Relationship between heavy metals concentrations in egret species,their environment and food chain differences from two Headworks of Pakistan

Concentration of ten metals (Cd, Cr, Co, Cu, Fe, Li, Mn, Ni, Pb and Zn) were analyzed in the egg contents, prey and soil samples of little egret (Egretta garzetta) and cattle egret (Bubulcus ibis) from two Headworks to determine habitat and species-specific differences; to assess the importance of prey and habitat contamination as an exposure source for heavy metals. Concentration of Cu, Mn, Cr and Pb in egg contents, Fe, Co, Cu, Mn, Zn in prey and Fe, Co, Cu, Ni, Li in surface soils were significantly different (P < 0.05). Mean metal concentrations of Cr, Pb and Cd were relatively higher in little egret whereas Cu and Mn were higher in the egg contents of cattle egret. The mean concentrations of Cu, Mn and Zn were higher in prey samples of cattle egrets and Cr, Cd and Pb in prey samples of little egrets. In soil samples collected from little egret heronries metal concentrations were higher except Cu and Ni. Correlation Analysis and Hierarchical Agglomerative Cluster Analysis (HACA) identified relatively similar associations of metals and their source identification. Metals such as Fe, Cu, Mn, and Li were related with geochemical origin from parent rock material as well as anthropogenic input whereas Cr, Cd, Pb, Ni, Co and Zn were associated mostly with anthropogenic activities. The study suggested that eggs are useful bio-monitor of local heavy metal contamination.     

Metal concentrations and mobility in marine sediment and groundwater in coastal reclamation areas: a case study in Shenzhen, China

The concentrations of metals in the buried marine sediment and groundwater were differently affected by land reclamation. Nine metals (V, Cr, Mn, Co, Ni, Cu, Zn, Cd and Pb) in sediment and coastal groundwater from reclamation areas in Shenzhen were examined. The gradually decreased concentrations (V, Cr, Mn, Ni, Cu, Zn) in sediment and relatively higher concentrations (V, Cr, Mn, Co, Ni, Cu and Cd) in groundwater within reclamation areas were observed. The increase of V, Cr, Mn, Ni, Cu and Cd concentrations in groundwater within reclamation areas subsequently after land reclamation should be resulted from the mobilization of these metals accumulated in the sediment. These metals appear to be easily mobilized from solid phase to solution phase after reclamation. The physico-chemical changes such as reduction in pH and salinity in water environment induced by land reclamation appear to be responsible for metal mobility in the sediment-groundwater system.     

The influence of body size, condition index and tidal exposure on the variability in metal bioaccumulation in Mytilus edulis

Mussels are commonly used to monitor metal pollution despite high inter-individual variability in tissue concentrations. In this study, influences of body size, condition index and tidal height on concentrations of As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn were investigated. Body weight was inversely related to metal concentrations and for Cd, Mn, Pb and Zn the regression was affected by tidal height. Except for As, Fe and Mn metal concentrations were inversely related to physiological status though no differences between essential and non-essential metals were obvious. After correcting for body size, tidal height was related positively to As, Cd and Zn, negatively related to Cu, Fe and Mn while Co, Cr, Ni and Pb were independent of tidal height. The study recommends stringent measures during sampling for biomonitoring or metal concentrations at each location must be normalized to a common body size, CI and tidal height.     

Estimation of metal uptake efficiencies from precipitation in mosses in Lithuania

The main sources contributing to heavy metal content in mosses in Lithuania were examined by a comparison of heavy metal concentrations in moss and corresponding deposition levels calculated from bulk deposition analysis. Bulk deposition was collected in open areas as well as under the canopy of trees. Uptake efficiencies in moss were calculated for Cd, Cr, Cu, Fe, Mn, Ni, V and Zn. All elements in moss except Pb and Cd appeared to be more or less influenced by sources other than air pollution. The general order of this influence on the heavy metal content in moss was observed as follows: Ni < V < Cr < Zn < Fe < Mn. The contents of Mn and Zn in moss were greatly influenced by leaching from the canopy while Pb was the only element which showed a net metal retention by the canopy. Concentrations of Fe and Cr in moss were dominating due to contribution from soil dust.     

Survey of heavy metal pollution and assessment of agricultural soil in Yangzhong district, Jiangsu Province, China

We investigated concentrations of Hg, Cd, Pb, Zn, Cu, As, Ni, and Cr in samples of soil, cereal, and vegetables from Yangzhong district, China. Compared to subsoils, the sampled topsoils are enriched in Hg, Cd, Cu, Pb, Zn, and As. High levels of Cd and Hg are observed in most agricultural soils. Concentrations of Cr and Ni show little spatial variation, and high Cu, Pb, and Zn contents correspond well to areas of urban development. High As contents are primarily recorded at the two ends of the sampled alluvion. The contents of Cd, Hg, and total organic carbon (TOC) increase gradually to maximum values in the upper parts of soil profiles, while Cr and Ni occur in low concentrations within sampled profiles. As, Pb, Cu, and Zn show patterns of slight enrichment within the surface layer. Compared to data obtained in 1990, Cd and Hg show increased concentrations in 2005; this is attributed to the long-term use of agrochemicals. Cr and Ni contents remained steady over this interval because they are derived from the weathering of parent material and subsequent pedogenesis. The measured As, Cu, Pb, and Zn contents show slight increases over time due to atmospheric deposition of material sourced from urban anthropogenic activity. Low concentrations of heavy metals are recorded in vegetables and cereals because the subalkaline environment of the soil limits their mobility. Although the heavy metal concentrations measured in this study do not pose a serious health risk, they do affect the quality of agricultural products.     

Use of sequential extraction to assess metal partitioning in soils

The state of heavy metal pollution and the mobility of Cd, Cu, Ni, Cr, Pb and Zn were studied in three texturally different agricultural soil profiles near a Cu-Ni smelter in Harjavalta, Finland. The pseudo-total concentrations were determined by an aqua regia procedure. Metals were also determined after division into four fractions by sequential extraction with (1) acetic acid (exchangeable and specifically adsorbed metals), (2) a reducing agent (bound to Fe/Mn hydroxides), (3) an oxidizing agent (bound to soil organic matter) and (4) aqua regia (bound to mineral structures). Fallout from the smelter has increased the concentrations of Cd, Cu and Ni in the topsoil, where 75-90% of Cd, 49-72% of Cu and 22-52% of Ni occurred in the first two fractions. Slight Pb and Zn pollution was evident as well. High proportions of mobile Cd, Cu and Ni also deeper in the sandy soil, closest to the smelter, indicated some downward movement of metals. The hydroxide-bound fraction of Pb dominated in almost all soils and horizons, while Ni, Cr and Zn mostly occurred in mineral structures. Aqua regia extraction is usefully supplemented with sequential extraction, particularly in less polluted soils and in soils that exhibit substantial textural differences within the profiles.     

Processes controlling metal transport and retention as metal-contaminated groundwaters efflux through estuarine sediments

Factors affecting the transport and retention of Cd, Cr, Cu, Ni, Pb and Zn in acidic groundwaters as they pass through estuarine sediments were investigated using column experiments. Acidic groundwaters caused the rapid dissolution of iron sulfide (AVS) and other iron and manganese phases from sediments that are important for metal binding and buffering. Metal breakthrough to overlying water occurred in the order of Ni>Zn>Cd>Cu>Cr/Pb. Metal transport increased as the sediment permeability increased, reflecting the low resistance to flow caused by larger sand-sized particles and the decreased abundance of metal adsorption sites on these materials. Metal mobility increased as the groundwater pH decreased, as flow rate or metal concentrations increased, and as the exposure duration increased. Groundwater Cr and Pb were promptly attenuated by the sediments, the mobility of Cu was low and decreased rapidly as sediment pH increased above 4.5, while Cd, Ni and Zn were the most easily transported to the surface sediments and released to the overlying waters. For groundwaters of pH 3, metal migration velocities through sandy sediments were generally 0.5-2% (Cr, Pb), 1-6% (Cu) and 4-13% (Cd, Ni, Zn) of the total groundwater velocity (9-700 m/yr). The oxidative precipitation of Fe(II) and Mn(II) in the groundwaters did not affect metal mobility through the sediments. The results indicated that the efflux of acidic and metal-contaminated groundwater through estuarine sediments would affect organisms resident in sandy sediments more greatly than organisms resident in fine-grained, silty, sediments.     

Residual metal concentrations in soils and leaf accumulations in tobacco a decade following farmland application of municipal sludge

The objectives of this investigation were to examine the long-term residual effects of metal loading through sewage sludge applications on the total vs. diethylene triamine pentacetic acid (DTPA) extractable metal concentrations in soil and leaf accumulations in tobacco. Maryland tobacco (Nicotiana tabacum L.), cv. 'MD 609', was grown in 1983 and 1984 at two sites in Maryland that had been amended in 1972 with dewatered, digested sewage sludge from washington, DC, at rates equal to 0, 56, 112 and 224 mg ha(-1). The metal concentrations in the sludge, in mg kg(-1) dry weight, were: 1300 Zn, 570 Cu, 280 Pb, 45 Ni and 13 Cd. Soil samples collected from the surface horizon and composite leaf samples of cured tobacco were analyzed for total Zn, Cu, Mn, Fe, Pb, Ni and Cd concentrations. The soil samples were also examined for soil pH and DTPA extractable metals. Equations were generated using polynomic and stepwise regression analyses which described the relationships between total vs. DTPA extractable soil metals, and between DTPA soil and soil pH vs. plant metal concentrations, respectively. Significant increases were observed for both total and DTPA extractable metal concentrations for all metals, with all but total Mn and Ni being significant for linear and quadratic effects regarding sludge rates. However, linear relationships were found between DTPA extractable vs. total soil concentrations for all elements except Pb and Ni which were quadratic. Significant increases in plant Zn, Cu, Mn, Ni and Cd and decreases in Fe were observed with increased sludge rates. Plant Pb levels were unaffected by sludge applied Pb. Linear relationships were observed between plant Zn and Cd and DTPA soil metal levels: however, Mn and Cu levels were described by quadratic and cubic relationship, respectively. Relationships between plant Fe and Pb and DTPA extractable concentrations were nonsignificant. Additional safeguards to protect crop contamination from heavy metals such as Cd were discussed.     

Selected trace metals in oysters (Crassostrea iridescens) and sediments from the discharge zone of the submarine sewage outfall in Mazatlán Bay (southeast Gulf of California): chemical fractions and bioaccumulation factors

Concentrations of Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn in the soft tissue of Crassostrea iridescens and the associated surface sediments (bulk and bioavailable metal concentrations) from an area influenced by a sewage outfall in Mazatlán Bay (southeast Gulf of California), were determined by atomic absorption spectrophotometry. Significant spatial differences in metal concentrations in both the bulk and bioavailable forms in the sediments were identified. An enrichment of Cu, Ni, Pb and Zn in sites located on a south-north transect was detected indicating a dominant influence of the sewage outfall toward the north. C. iridescens accumulated more Zn, Cu, Ni, Fe, Cd; and less Mn, Cr and Pb than were bioavailable in the sediments, as measured using conventional extraction analysis. The degree of enrichment and the bioavailable metal concentrations in the sediments of the south portion of Mazatlán Bay is discussed. The potential ability of C. iridescens as a biomonitor of metallic pollutants is postulated.     

Mobility of heavy metals from polluted sediments of a semi-enclosed basin: in situ benthic chamber experiments in Taranto’s Mar Piccolo (Ionian Sea,Southern Italy)

In situ benthic flux experiments were conducted at two stations in the Mar Piccolo of Taranto (Italy), one of the most industrialised and contaminated coastal areas of the Mediterranean. Sediments of the two stations are notably different in their trace metal content, with a station closer to a Navy harbour showing higher mean concentrations of almost all investigated metals (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn). Conversely, both stations are characterised by significant Hg contamination, compared to the local baseline. Results of a sequential extraction scheme on surface sediments suggest a relatively scarce mobility of the examined metals (Zn > Ni > Cr > As > Cu > Pb). A Hg-specific extraction procedure showed that most of the element (93.1 %) occurs in a fraction comprising Hg bound to Fe/Mn oxi-hydroxides. Reduction of these oxides may affect Hg remobilisation and redistribution. Porewater profiles of dissolved trace metals were quite similar in the two sites, although significant differences could be observed for Al, Cu, Fe and Hg. The highest diffusive fluxes were observed for As, Fe and Mn. Mobility rates of several trace elements (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn) were directly measured at the sediment–water interface. Results from benthic in situ incubation experiments showed increasing dissolved metal concentrations with time, resulting in higher fluxes for Cu, Fe, Hg, V and Zn in the most contaminated site. Conversely, fluxes of Mn, Ni and Pb were comparable between the two stations. The estimated flux of Hg (97 μg m^?2 day^?1) was the highest observed among similar experiments conducted in other highly contaminated Mediterranean coastal environments. Benthic fluxes could be partially explained by considering rates of organic matter remineralisation, dissolution of Fe/Mn oxy-hydroxides and metal speciation in sediments. Seasonal and spatial variation of biogeochemical parameters can influence metal remobilisation in the Mar Piccolo area. In particular, metals could be promptly remobilised as a consequence of oxygen depletion, posing a serious concern for the widespread fishing and mussel farming activities in the area.     

Evaluation of diffusive gradients in thin film (DGT) samplers for measuring contaminants in the Antarctic marine environment

This work has been the first application of DGT samplers for measuring metals in water and sediment porewater in the Antarctic environment, and whilst DGT water sampling was restricted to quantification of Cd, Fe and Ni, preconcentration using Empore chelating disks provided results for an additional nine elements (Sn, Pb, Al, Cr, Mn, Co, Cu, Zn, As). Although higher concentrations were measured for some metals (Cd, Ni, Pb) using the Empore technique, most likely due to particulate-bound or colloidal species becoming entrapped in the Empore chelating disks, heavy metal concentrations in the impacted Brown Bay were found to be comparable with the non-impacted O'Brien Bay. Sediment porewater sampling using DGT also indicated little difference between Brown Bay and O'Brien Bay for many metals (Cd, Al, Cr, Co, Ni, Cu), however, greater amounts of Pb, Mn, Fe and As were accumulated in DGT probes deployed in Brown Bay compared with O'Brien Bay, and a higher accumulation of Sn was observed in Brown Bay inner than any of the other three sites sampled. Comparison of DGT derived porewater concentrations with actual porewater concentrations showed limited resupply of Cd, Pb, Al, Cr, Mn, Co, Ni, Cu, Zn and As from the solid phase to porewater, with these metals appearing to be strongly bound to the sediment, however, resupply of Fe and Sn was apparent. Based upon our observations here, we suggest that Sn, and to a lesser extent Pb, are critical contaminants.     

The asiatic clam, Corbicula fluminea: An indicator of trace metal pollution in the Shatt al-Arab River, Iraq

The potential of Corbicula fluminea (Müller) as an indicator for trace metal pollution was investigated. Laboratory experiments show that Corbicula has the capability to accumulate and eliminate trace metals in relation to their concentrations in ambient water. However, an effect of individual size was observed. Seasonal variations in the concentrations of Cd, Co, Cu, Fe, Mn, Ni, Pb, V and Zn in Corbicula, water and particulate matter from the upper section of the Shatt al-Arab River were studied. Sediment samples were also analysed. Metal concentrations were determined by means of flameless AAS. It was found that Corbicula is a suitable bio-indicator for monitoring of trace metal pollution. Metal concentrations in Corbicula tissues correlated better with their corresponding concentrations in particulate matter than with the dissolved form. Temporal variations in metal concentrations were attributed to several factors, including fluctuations in metal inputs, and in geochemical and hydrological characteristics of the water. The obtained levels of trace metals were comparable to those reported for control sites, with the exception of Cd, Cu and Zn whose concentrations were higher in both Corbicula and particulate matter.     

Trace metal behaviour in the Conwy estuary,North Wales

The distribution of trace metals Zn, Ni, Mn, Fe, Cu, Pb, Cd and Cr between suspended particulate matter (SPM) and water in the Conwy estuary, North Wales, has been studied in three surveys in 1998. Dissolved Cu and Mn showed some monthly variations. Most of the dissolved trace metals displayed a negative association with salinity, indicating rivers as a major source of inputs for them. Particulate Zn, Mn and Fe showed a decreasing concentration seaward, whilst the levels of Ni, Cu, Cr and Pb increased with salinity. SPM concentration was the most important variable significantly related to trace metal concentrations in SPM, with an inverse relationship between the two parameters. This was explained by the relative enrichment of trace metals in fine particles at low SPM concentrations and relative depletion of trace metals in coarse particles at high SPM concentrations. Particulate Zn, Mn and Pb were dominated by the fraction available to acetic acid (non-detrital), whilst particulate Ni, Fe and Cr were dominated by the fraction available to nitric acid (detrital). The partition coefficient of trace metals between SPM and water declined with increasing SPM concentration, consistent with the so-called "particle concentration effect". Such a phenomenon may be explained by the presence of fine particles (including colloids) enriched with trace metals at low SPM concentrations, and the salinity-induced desorption.     

Growth and trace metal accumulation of two Salix clones on sediment-derived soils with increasing contamination levels

The growth and metal uptake of two willow clones (Salix fragilis 'Belgisch Rood' and Salix viminalis 'Aage') was evaluated in a greenhouse pot experiment with six sediment-derived soils with increasing field Cd levels (0.9-41.4 mg kg-1). Metal concentrations of eight elements were measured in roots, stems and leaves and correlated to total and soil water metal concentrations. Dry weight root biomass, number of leaves and shoot length were measured to identify eventual negative responses of the trees. No growth inhibition was observed for both clones for any of the treatments (max. 41.4 mg kg-1 Cd, 1914 mg kg-1 Cr, 2422 mg kg-1 Zn, 655 mg kg-1 Pb), allowing their use for phytoextraction on a broad range of contaminated sediments. However, dry weight root biomass and total shoot length were significantly lower for S. viminalis compared to S. fragilis for all treatments. Willow foliar Cd concentrations were strongly correlated with soil and soil water Cd concentrations. Both clones exhibited high accumulation levels of Cd and Zn in aboveground plant parts, making them suitable subjects for phytoextraction research. Cu, Cr, Pb, Fe, Mn and Ni were found mainly in the roots. Bioconcentration factors of Cd and Zn in the leaves were highest for the treatments with the lowest soil Cd and Zn concentration.     

A comparison of Cu, Pb, As, Cd, Zn, Fe, Ni and Mn determined by acid extraction/ICP-OES and ex situ field portable X-ray fluorescence analyses

Total concentrations of Cu, Pb, As, Cd, Zn, Fe, Ni and Mn were determined for 81 soil samples using two types of field portable X-ray fluorescence (FPXRF) system; dual isotope and X-ray tube. FPXRF metal concentrations were statistically compared with analytical results from aqua regia extractions followed by Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-OES) analysis. The ability of each FPXRF instrument to produce analytical results comparable to the reference method was assessed by linear regression. A high degree of linearity was found for Fe and Pb with the X-ray tube instrument and for Fe, Cu, Pb, Zn, Cd and Mn with the dual source instrument. FPXRF analyser performance improved with increased analysis time for Cu, Mn and Pb, whilst Fe, Zn, Cd, Ni and As showed no significant improvement. Particle size did not influence FPXRF analyser performance. Both the dual isotope and the X-ray tube FPXRF instruments are effective tools for rapid, quantitative assessment of soil metal contamination and for monitoring the efficacy of remediation strategies.     

Heavy metal distribution in marine sediments from the southwest coast of Spain

The latest version (1999) of the BCR-sequential extraction technique was used to determine the distribution of metals (Cu, Zn, Cd, Pb, Fe, Ni, Cr, and Mn) with major sedimentary phases (acid-soluble, reducible, oxidisable and residual) in samples from the southwest coast of Spain. The total metal content was also determined. The results showed that an extensive area along the coast (35 km long), near the joint mouth of the Tinto and Odiel Rivers, contains sediments with high concentrations of metals, with maximums of 649 mg/kg of Zn, 336 mg/kg of Cu, 197 mg/kg of Pb and 2.5 mg/kg of Cd. The values found for Cr, Ni and Mn are comparable to those in unpolluted areas. Based on the chemical distribution of metals, we found that Zn is the most mobile (i.e., it can pass easily into the water under changing environmental conditions). This metal showed the highest percentages in the acid-soluble fraction (the most labile), especially in the central coastal area, where the samples contained over 50% of this element associated with this fraction. This area close to the Tinto and Odiel river mouths also shows a significant increase in the mobility of Cd and Cu. In both cases the amount present in the residual fraction is lower, and the acid-soluble fraction is increased for Cd and the oxidisable fraction for Cu. However, the highest percentages of Fe, Cr and Ni are found in the residual fraction (84%, 89% and 75%, respectively), which implies that these metals are strongly bound to the sediments.     

Heavy metal contamination in surface sediments of Yangtze River intertidal zone: An assessment from different indexes

Surface sediments (0-5 cm) from 59 stations within the Yangtze River intertidal zone (YRIZ) were sampled for metal contamination analysis in April and August 2005. The concentrations ranged (in mg kg⁻¹ dry weight): Al, 40,803-97,213; Fe, 20,538-49,627; Cd, 0.12-0.75; Cr, 36.9-173; Cu, 6.87-49.7; Mn, 413-1,112; Ni, 17.6-48.0; Pb, 18.3-44.1; and Zn, 47.6-154; respectively. Among the 59 sampling stations, enrichment factors (EF) indicate enrichment of Cd (52 stations), Cr (54 stations), Cu (5 stations), Ni (26 stations), Pb (5 stations) and Zn (5 stations). Geoaccumulation indexes (I_geo) also suggest individual metal contamination in localized areas. This study indicates that Cd, Cr and Ni enrichment in the YRIZ sediment is widespread whereas Cu, Mn, Pb and Zn enrichment is localized or nonexistent. Factor and cluster analyses indicate that Cd is associated with total organic carbon whereas Cu, Cr, Ni, Pb and Zn have a close association with Mn.     

Trace metal concentrations and their distribution in the lobster Panulirus inflatus (Bouvier, 1895) from the Mexican Pacific coast

The concentration and distribution of Fe, Mn, Ni, Cu, Co, Cd, Cr and Zn among the tissues of female and male lobster Panulirus inflatus from the Pacific coast of México were determined. Distinct inter-tissue and intersize differences in metal concentrations were observed. In general, highest Zn concentrations were found in viscera while highest Cu levels occurred in the gill and gonadal material. The highest Mn, Ni, Cr and Co concentrations were observed in exoskeleton and highest in eggs and gills. Cadmium was undetectable (<0.05 microg g(-1)) in most tissues, only muscle and viscera contained low but detectable amounts. A positive relationship between size and metal concentration was observed only for Zn contained in the muscle of females and males, for Zn contained in the gonad of females, for Mn contained in the gonad of males and for Cu associated with muscle of males. These results are discussed with regard to trace metal concentrations found in temperate and tropical regions.     

Heavy metal monitoring of marine algae from the Turkish Coast of the Black Sea, 1998-2000

Concentrations of Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn were determined in macroalgae samples collected from the Turkish Coast of the Black Sea. Certain algae species were chosen among the green, brown and red algae species at Sile and Sinop sampling stations from 1998 to 2000. In general, as regards the influence of the collection sites on the whole metal accumulation, Sinop is considered to be more polluted than Sile. The concentrations of the heavy metals in Cystoseira barbata algae are compared with previous studies in the same stations. The results showed that all metal levels have gradually decreased during past years. At the same time, Cd, Co, Cr, Cu, Fe, Ni and Pb levels in the present study are lower than in Bosphorus and Marmara Sea algae. However, Mn and Zn concentrations are higher than Bosphorus but lower than at Marmara. According to these findings the heavy metal pollution decreased in Turkish Coast of the Black Sea during the years investigated.