, 4.61, 14.01, 2.19, 3.90, 113.92, and 20.28 μg/L, respectively. In the study area, Ba, Cd, Co, Cr, Cu, Mo, Ni, Pb, and Zn excreted in the urine were likely to be mainly derived from drinking water with high levels of arsenic. The median concentrations of Ba, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, Zn, and As in the hair samples from the study area were 4.16, 0.03, 0.09, 1.09, 6.54, 1.97, 0.06, 0.53, 1.64, 144.28, and 1.67 mg/kg, respectively. The corresponding values from the control area were 4.76, 0.03, 0.02, 1.41, 8.31, 1.34, 0.07, 0.39, 0.86, 154.58, and 0.29 mg/kg, respectively. Significant positive correlations were observed between As and Ba, Cd, Co, Cr, Cu, Mo, Ni, Pb, and Zn in the urine in the study area. However, As was not positively associated with these metals in the hair samples. Exposure to high levels of As in drinking water increased the accumulation of Ba and Mn in the hair and the excretion of Cd, Cu, and Mo in the urine in the study area. The population in the study area might experience Cu and Mo deficiencies for an increasing excretion of Cu and Mo.     

Effect of lead in water on the absorption of copper, iron, manganese and zinc by sheep (Ovis aries) infected with sheep tapeworm (Moniezia expansa)

The sheep tapeworm (Moniezia expansa) and its host Ovis aries were analyzed by inductively coupled plasma optical emission spectrometry (ICP-OES) for their copper, iron, manganese, zinc and lead levels. Element concentrations in cestode parasites were compared to those in various organs (liver, kidney, and muscle) of sheep. Tapeworms in the small intestine of sheep that were administered 2g of Pb(CH(3)COO)(2) per os daily (7 days) had significantly higher lead concentrations than sheep tissues. Cu levels significantly increased after Pb administration in sheep muscle and sheep tapeworms. Contrarily, Zn content significantly decreased in sheep muscle, but significantly increased in sheep tapeworms. However, Mn content significantly decreased after Pb administration in sheep tapeworms. Furthermore, Fe content significantly decreased after Pb administration in sheep liver and kidneys.     

Trace Elements in Fruit Juices

Fruit juices are widely consumed in tropical countries as part of habitual diet. The concentrations of several minerals in these beverages were evaluated. Four commercially available brands of juices were analyzed for cadmium, lead, copper, zinc, aluminum, iron, chromium, manganese, and molybdenum. The levels ranged from 0.02 to 0.08 mg/L for copper, from 0.05 to 0.23 mg/L for zinc, from 0.1 to 0.4 mg/L for aluminum, from 0.02 to 0.45 mg/L for iron, and from 0.01 to 0.22 mg/L for manganese. The levels of cadmium, lead, and chromium in all samples were very low or undetectable. The metal contents of fruit juices depend on a number of factors, including the soil composition, the external conditions during fruit growing and fruit harvesting, as well as on details of the fruit juice manufacturing processes employed. The concentrations of none of the metals in juice samples analyzed exceeded the limits imposed by local legislation.     

Concentration of selected elements in the roots and crowns of both primary and permanent teeth with caries disease

We examined the differences between the concentrations of chemical elements in caries-changed primary teeth and permanent ones with a division into the root and the crown. The study comprised 27 children aged from 4 to 11 yr and 36 adults aged from 36 to 71 yr. We examined the elements with the total reflection X-ray fluorescence method. The lowest concentrations of calcium, manganese, strontium, lead, and copper were in the roots of primary teeth compared to the roots of permanent ones. The calcium, nickel, zinc, lead, and copper concentrations were significantly higher in the roots of primary teeth than in the roots of permanent teeth. However, the zinc concentration was higher both in the root and crown of primary teeth than in permanent teeth. On the basis of our investigations, we can conclude that the content of some elements (manganese, copper, strontium, and lead) is higher in caries permanent teeth than in primary ones. The nickel and zinc concentrations are higher in the teeth of the children than the adults. However, the content of other elements (calcium, chromium, iron) is similar in both kinds of teeth.     

Detection and Analysis of 12 Heavy Metals in Blood and Hair Sample from a General Population of Pearl River Delta Area

To detect the content of 12 heavy metals in blood and hair sample from a general population of Pearl River Delta area, and to analyze the influence of duration of residence, gender, age, smoking and drinking on the heavy metal content. Use inductively coupled plasma mass spectrometry to detect the content of 12 heavy metals lead (Pb), mercury (Hg), cadmium (Cd), aluminum (Al), arsenic (As), copper (Cu), chrome (Cr), manganese (Mn), nickel (Ni), zinc (Zn), tin (Sn) and antimony (Sb) in blood and hair samples of a total of 50 subjects from a general population, collected by multistage stratified cluster random sampling method. The geometric mean of heavy metal content in blood samples of general population (μg/L): blood aluminum 214.00; blood chrome 92.82; blood manganese 21.43; blood nickel 20.59; blood copper 0.67; blood zinc 11.50; blood arsenic 0.55; blood cadmium 2.45; blood tin 0.00; blood antimony 1.92; blood lead 158.84; and blood mercury 1.19. The geometric mean of heavy metal content in hair samples of general population (μg/g): hair aluminum is 84.65; hair chrome 0.00; hair manganese 2.44; hair nickel 0.61; hair copper 28.49; hair zinc 136.65; hair arsenic 0.75; hair cadmium 0.46; hair tin 1.04; hair antimony 0.05; hair lead 8.97; and hair mercury 0.69. Some heavy metals were correlated with duration of residence, gender, age, smoking and drinking. This was the first time that simultaneously detecting heavy metal content in blood and hair was used to analyze the internal heavy metal burden in resident population of Pearl River Delta area. These data can serve as reference for further research.     

Heavy metals in some Chinese herbal plants

The concentrations of nine heavy metals, cadmium, cobalt, copper, iron, manganese, nickel, lead, zinc and mercury in 42 Chinese herbal medicinal plants were determined. Generally, all the samples studied had, relative to the other trace metals, higher concentrations of iron, manganese, and zinc. The concentration range of the metals determined was comparable to that in many of the East Asian vegetables and fruits. A few samples were found to contain relatively higher concentrations of the toxic metals such as cadmium, lead, and mercury. This was probably caused by contamination during air-drying and preservation.     

Spatial distribution of heavy metals in sediments from the Gulf of Paria, Trinidad

The Gulf of Paria receives heavy metal input from urban runoff, industrial and agricultural activity, sewage and domestic wastes: both from the west coast and from inland areas of Trinidad. Non-residual concentrations of nine metals, as well as total mercury concentrations, were used to determine spatial distributions of heavy metals in sediments in the Gulf of Paria. Surficial sediment samples were collected at 37 stations, which included the mouths of 11 major rivers that flow into the Gulf of Paria. Stations were sampled twice during the wet season (July 1998 and November/ December 1998) and twice during the dry season (March 1999 and April 1999). Sediments were analyzed for aluminium (Al), cadmium (Cd), chromium (Cr), copper (Cu), iron (Fe), lead (Pb), manganese (Mn), nickel (Ni), zinc (Zn) and mercury (Hg). Total Organic Carbon (TOC) and grain size analyses were also performed on the sediments. Principal component analysis showed that sediments from river mouths subject to greatest land use and anthropogenic input, were distinct from other sediments in the Gulf of Paria. This was due to higher Pb, Zn, Cu and Hg concentrations (3.53-73.30 microg g(-1), 45.8-313.9 microg g(-1), 8.43-39.71 microg g(-1) and 0.03-0.10 microg g(-1), respectively). Sediments further from the coast were also distinct due to their higher Al, Fe, Cr and Mn concentrations (1.37-3.16 mg g(-1), 9.51-18.91 mg g(-1) , 17.22-28.41 microg g(-1) and 323.6-1,564.2 microg g(-1), respectively). Cd and Pb were higher in the wet season while Ni was higher in the dry season. Pb, Zn, Cu and Hg were correlated with each other and with TOC. Correlation was also observed between Al, Fe, Cr, Mn and Ni. Al, Fe, Cr and Mn were correlated with percentage clay in sediments. The results suggest that Pb, Zn, Cu and Hg are preferentially removed by organic matter, which settles at the river-mouths, while Al, Fe, Cr, Mn, and Ni become associated with clay minerals and are transported away from the coast.     

The effects of age and sex on seven elements of Sprague-Dawley rat organs

This study reports age-related changes in 7 element (iron, copper, zinc, manganese, mercury, cadmium and lead) concentrations in the liver, kidney and brain of male and female Sprague-Dawley rats from 1 to 364 days of age. Atomic absorption spectrometry was used for the measurements. Copper, mercury and cadmium in the male and female kidneys increased from weaning until 127 days of age, as did iron concentrations in the female liver and kidney. After 127 days, especially, the copper concentration in the female kidney and cadmium concentration in the male and female kidney increased further. Consistent and statistically significant (P less than 0.05) sex differences in element concentrations were found for three elements (iron, copper and zinc). Except for the zinc concentration in the liver from 50 to 72 days, iron (in liver and kidney), zinc (in kidney) and copper (in liver, kidney and brain) concentrations in female rats during the adult stage, were all higher than those of male rats. Isolated differences for other elements (manganese, mercury and cadmium) were also found. The data will be helpful when setting up long-term animal investigations of the biological effect of elements.     

Assessment of trace elements in human brain using inductively coupled plasma mass spectrometry

Recent brain research reveals a major role of trace elements in various diseases such as multiple sclerosis, Alzheimer's and Wilson's disease. The majority of published tissue concentrations dates back decades, and was assessed with various methods. Little is known about hemispherical differences, the correlation of trace elements or age-dependent changes in the human brain. Thus, the aim of this study was to examine trace element concentrations in different human brain regions after whole brain formalin fixation.549 samples of 13 brain regions were investigated in 11 deceased subjects without known history of brain pathology. Regional wet-to-dry mass ratios and concentrations of iron, copper, magnesium, manganese, calcium and zinc were determined using inductively coupled plasma mass spectrometry.Cortical gray matter revealed higher water content (wet-to-dry mass ratios 5.84–6.40) than white matter regions (wet-to-dry mass ratios 2.95–3.05). Element concentrations displayed specific regional differences. Good linear correlation of concentrations between elements was found for iron/copper as well as for manganese/magnesium (Spearman's rank correlation coefficient 0.74 and 0.65, respectively). Significant inter-hemispherical differences were found for copper in occipital white matter, for magnesium and calcium in putamen and for iron and copper in temporal white matter. An age dependent increase was seen in cortical gray matter for calcium, for magnesium in all regions except in cortical gray matter, for copper in substantia nigra and for zinc in occipital cortex.The presented trace element concentrations can serve as a fundamental basis for further brain research. Wet-to-dry mass ratios allow a comparison with reference data from other studies.     

Variability of selected trace elements of different meat cuts determined by ICP-MS and DRC-ICPMS

The aim of this study was to determine the levels of cadmium, lead, iron, zinc, selenium, manganese, copper and molybdenum in different cuts of beef, pork, lamb, chicken and foal collected from supermarkets and butcheries in Switzerland. The concentrations of manganese, copper, molybdenum, zinc, iron, selenium, cadmium and lead were determined by inductively coupled plasma mass spectrometry (ICP-MS) after microwave digestion. Mean values and their respective coefficients of variation were calculated from the measured concentrations. The concentrations found for cadmium and lead ranged from 0.6 to 3.9 μg/100 g and 1.0 to 2.1 μg/100 g, respectively. Concentrations ranged between 0.5 and 3.3 mg/100 g for iron, 0.7 and 5.1 mg/100 g for zinc, 9 and 44 μg/100 g for selenium, 3.1 and 16.7 μg/100 g for manganese, 0.3 and 132 μg/100 g for copper and 0.9 and 3.2 μg/100 g for molybdenum. Differences found for the concentrations in meat from different species as well as between the individual meat cuts were notable for iron, zinc, selenium and copper. Manganese concentrations were found to vary unsystematically within muscles and species. Molybdenum concentrations were higher in chicken meat in comparison with the mammalian meats. The highest coefficients of variation were found for manganese (13% to 142%) and copper (13% to 224%), while the lowest was found for zinc (4% to 45%). In conclusion, in order to provide an accurate overview and to be able to calculate reliable dietary intakes, it is important to include the variability in food composition data.     

Contents of metals in some wild mushrooms

The concentrations of 7 metals (lead, cadmium, manganese, copper, nickel, silver, and chromium) were determined in 32 different species of wild mushrooms. The mushroom samples, which have been using for food and some medical purposes, were collected from Konya, an Inner Anatolian region of Turkey. The highest metal concentrations were determined as 39 mg/kg Pb and 3.72 mg/kg Cd in Trichaptum abietinum, 467 mg/kg Mn in Panaeolus sphinctrinus, 326 mg/kg Cu in Trametes versicolor, 69.4 mg/kg Ni in Helvella spadicea, 6.97 mg/kg Ag in Agaricus campestris, and 84.5 mg/kg Cr in Phellinus igniarius. The maximum contents are 1.52, 2.22, and 60.2 mg/kg in Pleurotus eryngii (for Pb), Amanita vaginata (for Cd), and Helvella leucomelana (for Cu), respectively. These results were compared according to the WHO/FAO standard.     

Identifying Metals Contamination in Soil: A Geochemical Approach

The geochemical evaluation methodology described in this paper is used to distinguish contaminated samples from those that contain only naturally occurring levels of inorganic constituents. Site-to-background comparisons of trace elements in soil based solely on statistical techniques are prone to high false positive indications. Trace element distributions in soil tend to span a wide range of concentrations and are highly right-skewed, approximating lognormal distributions, and background data sets are typically too small to capture this range. Geochemical correlations of trace versus major elements are predicated on the natural elemental associations in soil. Linear trends with positive slopes are expected for scatter plots of specific trace versus major elements in uncontaminated samples. Individual samples that may contain a component of contamination are identified by their positions off the trend formed by uncontaminated samples. In addition to pinpointing which samples may be contaminated, this technique provides mechanistic explanations for naturally elevated element concentrations, information that a purely statistical approach cannot provide. These geochemical evaluations have been successfully performed at numerous facilities across the United States. Removing naturally occurring constituents from consideration early in a site investigation reduces or eliminates unnecessary investigation and risk assessment, and focuses remediation efforts.     

The role of trace elements on hepatitis virus infections: a review

The significance of the nutritional roles of trace metals (includes some heavy metals) is widely recognized, since these elements are as constituent components of many metal proteins and metalloenzymes serum trace metals levels, and their ratios are frequently reported to be good marker for diagnosing various diseases. Trace metals play an important role in liver disease particularly liver degeneration. Influence of trace elements has been studied in a large number of viruses belonging to different groups. This review reported the role of some trace elements iron (Fe), copper (Cu), cobalt (Co), manganese (Mn) and zinc (Zn) as well as toxic elements Pb on hepatitis virus infections.     

Heavy metal distribution in superficial sedimenta ta Saco, Gulf of Cariaco, Sucre, Venezuela

The Gulf of Cariaco is a marine ecosystem with high primary productivity, which gives it an ecological and socioeconomic importance. Nevertheless, anthropogenic activities around the Gulf produce wastes that are deposited directly or by runoff into the sediments, and consequently, increases concentrations of metals in this ecosystem. The objective of this study was to determine the distribution of cadmium, copper, lead, manganese, nickel and zinc in geochemical fractions of surface sediments, using modified BCR sequential extraction procedure. The concentrations were measured using flame atomic absorption spectroscopy. In addition, the contents of soluble and exchangeable metals associated to carbonate fractions, determined by BCR, were compared with those determined by the method of Campanella. Samples were collected in 12 stations during June 2007. The applied methodologies were evaluated with a certified reference material of marine sediments (HISS-1) and the results indicated that these methods provide adequate accuracy and precision for the extraction of metals. The total metal concentrations (microg g(-1)) were, Cd: < limit of detection (LD)-5.0; Pb: 1.79-60.41; Cu: no detected (ND)-42.18; Zn: 25.13-104.57; Mn: 66.31-80.29 and Ni: 3.29-24.58. Cd, Cu, Ni and Pb at several stations, exceeded the Canadian Sediment Quality Guidelines of the Lowest Effect Levels (LEL). Cadmium was identified as being the most mobile of the elements, having the highest concentrations in soluble and exchangeable cations and carbonates. However, Pb, Cu, Mn and Zn levels were found highly associated to organic matter and sulfide fractions. The methods did not show significant statistical differences for the extraction of soluble and exchangeable cations and the metals associated to carbonate fraction. There are several significant correlations between heavy metals, which suggest their common origin.     

Trace Elements in the Hair of Hemodialysis Patients

Trace element disturbance is often observed in hemodialysis patients. While trace element concentrations have been reported in blood samples from hemodialysis patients, they have not been well investigated in scalp hair. In the present study, 22 trace elemental concentrations were measured by inductively coupled plasma-atomic emission spectrometry in the scalp hair of 80 male hemodialysis patients and compared with those of 100 healthy male subjects. In hemodialysis patients, the concentrations of beryllium, arsenic, magnesium, chromium, manganese, iron, selenium, molybdenum, iodine, vanadium, and cobalt were significantly higher than those in healthy subjects, while lead, mercury, copper, germanium, and bromine were significantly lower than those in the former group. No significant differences were observed for lithium, aluminum, cadmium, zinc, boron, or nickel. There were significant positive correlations between the duration of hemodialysis and the magnesium and manganese concentrations. There was a significant negative correlation between cadmium concentration and the duration of hemodialysis. There were significant positive correlations between dialysis efficacy (Kt/V) and magnesium, manganese, zinc, and selenium concentrations. In conclusion, trace element concentrations of the scalp hair are different between hemodialysis patients and healthy subjects. Essential trace elements, such as magnesium, manganese, zinc, and selenium, may be affected by the duration of hemodialysis and Kt/V.     

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.     

Trace metal concentrations in the tropical sponge Spheciospongia vagabunda at a sewage outfall: synchrotron X-ray imaging reveals the micron-scale distribution of accumulated metals

Major and trace elements were measured in sponges, seawater and sediment in Darwin Harbour (Australia) to test the hypothesis that metals are elevated in sponges closer to a sewage outfall compared with unimpacted sites. Seawater and sediment at the sewage discharge site contained high, but localised, concentrations of phosphorus (P), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), arsenic (As) and lead (Pb) compared with background sites. Metal concentrations in the sponge Spheciospongia vagabunda were highly elevated compared with other sponges and, although site specific, high metal concentrations were unrelated to the presence of sewage effluent. X-ray fluorescence microprobe imaging was used to investigate the metal distribution pattern in S. vagabunda. High Fe, Ni and Zn concentrations were either localised in circular patches (100–200 μm size) near water canals or in the pinacoderm, or scattered in spots (approximately 10 μm) throughout the tissue. This supports a microflora-mediated metal bioaccumulation hypothesis. In contrast, Co and Mn were highly dispersed and probably associated with aluminium- and iron-oxide rich sediment inclusions. Although the lack of association between sewage effluent and metal accumulation precludes the use of S. vagabunda as a biomonitor, the apparent differential mechanisms of metal accumulation warrants further investigation.     

Baseline Levels of Potentially Toxic Elements in Pampas Soils

The soils of the Pampas are thought to be generally non-contaminated but there is growing evidence of trace element accumulation at some specific sites. The goal of this study was to measure the current levels of the main Potentially Toxic Elements (PTE) in the top horizon and in specific soil profiles so that we would establish the baseline concentrations of these elements. Eighty-eight top soils and three soil profiles were sampled. The samples were acid digested. Arsenic, boron, barium, cadmium, cobalt, chromium, copper, lead, manganese, mercury, molybdenum, nickel, silver, selenium and zinc were determined with inductively coupled argon plasma emission spectrometry (ICPES).

All of the values found are within the normal range for uncontaminated soils as reported from several continents. Elements with high environmental risk potential are lower than the admissible range of the European Union and some of them are orders of magnitude lower than those of the United States Environmental Protection Agency (US-EPA) 501 levels. Potentially Toxic Elements contents increased with depth or showed a maximum concentration at the B2 horizon. This is related to the parent material and the pedogenetic processes but not to recent contamination. Soil profiles showed higher concentrations of PTE in clayey horizons. However, these relationships did not appear in top soil samples in any soil Great Group studied. The shown data establishes a baseline for PTE concentrations for Pampas soils.