Effects of sewage sludge on pH and plant availability of metals in oxidising sulphide mine tailings

A field study was conducted adjacent to the tailings deposit of the Aitik copper mine in the north of Sweden to investigate the effects of sewage sludge on pH and plant availability of Al, Mn, Cu, Zn, Ni, Pb, As, Cr and Cd in the oxidising sulphide tailings. One treatment was supplied with sewage sludge, while the control received NPK-fertiliser. The tailings samples were collected at the beginning and the end of the growing season and extracted by NH(4)NO(3), NH(4)Ac-EDTA and HNO(3). Plant tissue concentrations of the elements were determined in the above-ground parts of barley (Hordeum vulgare) and red fescue (Festuca rubra). The application of sewage sludge resulted in higher crop yields compared to the control, although the buffering capacity and the metal immobilising effect of the sludge were limited. The pH decreased from 6.6 to 4.3 in the control and from 6.4 to 4.8 in the sludge-treated tailings during the growing season, probably due to sulphide oxidation in the tailings. This resulted in increased levels of soluble elements in all treatments studied. Application of sewage sludge resulted in elevated levels of soluble Zn and lower values of soluble As and Cd in the unaltered tailings but increased levels of specifically adsorbed Cu, Ni and As in the oxidised tailings. This was partly reflected in the plants, as the application of sewage sludge resulted in 67 mg Zn kg(-1) in barley grains and 60 mg Zn kg(-1) in red fescue shoots, both values twice as high as the corresponding values in the control, but lower As contents in both straw (0.3 mg kg(-1)) and grain (0.06 mg kg(-1)) of barley compared to the control (0.6 and 0.2 mg kg(-1), respectively). In addition, red fescue grown in sludge-treated plots contained significantly higher levels of Al, Cu, Pb, As and Cr compared to the control. The levels of several metals in barley and red fescue grown in both treatments exceeded background values found in the literature. The Cu content in barley straw exceeded 100 mg kg(-1) in both treatments and might be toxic to grazing animals. Thus, this study suggests that adding sewage sludge to the mine tailings at Aitik would not counteract the effects of the sulphide oxidation in the tailings. Furthermore, using a sequential extraction technique proved preferable to using total metal analysis in order to predict plant uptake of the elements in the tailings.     

Metals and selenium in the liver and bone of three dolphin species from South Australia, 1988-2004

Metal and selenium concentrations (wet weight) were determined in the liver (Cd, Hg, Pb, Zn, Cu and Se) and bone (Pb and Cd) of common dolphins (Delphinus delphis, N=71) and bottlenose dolphins (Tursiops truncatus, N=12, and Tursiops aduncus, N=71) stranded or by-caught in South Australia from 1988 to 2004. Differences in metal burdens existed between species, stranding location, and relative age. T. aduncus had the greatest mean tissue burdens of liver Pb (0.45 mg/kg), Cd (6.45 mg/kg), Hg (475.78 mg/kg), Se (178.85 mg/kg) and Zn (93.88 mg/kg) and bone Pb (2.78 mg/kg), probably reflecting their coastal habitat and benthic prey. Mean Cu was highest in T. truncatus (21.18 mg/kg). Bone Cd was measured only in T. aduncus and averaged 0.05 mg/kg. Stranding location impacted metal burdens. Dolphins from Spencer Gulf had higher mean levels of liver Pb (0.39 mg/kg) while Gulf St Vincent dolphins had greater liver Hg (444.64 mg/kg), liver Se (163.12 mg/kg), and bone Pb (2.85 mg/kg). This may be due to high anthropogenic inputs of Pb and Hg into Spencer Gulf and Gulf St Vincent respectively. Liver Cd, Hg, Se and Pb increased with age in all species while Cu decreased with age, in keeping with previous studies. Se and Hg were positively correlated. The possibility that metallothioneins are driving observed correlations between Zn, Cd, Hg and Cu are discussed. Future research must investigate the toxicological consequences of the metal concentrations reported.     

Solubility of metals in an anoxic sediment during prolonged aeration

This work was conducted to study the evolution of the solubility of selected metals during the aeration of an anoxic sediment. Batch experiments were carried out for 76 days with a metal-polluted dredged sediment. The pH, Eh and concentration of Al, Cu, Fe, Hg, Pb and Zn were periodically recorded. Results showed that during the early stages of aeration, the solubility of metals increased rapidly but was then followed by fast re-adsorption. As a consequence, after 14 days most of the metals excepted Cu and Zn were present at low or undetectable concentrations in solution. Re-adsorption of Zn was observed to be much slower during the first two weeks, whereas solubilisation of Cu increased gradually during months after land disposal. According to speciation calculations, Cu solubilisation was in part due to complexation in solution by carbonates. In the case of Hg, although complexation by dissolved organic matter (DOM) could be expected, re-adsorption was the dominant process. However, more knowledge about the behaviour of the DOM present in anoxic sediments is needed in order to make more quantitative statements about the mobility of heavy metals contained in dredged material.     

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.     

Historical perspective of heavy metals contamination (Cd, Cr, Cu, Hg, Pb, Zn) in the Seine River basin (France) following a DPSIR approach (1950-2005)

The Driver-Pressures-State-Impact-Response approach is applied to heavy metals in the Seine River catchment (65,000 km(2); 14 million people of which 10 million are aggregated within Paris megacity; 30% of French industrial and agricultural production). The contamination pattern at river mouth is established on the particulate material at different time scales: 1930-2000 for floodplain cores, 1980-2003 for suspended particulate matter (SPM) and bed-sediments, 1994-2003 for atmospheric fallout and annual flood deposits. The Seine has been among the most contaminated catchments with maximum contents recorded at 130 mg kg(-1) for Cd, 24 for Hg, 558 for Pb, 1620 for Zn, 347 for Cu, 275 for Cr and 150 for Ni. Today, the average levels for Cd (1.8 mg kg(-1)), Hg (1.08), Pb (108), Zn (370), Cu (99), Cr (123) and Ni (31) are much lower but still in the upper 90% of the global scale distribution (Cr and Ni excepted) and well above the natural background values determined on pre-historical deposits. All metal contents have decreased at least since 1955/65, well before metal emission regulations that started in the mid 1970's and the metal monitoring in the catchment that started in the early 1980's. In the last 20 y, major criteria changes for the management of contaminated particulates (treated urban sludge, agricultural soils, dredged sediments) have occurred. In the mid 1990's, there was a complete shift in the contamination assessment scales, from sediment management and water usage criteria to the good ecological state, now required by the 2000 European Directive. When comparing excess metal outputs, associated to river SPM, to the average metal demand within the catchment from 1950 to 2000, the leakage ratios decrease exponentially from 1950 to 2000 for Cd, Cr, Cu, Pb and Zn, meanwhile, a general increase of the demand is observed: the rate of recycling and/or treatment of metals within the anthroposphere has been improved ten-fold. Hg environmental trajectory is very specific: there is a marked decontamination from 1970 to 2000, but the leakage ratio remains very high (10 to 20%) during this period. Drivers and Pressures are poorly known prior to 1985; State evolution since 1935 has been reconstructed from flood plain cores analysis; Impacts were maximum between 1950 and 1970 but remained unknown due to analytical limitation and lack of awareness. Some Responses are lagging 10 y behind monitoring and have much evolved in the past 10 y.     

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.     

The potential of Lolium perenne for revegetation of contaminated soil from a metallurgical site

A greenhouse study was carried out to determine the possibility of using Lolium perenne for revegetation of soil from a former ferrous metallurgical plant (Naples, South Italy) contaminated by Cu, Pb and Zn at levels above current Italian regulatory limits. Surface soil samples (0-40 cm) from the facility area where raw minerals were disposed (RM1 and RM2), from a nearby unpolluted cultivated soil (C) as control and a 1:3 mixture of the control with the polluted ones (RM1+C and RM2+C) were utilized for the experiment. Revegetation trials were conducted in the greenhouse. At 90 days from seeding, shoot length, chlorophyll content, biomass yield, plant metal uptake and changes of organic carbon content and metal distribution among soil extractable phases defined by sequential extraction were determined. In the mixed substrates (RM1+C and RM2+C) concentrations of Cu, Pb and Zn were still two to three times higher than the Italian regulatory limits. Plants were healthy with 100% survival in all substrates, with no macroscopic symptoms of metal toxicity. The high pH of the soil could be one of the most important parameters responsible for the limited plant availability of the metals. On RM1, RM2 and mixed media, plants experienced retarded growth, reduced shoot length and biomass yield and higher total chlorophyll content compared to those cropped on the control soil, without any evident phytotoxic symptoms. In RM1 and RM2, the plant contents of Cu (19.3 and 12.6 mg kg(-1)), Pb (0.98 and 0.67 mg kg(-1)) and Zn (99 and 88 mg kg(-1)) were higher than that of plants grown on non-contaminated soil (Cu 10.1, Pb < 0.2, Zn 79 mg kg(-1)), but still in the range of physiologically acceptable levels. The distribution of metals in soil was slightly affected by Lolium growth with changes only regarding the organic-bound Cu and Zn pool, with reduction up to 24%. Results indicated that an acceptable healthy vegetative cover can be achieved on the contaminated soil by the proposed revegetation approach and that metals will remain stable over the study period with slight variation of the more available metal forms.     

Accumulation of Pb, Cu, and Zn in native plants growing on a contaminated Florida site

Contamination of heavy metals represents one of the most pressing threats to water and soil resources as well as human health. Phytoremediation can be potentially used to remediate metal-contaminated sites. This study evaluated the potential of 36plants (17species) growing on a contaminated site in North Florida. Plants and the associated soil samples were collected and analyzed for total metal concentrations. While total soil Pb, Cu, and Zn concentrations varied from 90 to 4100, 20 to 990, and 195 to 2200mg kg(-1), those in the plants ranged from 2.0 to 1183, 6.0 to 460, and 17 to 598mg kg(-1), respectively. None of the plants were suitable for phytoextraction because no hyperaccumulator was identified. However, plants with a high bioconcentration factor (BCF, metal concentration ratio of plant roots to soil) and low translocation factor (TF, metal concentration ratio of plant shoots to roots) have the potential for phytostabilization. Among the plants, Phyla nodiflora was the most efficient in accumulating Cu and Zn in its shoots (TF=12 and 6.3) while Gentiana pennelliana was most suitable for phytostabilization of sites contaminated with Pb, Cu and Zn (BCF=11, 22 and 2.6). Plant uptake of the three metals was highly correlated, whereas translocation of Pb was negatively correlated with Cu and Zn though translocation of Cu and Zn were correlated. Our study showed that native plant species growing on contaminated sites may have the potential for phytoremediation.     

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.     

Heavy metals in urban soils: a case study from the city of Palermo (Sicily), Italy

Concentrations of V, Mn, Cd, Zn, Ni, Cr, Co, Cu, Pb, Hg and Sb were measured on 70 topsoil samples collected from green areas and parks in the city of Palermo (Sicily) in order to: (1) assess the distribution of these heavy metals in the urban environment; (2) discriminate natural and anthropic contributions; and (3) identify possible sources of pollution. Mineralogy, physico-chemical parameters, and major element contents of the topsoils were determined to highlight the influence of 'natural' features on the heavy metal concentrations and their distribution. Medians of Pb, Zn, Cu and Hg concentrations of the investigated urban soils are 202, 138, 63 and 0.68 mgkg(-1), respectively. These values are higher, in some case by different orders of size, than those of unpolluted soils in Sicily that average 44, 122, 34 and 0.07 mg kg(-1). An ensemble of basic and multivariate statistical analyses (cluster analysis and principal component analysis) was performed to reduce the multidimensional space of variables and samples, thus defining two sets of heavy metals as tracers of natural and anthropic influences. Results demonstrate that Pb, Zn, Cu, Sb and Hg can be inferred to be tracers of anthropic pollution, whereas Mn, Ni, Co, Cr, V and Cd were interpreted to be mainly inherited from parent materials. Maps of pollutant distribution were constructed for the whole urban area pointing to vehicle traffic as the main source of diffuse pollution and also showing the contribution of point sources of pollution to urban topsoils.     

Geochemical signals and source contributions to heavy metal (Cd, Zn, Pb, Cu) fluxes into the Gironde Estuary via its major tributaries

Daily measurements of water discharges and suspended particulate matter (SPM) concentrations and monthly sampling for trace element analyses (Cd, Zn, Pb and Cu) were conducted from 1999 to 2002 on the Garonne, Dordogne and Isle Rivers, the three main tributaries of the Gironde Estuary, France. Dissolved and particulate Cd, Zn, Pb and Cu concentrations in the Isle River were generally higher than those in the Garonne River, despite the known historical polymetallic pollution affecting the Lot-Garonne River system. Even if the relatively high dissolved metal concentrations in the Isle River may be of importance for the local ecosystem, metal inputs into the estuarine and coastal zones are mainly controlled by fluvial transport via the Garonne River. Characteristic element concentration ratios (e.g., Zn/Pb) in SPM and stream sediments from the Dordogne and Isle Rivers suggest two different metal source areas with distinct geochemical signals. Low Zn/Pb ratios (<8) and low Cu/Pb ratios (<0.8) have been attributed to upstream source zones in the Massif Central, featuring various ore deposits and mining areas. High Zn/Pb ratios were assigned to downstream sources (e.g., vineyards), partly explaining high Zn and Cu concentrations and high Cu/Pb ratios (>0.8) in SPM. Although SPM derived from the upstream parts of the studied watersheds may greatly contribute to the observed fluvial metal transport (up to approximately 80% for Pb), the results suggest that intensive agriculture also considerably influences gross metal (e.g., Zn, Cu) fluxes into the Gironde Estuary. Relative contributions of upstream and downstream source zones may vary from one year to another reflecting hydrological variations and/or reservoir management. Monitoring fluxes and identifying distinct geochemical signals from source areas in heterogeneous watersheds may greatly improve understanding of contaminant transport to the coast.     

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 extraction by Alyssum serpyllifolium ssp. lusitanicum on mine-spoil soils from Spain

The efficiency of Alyssum serpyllifolium ssp. lusitanicum (Brassicaceae) for use in phytoextraction of polymetallic contaminated soils was evaluated. A. serpyllifolium was grown on two mine-spoil soils (MS1 and MS2): MS1 is contaminated with Cr (283 mg kg(-1)) and MS2 is moderately contaminated with Cr (263 mg kg(-1)), Cu (264 mg kg(-1)), Pb (1433 mg kg(-1)) and Zn (377 mg kg(-1)). Soils were limed to about pH 6.0 (MS1/Ca and MS2/Ca) or limed and amended with NPK fertilisers (MS1/NPK and MS2/NPK). Biomass was reduced on MS2/Ca due to Cu phytotoxicity. Fertilisation increased biomass by 10-fold on MS1/NPK, but root growth was reduced by 7-fold compared with MS1/Ca. Plants accumulated Mn, Ni and Zn in shoots, and both metal content and transportation were generally greater in MS2 than in MS1. Zinc bioaccumulation factors (BF, shoot([metal])/soil([metal])) were significantly greater in MS2 than in MS1. However, metal yields were greatest in plants grown on MS1/NPK. Concentrations of EDTA-, NH(4)Cl- and Mehlich 3 (M3)-extractable Mn and Zn were greater after plant growth. Concentrations of M3-extractable Cr, Ni, Pb and Zn were increased at the rhizosphere. Sequential extractions showed changes in the metal distribution among different soil fractions after growth. This could reflect the buffering capacity of these soils or the plants' ability to mobilise metals from less plant-available soil pools. Results suggest that A. serpyllifolium could be suitable for phytoextraction uses in polymetallic-contaminated soils, provided Cu concentrations were not phytotoxic. However, further optimisation of growth and metal extraction are required.     

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.     

Metal contamination in water and bioaccumulation of metals in the planktons,molluscs and fishes in Jamshedpur stretch of Subarnarekha River of Chotanagpur plateau,India

Subarnarekha River is a rain‐fed peninsular river passing through industrial city Jamshedpur, an important industrial centre of Jharkhand, India. Heavy metal concentrations like Zn, Pb, Cr, Cd, Ni and Cu in water, sediment and in different food webs were determined using inductively coupled plasma‐mass spectrophotometer for two sampling sites that are found stressed with high contamination due to urbanization and anthropogenic activities. Present study mainly focuses on the metal concentration in water, sediment, plankton with bioaccumulation factor (BAF) in body parts of molluscs and fishes. The study revealed that Zn and Pb were found in highest concentration in plankton (Zn: 20.6 g/kg, Pb: 6.0 g/kg), molluscs (Zn: 4.6 g/kg, Pb: 0.6 g/kg) and in fish (Zn: 6.1 g/kg, Pb: 3.0 g/kg) as biomagnification. Calculated BAF indicated that in fish species Zn has highest BAF value followed by Pb, which may be harmful for human consumption.     

Animal excrement: a potential biomonitor of heavy metal contamination in the marine environment

To assess the feasibility of using animal excrement to biomonitor the extent of heavy metal contamination in the marine environment, concentrations of mercury (Hg), lead (Pb), copper (Cu) and zinc (Zn) in the fresh excrement of seabirds and marine mammals, along with other biomaterials, from the Arctic, Antarctica (West and East), and Xisha Archipelago of the South China Sea were determined. Results show that the excrement of marine animals at higher trophic levels generally contained high levels of Hg, demonstrating the biomagnification of Hg through food chains in different remote regions. Significant variations in metal accumulation in the excrements were observed among the distinctive geographical areas, with the highest Hg concentration in Xisha Archipelago and the highest Pb concentration in the Arctic, which reflects different levels of air metal pollution at various sampling locations. Concentrations of Cu in the excrements primarily correlate to the geochemical background levels in the regions. High Cu concentrations were found near the Great Wall Station in West Antarctica where a copper mineralized belt exists. No clear spatial variation pattern was found for Zn accumulation in the excrement. This study shows that animal excrement can be used as bioindicators for the level of metal contamination in the marine environment, with the advantages of easy sampling, accurate detection (i.e., with high levels of metal accumulation), and reconstructing historical metal contamination trends by long-term monitoring of sedimentary excrements.     

Metal concentrations in soils around the copper smelter and surrounding industrial complex of Port Kembla, NSW, Australia

Anthropogenic emissions of metals from sources such as smelters are an international problem, but there is limited published information on emissions from Australian smelters. The objective of this study was to investigate the regional distribution of heavy metals in soils in the vicinity of the industrial complex of Port Kembla, NSW, Australia, which comprises a copper smelter, steelworks and associated industries. Soil samples (n=25) were collected at the depths of 0-5 and 5-20 cm, air dried and sieved to <2 mm. Aqua regia extractable amounts of As, Cr, Cu, Pb and Zn were analysed by inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma atomic emission spectrometry (ICP-AES). Outliers were identified from background levels by statistical methods. Mean background levels at a depth of 0-5 cm were estimated at 3.2 mg/kg As, 12 mg/kg Cr, 49 mg/kg Cu, 20 mg/kg Pb and 42 mg/kg Zn. Outliers for elevated As and Cu values were mainly present within 4 km from the Port Kembla industrial complex, but high Pb at two sites and high Zn concentrations were found at six sites up to 23 km from Port Kembla. Chromium concentrations were not anomalous close to the industrial complex. There was no significant difference of metal concentrations at depths of 0-5 and 5-20 cm, except for Pb and Zn. Copper and As concentrations in the soils are probably related to the concentrations in the parent rock. From this investigation, the extent of the contamination emanating from the Port Kembla industrial complex is limited to 1-13 km, but most likely <4 km, depending on the element; the contamination at the greater distance may not originate from the industrial complex.     

Dissolved and particulate metals (Fe, Zn, Cu, Cd, Pb) in two habitats from an active hydrothermal field on the EPR at 13 degrees N

The distribution of Fe, Cu, Zn, Pb, Cd between the dissolved (<2 microm) and the particulate (>2 microm) fractions was measured after in-situ filtration in two hydrothermal habitats. The total metal concentration ranges exhibit a clear enrichment compared with the seawater concentration, accounting for the hydrothermal input for all the metals considered. Iron is the predominant metal (5-50 microM) followed by Zn and Cu. Cd and Pb are present at the nM level. At the scale studied, the behavior of temperature, pH and dissolved iron is semi-conservative whereas the other dissolved and particulate metals are characterized by non-conservative patterns. The metal enrichment of the >2 microm fraction results from the settlement and accumulation of particulate matter close to the organisms, acting as a secondary metal source. The enrichment observed in the dissolved fraction can be related to the dissolution or oxidation of particles (mainly polymetallic sulfide) or to the presence of small particles and large colloids not retained on the 2 microm frit. SEM observations indicate that the bulk particulate observed is characteristic of crystalline particles settling rapidly from the high temperature smoker (sphalerite, wurtzite and pyrite), amorphous structures and eroded particles formed in the external zone of the chimney. Precipitation of Zn, Cu, Cd and Pb with Fe as wurtzite, sphalerite and pyrite is the main process taking place within the area studied and is semi-quantitative. The distribution of the dominant observed fauna has been related to the gradient resulting from the dilution process, with the alvinellids worms colonizing the hotter and more variable part of the mixing zone, but also to the metallic load of the mixing zone. Dissolved and particulate metal concentrations are therefore necessary abiotic factors to be studied in a multiparametric approach to understand the faunal distribution in hydrothermal ecosystems.     

Metal uptake by young trees from dredged brackish sediment: limitations and possibilities for phytoextraction and phytostabilisation

Five tree species (Acer pseudoplatanus L., Alnus glutinosa L. Gaertn., Fraxinus excelsior L., Populus alba L. and Robinia pseudoacacia L.) were planted on a mound constructed of dredged sediment. The sediment originated from a brackish river mouth and was slightly polluted with heavy metals. This preliminary study evaluated the use of trees for site reclamation by means of phytoextraction of metals or phytostabilisation. Although the brackish nature of the sediment caused slight salt damage, overall survival of the planted trees was satisfactory. Robinia and white poplar had the highest growth rates. Ash, maple and alder had the highest survival rates (>90%) but showed stunted growth. Ash, alder, maple and Robinia contained normal concentrations of Cd, Cu, Pb and Zn in their foliage. As a consequence these species reduce the risk of metal dispersal and are therefore suitable species for phytostabilisation under the given conditions. White poplar accumulated high concentrations of Cd (8.0 mg kg(-1)) and Zn (465 mg kg(-1)) in its leaves and might therefore cause a risk of Cd and Zn input into the ecosystem because of autumn litter fall. This species is thus unsuitable for phytostabilisation. Despite elevated metal concentrations in the leaves, phytoextraction of heavy metals from the soil by harvesting stem and/or leaf biomass of white poplar would not be a realistic option because it will require an excessive amount of time to be effective.     

Land inputs of trace metals, major elements, particulate organic carbon and suspended solids to an industrial coastal bay of the NE Atlantic

Rivers, streams and municipal and industrial effluents flowing into the Ferrol Ria (NW Spain) were analyzed for dissolved and particulate trace elements (Cd, Cu, Pb, Zn), particulate major elements (Al, Fe, Si), particulate organic carbon and nitrogen (POC and PON), and total suspended solids. Trace metal clean techniques were applied. Mean annual fluxes of these components were calculated. Dissolved trace metal concentrations in the major freshwater inputs were found to be within typical values for uncontaminated rivers: Cd: 0.020-0.035 nM; Cu: 11.7-19.2 nM; Pb: 0.40-0.71 nM and Zn: 18-54 nM. Two sources of suspended particulate matter (SPM) were observed: (i) a detrital SPM, which becomes more important at high river discharges, with metal concentrations tending to lithogenic values; (ii) an organic- and metal-rich SPM, which becomes dominant at low discharges. Municipal and industrial effluents in the northern shore, despite of constitute a minor freshwater contribution to the bay, were responsible for more than 50% of total inputs of Cu, Cd, Pb, Zn, POC and PON. The fluxes of trace metals obtained for the Ferrol Ria are in the range of other inhabited world semi-enclosed embayments.