Trace element concentrations in skin of free-ranging bottlenose dolphins (Tursiops truncatus) from the southeast Atlantic coast

Concentrations of trace elements (Al, As, Ba, Be, Cd, Co, Cr, Cu, Fe, Li, Mn, Ni, Pb, Sb, Se, Sn, Tl, U, V, Zn) and total mercury (THg) were determined in skin samples collected from free-ranging bottlenose dolphin (Tursiops truncatus) populations. Dolphins were captured in the estuarine waters of Charleston (CHS), South Carolina (n=74) and the Indian River Lagoon (IRL), Florida (n=75) during 2003, 2004 and 2005. A subset of the skin tissue samples were used to determine methylmercury (MeHg) levels in CHS (n=17) and IRL (n=8) bottlenose dolphins. Distributions of trace element concentrations by age (adult vs. juvenile), gender (male vs. female) and study area (CHS vs. IRL) were examined. In general, higher elemental skin concentrations were found in CHS adult males than those of IRL adult males, except for THg and MeHg. For CHS dolphins, adult females showed significantly higher THg levels than juvenile females while higher Mn levels were found in juvenile females. For IRL dolphins, adult males showed significantly higher As concentrations than that in juvenile males and females while higher Co and V levels were found in juvenile males than adult males. Of all elements measured in this study, significantly higher levels of Fe, Se and Zn concentrations in skin tissue of both dolphin populations were similar to other studies reported previously. Percentage of MeHg/THg in skin tissue of CHS and IRL dolphin was about 72% and 73%, respectively. Dietary levels of trace elements may play an important role in contributing to concentration differences for As, Co, Mn, Sb, Se, THg and Tl between CHS and IRL dolphins. Total Hg concentrations were significantly correlated with the age of CHS dolphins, while an inverse relationship was detected for Cu, Mn, Pb, U and Zn. The only significant correlation found between trace element concentration and IRL dolphins' age was Mn. Geographic differences in several trace element concentrations (As, Co, Mn, Sb, Se, THg and Tl) in skin tissue may be potentially useful to discriminate between dolphin populations and is a possibility that warrants further investigation.     

Heavy metals in soft tissues of Tursiops truncatus and Delphinus delphis from west Atlantic Ocean by X-ray spectrometry

In this work, the concentration of heavy metals in muscle, liver, fat tissue and skin is studied in 15 Delphinus delphis and two Tursiops truncatus dolphins, stranded along the Portuguese coast of the Atlantic Ocean. Sample collection was performed post-mortem and the tissues were kept frozen until analysed. Sample preparation included lyophilising and grounding in a Teflon mill to avoid contamination by metals. The obtained powder was prepared as pellets for each sample and analysed directly by X-ray fluorescence spectrometry. The concentrations of K, Ca, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Br, Rb, Sr, Hg and Pb were obtained. Significant differences between the muscle, the skin and the fat tissues were detected. Cobalt concentrations were similar in liver, skin and muscle. The levels of Ni, Rb and Sr are at the level of the detection limit and whenever measurable are rather constant in all the analysed tissues. The results show that the highest concentrations of Mn, Cu and Hg are always in liver tissues. Zinc and Se concentrations are higher in skin and Pb is present in very low concentrations in all the analysed tissues except in skin; Fe and As are enhanced in muscle and liver. In general, the two studied species did not seem to differ significantly in their heavy metals concentration in a given tissue.     

Metals contained and leached from rubber granulates used in synthetic turf areas

The aim of this study was to quantify metals contained in and leached from different types of rubber granulates used in synthetic turf areas. To investigate the total content of metals, ca 0.5 g of material was added with HNO₃, HF and HClO₄ and microwave digested with power increasing from 250 W to 600 W. Leachates were prepared by extraction of about 5.0 g of material at room temperature for 24 h in an acidic environment (pH 5). Leaching with deionized water was also performed for comparison. Aluminium, As, Ba, Be, Cd, Co, Cr, Cu, Hg, Fe, Li, Mg, Mn, Mo, Ni, Pb, Rb, Sb, Se, Sn, Sr, Tl, V, W and Zn were quantified by high-resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) and ICP optical emission spectrometry (ICP-OES).Results indicated that the developed method was accurate and precise for the multi-element characterization of rubber granulates and leachates. The total amount and the amount leached during the acidic test varied from metal to metal and from granulate to granulate. The highest median values were found for Zn (10,229 mg/kg), Al (755 mg/kg), Mg (456 mg/kg), Fe (305 mg/kg), followed by Pb, Ba, Co, Cu and Sr. The other elements were present at few units of mg/kg. The highest leaching was observed for Zn (2300 μg/l) and Mg (2500 μg/l), followed by Fe, Sr, Al, Mn and Ba. Little As, Cd, Co, Cr, Cu, Li, Mo, Ni, Pb, Rb, Sb and V leached, and Be, Hg, Se, Sn, Tl and W were below quantification limits. Data obtained were compared with the maximum tolerable amounts reported for similar materials, and only the concentration of Zn (total and leached) exceeded the expected values.     

Trace elements, PCBs and organochlorine pesticides in New Zealand common dolphins (Delphinus sp.)

Trace elements, polychlorinated biphenyls (PCBs) and organochlorine (OC) pesticide levels were determined in tissues collected from stranded and bycaught common dolphins (Delphinus sp.) from New Zealand waters between 1999 and 2005. The concentrations of mercury (Hg), selenium (Se), chromium (Cr), zinc (Zn), nickel (Ni), cadmium (Cd), cobalt (Co), manganese (Mn), iron (Fe), copper (Cu), tin (Sn), lead (Pb), arsenic (As) and silver (Ag) were determined in blubber, liver and kidney tissue. PCBs (45 congeners) and a range of OC pesticides including dieldrin, hexachlorocyclohexane (HCH) and dichlorodiphenyltrichloroethane (DDT) and its metabolites DDE and DDD were determined in blubber samples. Cr and Ni were not detected in any of the samples and concentrations of Co, Sn and Pb were generally low. Concentrations of Hg ranged from 0.17 to 110 mg/kg wet weight. Organochlorine pesticides dieldrin, HCB, o,p'-DDT and p,p'-DDE were present at the highest concentrations. Sum DDT concentrations in the blubber ranged from 17 to 337 and 654 to 4430 microg/kg wet weight in females and males, respectively. Similarly, Sigma45CB concentrations ranged from 49 to 386 and 268 to 1634 microg/kg wet weight in females and males, respectively. The mean transmission of SigmaDDTs and ICES7CBs between a genetically determined mother-offspring pair was calculated at 46% and 42%, respectively. Concentrations of organochlorine pesticides determined in the present study are within similar range to those reported for Hector's dolphins (Cephalorhyncus hectori) from inshore New Zealand waters.     

Establishing baseline levels of trace elements in blood and skin of bottlenose dolphins in Sarasota Bay, Florida: implications for non-invasive monitoring

Several major unusual mortality events occurring in recent years have increased the level of concern for the health of bottlenose dolphin populations along the United States Atlantic and Gulf of Mexico coasts. Trace element concentrations were examined in a population of free-ranging dolphins in Sarasota Bay, Florida, in order to develop a benchmark for future comparisons within and between populations. Whole blood (n=51) and skin (n=40) samples were collected through capture and release health assessment events during 2002-2004. Samples were analyzed for Al, V, Cr, Mn, Cu, Zn, As, Se, Rb, Sr, Mo, Cd, and Pb by inductively coupled plasma mass spectrometry (ICPMS) and Hg via atomic fluorescence spectrometry (AFS). Trace element concentrations (wet mass) in skin were 2 to 45 times greater than blood, except Cu was approximately 1.5 times higher in blood. Statistically strong correlations (p<0.05) were found for V, As, Se, Rb, Sr, and Hg between blood and skin demonstrating that these tissues can be used as effective non-lethal monitoring tools. The strongest correlation was established for Hg (r=0.9689) and concentrations in both blood and skin were above the threshold at which detrimental effects are observed in other vertebrate species. Female dolphins had significantly greater Hg concentrations in blood and skin and Pb concentrations in skin, relative to males. Calves exhibited significantly lower V, As, and Hg concentrations in blood and V and Hg concentrations in skin, relative to other age classes. Rubidium and Cu concentrations in skin were greatest in subadults and calves, respectively. In blood, V, Zn, and As concentrations were significantly greater in winter, relative to summer, and the opposite trend was observed for Rb and Sr concentrations. In skin, Cu and Zn concentrations were significantly greater in winter, relative to summer, and the opposite trend was observed for Mn, Rb, Cd, and Pb concentrations. The baseline concentrations and trends established in this study will serve as a benchmark for comparison and aid in sampling design for future monitoring of this population and other coastal bottlenose dolphin populations.     

Pollutants in harp seals (Phoca groenlandica). II. Heavy metals and selenium

Between 1976 and 1978, 248 harp seals were sampled from five locations in the Northwest Atlantic and Arctic for heavy metal and selenium residue analyses in tissue. Significant loading was apparent only in blood, brain, kidney, liver and muscle. Samples were analysed for mercury (Hg), selenium (Se), copper (Cu), cadmium (Cd) and lead (Pb). The seals carried higher levels of Cd than of the other metals. Residue levels of Cd were highest in kidney tissue; levels of other metals were highest in liver. Both males and females bioaccumulated Cd, Hg and Se.Cd, Hg, Se and Cu residues were detected in tissue from neonatal seals, indicating that transplacental and transmammary transfer of these elements had occurred. Despite the passage of residues from mother to pup, females bore significantly higher levels of Hg and Cd than males. Conversely, levels of Cu, Se or Pb did not appear to differ significantly between sexes. There was considerable individual variation in residue levels. This, coupled with the extensive annual migration undergone by these animals, made it difficult to arrive at definite conclusions regarding geographic accumulation patterns.     

Heavy metals in the tissues of common dolphins (Delphinus delphis) stranded on the Portuguese coast.

The concentrations of Hg, Sn, Cr, Zn, Ni, Co, Cd, Mn, Fe and Cu were determined in the liver, kidney and muscle of 24 common dolphins stranded on the Portuguese coast between 1995 and 1998. Nitric acid was used to extract the metals from the tissues for analysis by inductively-coupled plasma/atomic emission spectroscopy (ICP/AES). Those metals with relatively higher concentrations included Fe, Zn and Hg, particularly in liver. Other metals including Cr, Ni and Cd tended to show much lower levels, or were even undetected (e.g. Co). Different metals seemed to show different temporal trends, although due to substantial variations of the mean concentrations for each year obtained, such temporal pattern has to be studied further. Total Hg concentration in the kidney, muscle and particularly liver, were higher in females than in males. Total Hg concentrations in all the organs increased with body length of dolphins, whilst those of Zn and Cu in muscle decreased with dolphin length. A strong correlation was found between essential metals Zn and Cu in muscle, possibly resulting from sequestration of these metals by metallothionein. In addition, significant co-associations existed between the same metal (e.g. Hg, Sn and Zn) in different organs.     

Kidney and liver levels of some major, minor and trace elements in two Ontario communities

The contents of Ag, As, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Mo, Na, Ni, P, Pb, Se, Sr, Th, Ti and Zn in 143 autopsied liver and kidney specimens from two Ontario communities (Kingston and Ottawa) were determined using the techniques of inductively-coupled plasma--atomic emission spectrometry, and electrothermal atomization--atomic absorption spectrometry coupled with hydride evolution (As, Se), reduction--aeration (Hg), or solvent extraction (Pb). The majority of samples came from individuals older than 50 y. In general, the data for the various elements were independent of age or sex but showed some dependence on location for elements such as Cu, Fe, K, Mg, Mn, Na, P, Se and Zn. Despite these differences the elemental values of the liver and kidney samples from both the communities were within the normal range.     

Application of high Cu compost to Swiss chard and basil

A greenhouse container experiment was conducted to evaluate the effect of high Cu compost on basil and Swiss chard productivity, and the accumulation of As, Ca, Fe, Hg, K, Mg, Na, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, S and Se in growth medium and plant tissue. The Cu content of the compost was over 1200 mg/kg, much higher than Canadian standards for type B compost quality. The treatments consisted of control soil (0% compost), and 20, 40 and 60% (by volume) of high Cu compost added to soil. All compost application treatments (20, 40 and 60%) resulted in increased dry matter yields in Swiss chard and basil. Addition of high Cu compost influenced basil plant development. Plants from the 20 and 40% treatments had higher numbers of buds and flowers. There were no differences between the control and 60% compost treatments with respect to flower initiation. Addition of 20, 40 and 60% compost to the soil resulted in increased EXCH fractions of Cu, but not of Mn and Zn. Compost additions resulted in increase in the HNO(3) extractable, CARB, FeMnOX, and in OM fractions of Cu, Mn and Zn in soils. Compost application increased soil pH and EC, soil HNO(3) extractable Ca, K, Mg, P, Na, B and Pb, but did not alter soil HNO(3) extractable Cd, Co, Cr, Mo, Ni, Se. Increased rates of compost application decreased tissue Ca in basil, tissue Na in both plants, increased tissue K, Mg in both plants, but, did not alter tissue P, Co, Cr, Mo, Ni of either plants, and B in basil. Tissue As, Hg, Pb, and Se from all treatments were under the detection limits of VGA-AAS (for As, Hg, Se) and ICP (for Pb). Compost additions altered basil oil chemical composition. Copper in the essential oil of basil was below 0.25 mg/l. In conclusion, the addition of high rates of relatively immature high Cu compost may not always increase Cu concentration in plants and in plant oils.     

Selenium in soils,spermatophytes and bryophytes around a Zn-Pb smelter,New South Wales,Australia

Blood and serum samples from 372 15-year-old adolescents were collected in two cities in Sweden and analyzed by inductively coupled plasma mass spectrometry (ICP-MS). The objective was to (1) determine the levels of 13 elements in blood and serum from the teenagers; and (2) for each element, investigate the correlation between the concentrations in blood and serum. The concentrations in blood and serum were generally in line with that usually reported for the essential elements Co, Cu, Zn and Se, and generally low for the 'non-essential' elements Cd, Hg, Pb. The median concentrations were in blood and serum, respectively: of Co 0.31 and 0.48 microg/l, Cu 0.92 and 1.0 mg/l, Zn 6.1 and 0.99 mg/l, Se 110 and 100 microg/l, Rb 2.8 and 0.24 mg/l, Hg 1.1 and 0.44 microg/l, Pb 16 and 0.33 microg/l. The median concentration of W in blood was <0.2 microg/l (below the detection limit) and in serum 0.087 microg/l. The median concentrations of Cd, Rh, Pd, Pt and Tl were below the detection limits. Statistically significant correlations were found between the concentrations in blood and serum for Co, Cu, Zn, Se, Rb, W, Hg and Pb. The levels presented in this study constitute baseline levels or levels generally not exceeded in adolescents for 13 elements, including essential, ubiquitous toxic, and rare elements.     

Health risk assessment of heavy metal exposure to street dust in the zinc smelting district, Northeast of China

Heavy metal contamination in the street dust due to metal smelting in the industrial district of Huludao city was investigated. Spatial distribution of Hg, Pb, Cd, Zn and Cu in the street dust was elucidated. Meanwhile, noncancer effect and cancer effect of children and adults due to exposure to the street dust were estimated. The maximum Hg, Pb, Cd, Zn and Cu contents in the street dust are 5.212, 3903, 726.2, 79,869, and 1532 mg kg^− 1, and respectively 141, 181, 6724, 1257 and 77.4 times as high as the background values in soil. The trends for Hg, Pb, Cd, Zn and Cu are similar with higher concentrations trending Huludao zinc plant (HZP). The exponential equation fits quite well for the variations of Pb, Cd, Zn and Cu contents with distance from the pollution sources, but not for Hg. The biggest contribution to street dust is atmospheric deposition due to metal smelting, but traffic density makes slight contribution to heavy metal contamination. According to the calculation on Hazard Index (HI), in the case of noncancer effect, the ingestion of dust particles of children and adults in Huludao city appears to be the route of exposure to street dust that results in a higher risk for heavy metals, followed by dermal contact. The inhalation of resuspended particles through the mouth and nose is almost negligible. The inhalation of Hg vapour as the fourth exposure pathway to street dust is accounting for the main exposure. Children are experiencing the potential health risk due to HI for Pb larger than safe level (1) and Cd close to 1. Besides, cancer risk of Cd due to inhalation exposure is low.     

Metal transfer to plants grown on a dredged sediment: use of radioactive isotope 203Hg and titanium

Improperly disposed of dredged sediments contaminated with metals may induce long-term leaching and an increase of metal concentrations in ground waters and vegetal cover plants. The objective of the study was to quantify the sediment-to-plant transfer of Cu, Pb, Hg and Zn with a particular focus on the pathway of Hg and to determine whether the establishment of vegetal cover modifies the metal availability. A pot experiment with rape (Brassica napus), cabbage (Brassica oleraccea) and red fescue (Festuca rubra) was set up using a sediment first spiked with the radioisotope 203Hg. Zinc concentrations (197-543 mg kg(-1) DM) in leaves were higher than Cu concentration (197-543 mg kg(-1) DM), Pb concentration (2.3-2.6 mg kg(-1) DM) and Hg concentration (0.9-1.7 mg kg(-1) DM). Leaves-to-sediment ratios decreased as follows: Zn > Cu > Hg > Pb. According to Ti measurements, metal contamination by dry deposition was less than 1%. Mercury concentration in plant leaves was higher than European and French thresholds. Foliar absorption of volatile Hg was a major pathway for Hg contamination with a root absorption of Hg higher in rape than in cabbage and red fescue. Growth of each species increased Cu solubility. Zinc solubility was increased only in the presence of rape. The highest increase of Cu solubility was observed for red fescue whereas this species largely decreased Zn solubility. Dissolved organic carbon (DOC) measurements suggested that Cu solubilisation could result from organic matter or release of natural plant exudates. Dissolved inorganic carbon (DIC) measures suggested that the high Zn solubility in the presence of rape could originate from a generation of acidity in rape rhizosphere and a subsequent dissolution of calcium carbonates. Consequently, emission of volatile Hg from contaminated dredged sediments and also the potential increase of metal solubility by a vegetal cover of grass when used in phytostabilisation must be taken into account by decision makers.     

Mercury and other trace elements in soils affected by the mine tailing spill in Aznalcóllar (SW Spain)

The Aznalcóllar accident (28th April 1998) occurred because the collapse of the tailing-dam dike of the Aznalcóllar-Los Frailes mines. Soils were affected by a slurry of acidic water loaded with trace elements, finely divided metal sulphides, and materials used in the refining /floating process. Studies carried out before and after the soil restoration activities (sludge removal, amending, tilling, and afforestation) showed severe trace-element contamination (mainly As, Cd, Cu, Pb, Tl and Zn) in the superficial layer of the sludge-affected soils. Despite Hg being an important component of the Los Frailes ore and therefore of the contaminant sludge, data on Hg content of sludge-affected soils are scarce and sometimes controversial. The aim of this study was to determine the effect of the spill and of restoration measures on the Hg content of soils and how this related to other elements. Concentration of Hg immediately after the spill was 8-fold above background (0.061+/-0.012 mg kg(-1); mean+/-SD) at the surface (0-5 cm) and 3-4-fold greater in deeper layers (0-20; 0-50 cm). After the remediation measures, mean values of Hg and other elements (As, Cd, Cu, Pb and Zn) were very variable and remained above background values. These anomalies are due to the sludge left on the soil surface or buried during restoration operations, resulting in an irregular distribution of trace elements. The highest values for the less mobile elements (up to 176 mg kg(-1) As, 2.36 mg kg(-1) Hg and 1556 mg kg(-1) Pb) were observed in the area 1 km downstream of the tailings dam.     

Trace element concentrations in hair of healthy Chinese centenarians

Trace element concentrations, as indicators of micronutrient status of healthy centenarians, have not been widely analyzed. This study aimed to assess trace element concentrations in the hair of healthy centenarians. The effects of gender and age on element concentrations were also investigated. Eleven trace elements (Al, Ba, Cd, Cr, Cu, Fe, Mo, Pb, Se, Sr and Zn) in the scalp hair of 107 healthy Chinese centenarians were examined. The overall reference values (RVs) in mg/kg for the hair concentrations of trace elements in centenarians were as follows: Al, 14.95; Ba, 2.68; Cd, 0.06; Cr, 0.59; Cu, 6.21); Fe, 19.37; Mo, 0.50; Pb, 4.64; Se, 0.37; Sr, 4.84; and Zn, 154.37. Data analysis found that only Cu and Zn concentrations show a normal distribution, and there is no significant difference between males and females in any element except Zn. However, the levels of Al, Cd, Cr, Fe, Mo, Pb decrease and the levels of Ba, Cu, Se, Sr, Zn increase with age in the centenarian cohort. Results also revealed that sufficient Zn and Se concentrations as well as low exposure to heavy metals pollution contribute to the longevity of centenarians. The results imply the possibility of manipulating trace element concentrations, especially Zn and Se concentrations in tissues, as a means for therapeutic modality in geriatric disease.     

Hepatic levels of metal and metallothioneins in two commercial fish species of the Northern Iberian shelf

Metal levels (Cd, Pb, Hg, Cr, Fe, Cu, Zn) together with metallothioneins (MTs) were determined in the liver of two commercial fish species collected along the Northern Iberian coast. The four-spotted megrim (Lepidorhumbos boscii) and the pouting (Trisopterus luscus) were selected as representative species of the middle/outer (200-500 m) and inner shelf (70-120 m), respectively. Metal pollution in the middle/outer shelf was mostly detected in the Asturias and Basque Country areas, whereas in the inner shelf, pollution was widely spread along the coast. Significantly high levels of Pb, Cd, Cr and Hg were detected in T. luscus from different sampling sites and associated to anthropogenic pressure. MTs were induced in fish that had higher amounts of Zn, Cd, Cr and Hg in their livers, supporting the use of MT as a biomarker of metal exposure. The study supports the usefulness of the selected fish species as sentinel organisms for future biomonitoring studies.     

Concentrations of heavy metals and plant nutrients in water, sediments and aquatic macrophytes of anthropogenic lakes (former open cut brown coal mines) differing in stage of acidification.

Concentration of heavy metals (Al, Ba, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sr, V and Zn) as well as macronutrients (N, P, K, Ca, Mg, S) were measured in water, bottom sediments and plants from anthropogenic lakes in West Poland. The collected plants were: Phragmites australis, Potamogeton natans, Iris pseudoacorus, Juncus effusus, Drepanocladus aduncus, Juncus bulbosus, Phalaris arundinacea, Carex remota and Calamagrostis epigeios. Two reference lakes were sampled for Nymphaea alba, Phragmites australis, Schoenoplectus lacustris, Typha angustifolia and Polygonum hydropiper. These plants contained elevated levels of Cd, Co, Cr, Cu and Mn, and part of the plants contained in addition elevated levels of Mn, Fe, Pb, Ni and Zn. Analyses of water indicated pollution with sulfates, Cd, Co, Ni. Zn, Pb and Cu, and bottom sediments indicated that some of the examined lakes were polluted with Cd, Co and Cr. Strong positive correlations were found between concentrations of Co in water and in plants and between Zn in sediments and plants, indicating the potential of plants for pollution monitoring for this metal. Heavy metal accumulation seemed to be directly associated with the exclusion of Ca and Mg.     

Soil contamination by metals: A survey in industrial and rural areas of southern Italy

Samples of soil from agricultural land around the industrial district of the city of Bari in Apulia and from rural areas of that region were analyzed, by atomic absorption spectrophotometry, for levels of As, Bi, Cd, Cu, Hg, Mn, Ni, Pb, Se, Sn, and Zn.All elements, except Se, were present in all samples from the industrial district, whereas Hg was not detectable in the rural soils; Bi, Cd, and Sn were found only in 50–60% of them. The average levels of Hg, Cd, Cu, Mn, and Ni in soils close to the industrial area always appeared to be higher than the mean levels in rural soils and the common ranges known for world soils.The findings suggest the existence of a metal contamination of soils in the industrial area.     

Heavy metals in the dump of an abandoned mine in Galicia (NW Spain) and in the spontaneously occurring vegetation

The concentrations of different forms of heavy metals (Fe, Mn, Zn, Cu, Cr, Ni, Cd and Pb) were determined in a mine dump material rich in chalcopyrite. The concentrations were compared with those of the natural vegetation colonising the dump. Samples taken from the dump are acid (pH(H(2)O) between 3.0 and 5.0), have carbon contents lower than 0.5%, N lower than 0.2%, effective cation exchange capacity between 0.74 and 4.96 cmol(+)kg(-1) and percent Al saturation in the exchange complex higher than 20% in 85% of the samples. Iron was the most abundant heavy metal, in both total and bioavailable forms, and the relative abundance of metals was: Fe>Cu>Mn>Zn>Cr. The total Fe concentrations ranged between 4315 and 31578 mg x kg(-1), the total Cu between 273 and 5241 mg x kg(-1), the total Mn between 294 and 2105 mg x kg(-1), the total Zn between 73 and 894 mg x kg(-1) and total Cr between 0.01 and 30 mg x kg(-1). Ni, Cd and Pb were below the analytical detection limits. The concentration of bioavailable Fe ranged between 40 and 1550 mg x kg(-1); Zn was the least abundant metal in this fraction (between 2 and 100 mg x kg(-1)). Copper was the most abundant heavy metal in the exchange complex and in the aqueous extracts, followed by Zn, Mn and Fe. Exchangeable Cu ranged between 17.7 and 1866 mg x kg(-1), whereas the maximum concentrations of exchangeable Zn, Mn and Fe did not exceed 140 mg x kg(-1). The Cu concentration in the aqueous extracts varied between 0.1 and 8.3 mg x l(-1) and the concentration of Fe was always less than 0.52 mg x l(-1). The heavy metal contents in the spontaneously occurring vegetation in the dump ranged between: 150 and 900 mg Fe x kg(-1), 84 and 2069 mg Mn x kg(-1), 20.5 and 106 mg Cu x kg(-1) and between 35 and 717 mg Zn x kg(-1), when considering all the plant samples analysed. Festuca sp. accumulated Fe, Salix atrocinerea accumulated Zn and Mn, and Frangula alnus and Quercus robur accumulated Mn. These native plant species may contribute to decrease the heavy metal contents in the dump material.     

Assessment of metal pollution in Onsan Bay, Korea using Asian periwinkle Littorina brevicula as a biomonitor.

Cadmium (Cd), lead (Pb), copper (Cu) and zinc (Zn) concentrations in the marine gastropod, Littorina brevicula Philippi, were determined to assess the metal pollution in Onsan Bay, Korea. Samples of L. brevicula employed as a biomonitor and seawater were collected from 12 to 20 stations of Onsan Bay in November 1997, respectively. Dissolved metal concentrations in surface seawater were highest at the station near Onsan Non-ferrous Industrial Complex: 1.15 micrograms l-1 for Cd, 2.49 micrograms l-1 for Pb, 3.75 micrograms l-1 for Cu and 23.98 micrograms l-1 for Zn. These values were 1-2 orders higher than those shown at outer regions of the Bay. Metal concentrations in the soft body of periwinkles were highly variable at different sampling locations: 0.48-27.11 micrograms g-1 for Cd, 1.41-24.91 micrograms g-1 for Pb, 57-664 micrograms g-1 for Cu and 83-246 micrograms g-1 for Zn. The values from stations near the industrial complex were higher than those expected from relationships between body sizes and metal body burdens in periwinkles collected from the whole Korean coast. Spatial distribution of metal concentrations in the periwinkle and seawater indicated that Onsan industrial complex near the Bay is the input source of these metals. Especially, Cd and Pb concentrations in the periwinkle and seawater were distinctly decreased with distance from the Onsan industrial complex. Non-essential metals such as Cd and Pb in the periwinkle showed a strong correlation with dissolved metal concentrations in seawater. Conversely, essential Cu and Zn in the periwinkle were hardly explained by those in seawater, except at the most contaminated sites.     

An evaluation of the reactivity of synthetic and natural apatites in the presence of aqueous metals

Metal removal from contaminated effluents was examined following reaction with natural apatites of biological and geological origin or a synthetic hydroxylapatite (HAP). Mammalian meat and bone meal (MBM), a by-product from meat industry, was the biological apatite source. The effect of incineration on metal removal capacity of MBM and HAP was also examined. The reactivity of apatites for all tested metals (Pb, Cd, Cu and Zn) followed the general order: synthetic > biological > mineral. For all apatites tested, Pb was removed best and preferentially from multi-metal solutions. MBM and HAP (0.5 g solid) removed Pb completely from both highly concentrated single metal solutions (50 ml, 1000 mg/L Pb) and from multi-metal solutions (50 ml) with 100 mg/L each of Cd, Cu and Zn in addition to Pb. The incineration of MBM (725 °C and 850 °C) reduced significantly its capacity for removal of Zn (by 47%, from 56 mg/g to 9 mg/g) and Cd (by 38%, from 53 mg/g to 13 mg/g) in particular and to a lesser extent for Cu (by 14%, from 61 mg/g to 46 mg/g) while the removal of Pb was not affected (100 mg/g). The same pattern was observed for incinerated HAP. SEM and XRD analysis indicated that HAP reacted with the metals by precipitation of pure metal phosphates—Pb hydroxylapatite, Zn phosphate (hopeite), a Cd phosphate (identified only by ED-SEM) and Cu phosphate (libenthenite).