Distribution of Co,Cu, Fe,Mn, Se,Zn, and Cd among cytosolic proteins of different molecular masses in gills of European chub (Squalius cephalus L.)

The distribution of essential elements Co, Cu, Fe, Mn, Se, and Zn, and nonessential element Cd among cytosolic proteins of different molecular masses in the gills of European chub (Squalius cephalus) sampled in the moderately contaminated Sutla River in September of 2009, was studied after the protein separation by size exclusion high-performance liquid chromatography (SEC-HPLC), and the metal determination in the obtained fractions by high-resolution inductively coupled plasma mass spectrometry (HR ICP-MS). The aims of the study were to characterize the distribution profiles of metals within different protein categories in gills in the conditions of low metal exposure in the river water, and to compare them with the previously published hepatic profiles. The distribution profiles of analyzed metals were mainly characterized with several peaks. However, some observations could be emphasized: both Cu and Cd were eluted near metallothionein elution time; elution time of one of Co peaks could be associated with Co-containing compound cobalamin; increasing cytosolic Fe concentrations resulted in possible Fe binding to storage protein ferritin; both Mn and Zn had poorly resolved peaks covering wide ranges of molecular masses and indicating their binding to various proteins; both Zn and Se increased in protein fractions of molecular masses <5 kDa following their concentration increase in the gill cytosol; expected clear metallothionein peak was not observed for Zn. Comparison of gill profiles with previously published hepatic profiles revealed similar and in case of some elements (e.g., Co, Fe, Mn, and Se) almost identical distributions in both organs regarding elution times. On the contrary, heights of obtained peaks were different, indicating possible metal binding to the same proteins in the gills and liver, but in different proportions. The results obtained in this study can be used as a basis for comparison in monitoring studies, for identification of changes that would occur after exposure of chub to increased metal concentrations.     

Molecular cloning and expression of novel metallothionein (MT) gene in the polychaete Perinereis nuntia exposed to metals

To report a novel metallothionein (MT) gene and evaluate its potency as a biomarker, we clone this MT gene and measured the expression levels in the metal-exposed polychaete Perinereis nuntia. Accumulated metal contents and metallothionein-like proteins (MTLPs), which have been recognized as potential biomarkers, were compared with the relative mRNA expressions of the MT gene of P. nuntia (Pn-MT). In addition, the metal-binding affinity was estimated by recombinant Pn-MT protein. Pn-MT having high cysteine residues with three metal response elements in the promoter region closely clusters with those of other invertebrates. The accumulation patterns of metals were dependent on the exposure times in lead (Pb), cadmium (Cd), and copper (Cu) exposure. Particularly, both MTLP levels and relative mRNA expressions of MT were increased with accumulated metal contents and exposure time in P. nuntia exposed to Pb and Cd. There was no significant modulation of the Pn-MT gene in polychaetes exposed to Zn and As. However, the metal-binding ability of the recombinant Pn-MT protein provides a clear evidence for a high affinity of MT to several metal elements. These results suggest that Pn-MT would play an important role in the detoxification and/or sequestration of specific metals (e.g., Pb and Cd) in P. nuntia and have potential as a molecular biomarker in the monitoring of the marine environment using a polychaete.     

Relevance of biotic parameters in the assessment of the spatial distribution of gastrointestinal metal and protein levels during spawning period of European chub (Squalius cephalus L.)

The present field study, conducted during the spawning period (April/May) of European chub (Squalius cephalus L.) from the Sava River in Croatia, indicates that seasonal changes of fish physiological state might cause variability in gastrointestinal metal (Cd, Cu, Fe, Mn and Zn), total cytosolic protein and metallothionein (MT) levels. During the period of fish spawning and increased metabolic activity, a significant relationship with chub hepatosomatic index was evident for Fe and Mn in gastrointestinal tissue (r?=?0.35 and 0.26, respectively) and in cytosolic fraction (r?=?0.32 and 0.41, respectively) and for Zn and Fe in the gut content (r?=?0.36 and 0.31, respectively). Total cytosolic protein and MT concentrations followed the same spatial distribution as Fe and Mn in all gastrointestinal fractions and as Zn in the sub-cellular fractions, with higher levels at upstream locations. Due to the role of essential metals in metabolic processes and gonad development, increased feeding and spawning activity in April/May resulted in higher gastrointestinal essential metal (Fe, Mn and Zn) and MT concentrations, which probably follow an increase in Zn concentrations, known as the primary MT inducer. Therefore, biotic factors should be considered as important confounding factors in metal exposure assessment, while their influence on gastrointestinal metal and protein levels should be interpreted depending on the season studied.     

Lead concentration increase in the hepatic and gill soluble fractions of European chub (Squalius cephalus)—an indicator of increased Pb exposure from the river water

Purpose

To examine if chronic exposure of feral fish to elevated Pb concentrations in the river water (up to 1???g?L^?1), which are still lower than European recommendations for dissolved Pb in surface waters (7.2???g?L^?1; EPCEU (Official J L 348:84, 2008)), would result in Pb accumulation in selected fish tissues.

Methods

Lead concentrations were determined by use of HR ICP-MS in the gill and hepatic soluble fractions of European chub (Squalius cephalus) caught in the Sutla River (Croatia?CSlovenia).

Results

At the site with increased dissolved Pb in the river water, soluble gill Pb levels (17.3???g?L^?1) were approximately 20 times higher compared to uncontaminated sites (0.85???g?L^?1), whereas the ratio between contaminated (18.1???g?L^?1) and uncontaminated sites (1.17???g?L^?1) was lower for liver (15.5). Physiological variability of basal Pb concentrations in soluble gill and hepatic fractions associated to fish size, condition, sex, or age was not observed, excluding the possibility that Pb increase in chub tissues at contaminated site could be the consequence of studied biotic parameters. However, in both tissues of Pb-exposed specimens, females accumulated somewhat more Pb than males, making female chubs potentially more susceptible to possible toxic effects.

Conclusions

The fact that Pb increase in gill and hepatic soluble fractions of the European chub was not caused by biotic factors and was spatially restricted to one site with increased dissolved Pb concentration in the river water points to the applicability of this parameter as early indicator of Pb exposure in monitoring of natural waters.     

Geochemical behavior of metals and metalloids in an estuary affected by acid mine drainage (AMD)

The Tinto and Odiel rivers in southwest Spain drain the world’s largest sulfide mineral formation: the Iberian Pyrite Belt which has been worked since 2,500 BC. The Tinto and Odiel estuarine zones include both an extensive area of salt marsh and an intensively industrialized urban area. As a consequence of pyrite oxidation, the Tinto and Odiel rivers are strongly acidic (pH?<?3) with unusually high and quite variable metal concentrations. In this study, seasonally varying concentrations of dissolved major and trace elements were determined in the acid mine drainage affected estuary of the Ría de Huelva. During estuarine mixing, ore-derived metal concentrations exhibit excellent correlations with pH as the main controlling parameter. As pH increases, concentrations of dissolved ore-associated elements are attenuated, and this process is enhanced during the summer months. The decrease in Fe and Al concentrations ranged from 80 to 100 % as these elements are converted from dissolved to sediment-associated forms in the estuary. Coprecipitation/adsorption processes also removed between 60 and 90 % of the originally dissolved Co, Cu, Mn, Pb, Zn, and Th; however, Cd and Ni exhibited a greater propensity to remain in solution, with an average removal of approximately 60 %. On the other hand, As and U exhibited a different behavior; it is likely that these elements remain in dissolved forms because of the formation of U carbonates and soluble As species. Concentrations of As remain at elevated levels in the outer estuary (average?=?48 μg L^?1) which exceeds concentrations present in the Tinto River. Nevertheless, the estuary has recently witnessed improvements in water quality, as compared to results of several previous studies reported in the 1990s.     

Human health risk from organ-specific accumulation of toxic metals and response of antioxidants in edible fish species from Chenab River,Pakistan

In the current study, the bioaccumulation of essential and nonessential metals and related antioxidant activity were analyzed in three organs (muscle, gills, and liver) of herbivorous (HF) and carnivorous (CF) edible fish of Chenab River. The comparative analysis revealed a more heterogeneous accumulation of metals in the muscles of HF fish than that of CF fish [chromium (Cr, 3.4 μg g^?1), cobalt (Co, 1.7 μg g^?1), copper (Cu, 3 μg g^?1), and iron (Fe, 45 μg g^?1) versus Cr (1.3 μg g^?1), Co (0.1 μg g^?1), Cu (1.1 μg g^?1), and Fe (33 μg g^?1), respectively, P?<?0.001]. These results implied an organ-specific accumulation of metals at different trophic levels. According to logistic regression analysis, the bioaccumulation of metals had marked differences in HF and CF. The antioxidant activity was significantly related to the tissue type and the metals to which the organs are exposed to. The liver of CF fish had a higher activity of antioxidant superoxide dismutase (SOD), catalase (CAT), glutathione (GSH), and lipid peroxidase (LPO) than that of HF (P?<?0.05). LPO and guaiacol peroxidase (POD) in both groups were associated with a number of metals, but in HF, cadmium (Cd), Cr, Pb, and Zn were more related with the LPO and SOD activities. Moreover, Cd, Co, Fe, Pb, Ni, Cu, and Zn were above the permissible limits set by various agencies. In numerous cases, our results were even higher than those previously reported in the literature. The results provide an insight into the pollution pattern of Chenab River. These results may be helpful in the future to identify biomarkers of exposure in aquatic organisms.

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 toxic metal (Hg, Cd, Pb), polychlorinated biphenyl (PCBs), and pesticide (DDTs) levels in aromatic herbs collected in selected areas of Southern Italy

This study provides, for the first time, data regarding levels of toxic metals (Hg, Cd, and Pb) and organochlorine compounds (PCBs and DDTs) in various aromatic herbs as rosemary (Rosmarinus officinalis), sage (Salvia officinalis), laurel (Laurus nobilis), oregano (Origanum vulgare), and spearmint (Mentha viridis) collected in some towns of the Southern Italy with different anthropogenic and population pressure. Metal and organochlorine compound concentrations were determined using atomic absorption spectrophotometer and gas-chromatography mass spectrometer (GC/MS), respectively. Pb emerged as the most abundant element, followed by Cd and Hg, while between organochlorine compounds, PCB concentrations were higher than those of DDTs. The pollutant concentrations were found to vary depending on the different herbs. The highest Pb levels were observed in rosemary (1.66 μg g^?1 dry weight) and sage (1.41 μg g^?1 dry weight), this latter showing also the highest Cd concentrations (0.75 μg g^?1 dry weight). For PCBs, the major concentrations were found in rosemary (2.75 ng g^?1 dry weight) and oregano (2.39 ng g^?1 dry weight). The principal component analysis applied in order to evaluate possible similarities and/or differences in the contamination levels among sampling sites indicated differences area-specific contamination.     

Assessing the enrichment of heavy metals in surface soil and plant (Digitaria eriantha) around coal-fired power plants in South Africa

Nine metals (Fe, Cu, Mn, Ni, Cd, Pb, Hg, Cr, and Zn) were determined in soil and Digitaria eriantha plants within the vicinity of three coal power plants (Matla, Lethabo, and Rooiwal), using ICP-OES and GFAAS. The total metal concentration in soil ranged from 0.05?±?0.02 to 1836?±?70 μg g^?1, 0.08?±?0.05 to 1744?±?29 μg g^?1, and 0.07?±?0.04 to 1735?±?91 μg g^?1 in Matla, Lethabo, and Rooiwal, respectively. Total metal concentration in the plant (D. eriantha) ranged from 0.005?±?0.003 to 535?±?43 μg g^?1 in Matla, 0.002?±?0.001 to 400?±?269 μg g^?1 in Lethabo, and 0.002?±?0.001 to 4277?±?201 μg g^?1 in Rooiwal. Accumulation factors (A) of less than 1 (i.e., 0.003 to 0.37) at all power plants indicate a low transfer of metal from soil to plant (excluder). Enrichment factor values obtained (2.4–5.0) indicate that the soils are moderately enriched with the exception of Pb that had significant enrichment of 20. Geo-accumulation index (I-geo) values of metals indicate that the soils are moderately polluted (0.005–0.65), except for Pb that showed moderate to strong pollution (1.74–2.53).     

Impact of spiked concentrations of Cd,Pb, As and Zn in growth medium on elemental uptake of Nasturtium officinale (Watercress)

This study is aimed at investigating the impact of water quality on the uptake and distribution of three non-essential and toxic elements, namely, As, Cd and Pb in the watercress plant to assess for metal toxicity. The plant was hydroponically cultivated under greenhouse conditions, with the growth medium being spiked with varying concentrations of As, Cd and Pb. Plants that were harvested weekly for elemental analysis showed physiological and morphological symptoms of toxicity on exposure to high concentrations of Cd and Pb. Plants exposed to high concentrations of As did not survive and the threshold for As uptake in watercress was established at 5 ppm. Translocation factors were low in all cases as the toxic elements accumulated more in the roots of the plant than the edible leaves. The impact of Zn on the uptake of toxic elements was also evaluated and Zn was found to have an antagonistic effect on uptake of both Cd and Pb with no notable effect on uptake of As. The findings indicate that phytotoxicity or death of the watercress plant would prevent it from being a route of human exposure to high concentrations of As, Cd and Pb in the environment.     

Relationship between geographical origin and contents of Pb,Cd, and Cr in honey samples from the state of Paraná (Brazil) with chemometric approach

The aim of this study was to determine the trace elements, Pb, Cd, and Cr in honey samples from eight different regions from the state of Paraná (Brazil), using slurry sampling graphite furnace atomic absorption spectrometry. Chemometric analysis (principal component analysis (PCA)) was applied to classify honey samples according to their levels of the trace elements Pb, Cd, and Cr, which is also related to the geographical origin of honey samples. The mean concentration for the elements followed the order Pb?>?Cr >?>?Cd. The mean values were 200?±?76, 88?±?14, and 4.1?±?4 ng g^?1 for Pb, Cr, and Cd, respectively. It could be verified that honey samples are geographically separated, especially with regard to Pb and Cd contents. Thus, honey can be considered a bioindicator of environmental contamination, suggesting possible contamination in soil, water, and air. This contamination can be related to natural or anthropogenic sources present in the study regions.     

Subcellular distribution of trace elements in kidney of a mother-fetus pair of Dall's porpoises (Phocoenoides dalli)

Total and subcellular renal Zn, Cu, Se, Mn, V, Hg, Cd and Ag were determined by a mother-fetus pair of Dall's porpoises (Phocoenoides dalli). All element concentrations in the maternal individual were higher than those in the fetal individual. Most of total renal elements studied were present in the cytosol of both animals. In maternal cytosol, Mn, Hg and Ag were present in high molecular weight substances (HMW); Se was in low molecular weight substances (LMW); Zn, Cu, and Cd were in metallothionein (MT), mostly; and the distribution of V in percentage among the three renal cytosolic fractions was similar. In fetal cytosol, Zn, Mn, Hg, V, Cd, and Ag were present in HMW, Cu was present in MT, mostly. In contrast, Se was observed mostly in both LMW and HMW. MT isoforms were characterized. Three obvious peaks in retention time were found in either the maternal or fetal MT. The highest elemental ion intensities were in the 7.8min peak for the mother, and in the 4.3min peak for the fetus, respectively, implying that different MT isoforms may be closely associated with elemental accumulation between maternal and fetal renal cytosols.     

Multivariate characterization of elements accumulated in Wolfiporia extensa mushroom from Yunnan province of China

ABSTRACT

Dried sclerotia of Wolfiporia extensa have been used as medicine in Asia from Eastern Han Dynasty, and also used as traditional snack called “fulingjiabing” in Beijing, China. In this paper, 18 macro and trace elements (Ag, As, Ba, Cd, Co, Cr, Cs, Cu, Fe, Li, Mn, Ni, Pb, Rb, Se, Sr, V, and Zn) in both flesh and peel of Wolfiporia extensa from seven sites of Yunnan province in China were determined by inductively coupled plasma mass spectrometer. The average recovery rates of certified reference materials for GBW10015 (spinach leaves) ranged from 90.5 to 113%, for GBW10028 (citrus leaves) from 92.8 to 106%, and for GBW07603 (bush branch and leaves) from 83.3 to 114.6%. Generally speaking, the concentration of all elements determined was at common level. The results of this survey indicate that mineral compositions in peel were higher than in flesh. In peel, the contents of investigated trace metals in mushroom samples were found to be in the range of 1,660–13,400 µg·g^?1 dry matter (dm) for Fe and 29.6–710 µg·g^?1 dm for Mn. The mean contents of Cr, Cu, Rb, V, and Zn in peel were between 10 and 20 µg·g^?1 dm, followed by As, Co, Li, Ni, Pb, Se, and Sr with mean contents between 1 and 10 µg·g^?1 dm, while Ag, Cd, and Cs had mean contents of <1 µg·g^?1 dm. In flesh, the concentration of Fe was in the range of 54–900 µg·g^?1 dm, and it was 1.5–49 µg·g^?1 dm for Mn, followed by Ba, Cu, Rb, and Zn in the range of 1 to 10 µg·g^?1 dm, while for Ag, As, Cd, Co, Cr, Cs, Li, Ni, Pb, Se, Sr, and V it was <1 µg·g^?1 dm. The concentration of toxic elements, such as As, Cd, and Pb, in both flesh and peel was below the permissible limits of World Health Organization. However, As and Pb contents in peel were higher than the limits permitted in the Chinese Pharmacopoeia. The results of principal component analysis showed that the flesh of Wolfiporia extensa from all the seven sites of the Yunnan province tend to cluster together, most probably because the origin of mineral elements in both flesh and peel is wood substrate (old and dead pine trees).     

Modification of trace metal accumulation in the green mussel Perna viridis by exposure to Ag, Cu, and Zn

To examine the Cd, Hg, Ag, and Zn accumulation in the green mussel Perna viridis affected by previous exposure to Cu, Ag, or Zn, the dietary metal assimilation efficiency (AE) and the uptake rate from the dissolved phase were quantified. The mussel's filtration rate, metallothionein (MT) concentration, and metal tissue burden as well as the metal subcellular partitioning were also determined to illustrate the potential mechanisms underlying the influences caused by one metal pre-exposure on the bioaccumulation of the other metals. The green mussels were pre-exposed to Cu, Ag, or Zn for different periods (1-5 weeks) and the bioaccumulation of Cd, Hg, Ag, and Zn were concurrently determined. Pre-exposure to the three metals did not result in any significant increase in MT concentration in the green mussels. Ag concentration in the insoluble fraction increased with increasing Ag exposure period and Ag ambient concentration. Our data indicated that Cd assimilation were not influenced by the mussel's pre-exposure to the three metals (Cu, Ag, and Zn), but its dissolved uptake was depressed by Ag and Zn exposure. Although Hg assimilation from food was not affected by the metal pre-exposure, its influx rate from solution was generally inhibited by the exposure to Cu, Ag, and Zn. Ag bioaccumulation was affected the most obviously, in which its AE increased with increasing Ag tissue concentration, and its dissolved uptake decreased with increasing tissue concentrations of Ag and Cu. As an essential metal, Zn bioaccumulation remained relatively stable following the metal pre-exposure, suggesting the regulatory ability of Zn uptake in the mussels. Zn AE was not affected by metal pre-exposure, but its dissolved uptake was depressed by Ag and Zn pre-exposure. All these results indicated that the influences of one metal pre-exposure on the bioaccumulation of other metals were metal-specific due to the differential binding and toxicity of metals to the mussels. Such factors should be considered in using metal concentrations in mussel's soft tissues to evaluate the metal pollution in coastal waters.     

Assessment of general condition of fish inhabiting a moderately contaminated aquatic environment

The assessment of general condition of fish in the moderately contaminated aquatic environment was performed on the European chub (Squalius cephalus) caught in September 2009 in the Sutla River in Croatia. Although increases of the contaminants in this river (trace and macro elements, bacteria), as well as physico-chemical changes (decreased oxygen saturation, increased conductivity), were still within the environmentally acceptable limits, their concurrent presence in the river water possibly could have induced stress in aquatic organisms. Several biometric parameters, metallothionein (MT), and total cytosolic protein concentrations in chub liver and gills were determined as indicators of chub condition. Microbiological and parasitological analyses were performed with the aim to evaluate chub predisposition for bacterial bioconcentration and parasitic infections. At upstream river sections with decreased oxygen saturation (～50 %), decreased Fulton condition indices were observed (FCI: 0.94 g?cm^?3), whereas gonadosomatic (GSI: 2.4 %), hepatosomatic (HSI: 1.31 %), and gill indices (1.3 %) were increased compared to oxygen rich downstream river sections (dissolved oxygen ～90 %; FCI: 1.02 g?cm^?3; GSI: 0.6 %; HIS: ～1.08 %; gill index: 1.0 %). Slight increase of MT concentrations in both organs at upstream (gills: 1.67 mg?g^?1; liver: 1.63 mg?g^?1) compared to downstream sites (gills: 1.56 mg?g^?1; liver: 1.23 mg?g^?1), could not be explained by induction caused by increased metal levels in the river water, but presumably by physiological changes caused by general stress due to low oxygen saturation. In addition, at the sampling site characterized by inorganic and fecal contamination, increased incidence of bacterial bioconcentration in internal organs (liver, spleen, kidney) was observed, as well as decrease of intestinal parasitic infections, which is a common finding for metal-contaminated waters. Based on our results, it could be concluded that even moderate contamination of river water by multiple contaminants could result in unfavourable living conditions and cause detectable stress for aquatic organisms.     

Total and subcellular distribution of trace elements (Cd, Cu and Zn) in the liver and kidney of green turtles (Chelonia mydas) from the Mediterranean Sea

This study investigated the subcellular distribution of Cd, Cu and Zn in liver and kidney of green turtles (Chelonia mydas) stranded along the Italian coast of the South Adriatic Sea (Eastern Mediterranean). Cd and Zn mean concentrations did not differ significantly between liver (4.26microgg(-1) and 34.53microgg(-1), respectively) and kidney (5.06microgg(-1) and 26.39microgg(-1), respectively), whereas the levels of Cu were significantly higher in liver (32.75microgg(-1)) than in kidney (8.20microgg(-1)) (p<0.009). Most of Cd, Cu and Zn was present in hepatic and renal cytosol, and their concentrations increased with total levels in both organs, indicating that cytosol has a crucial role in metal accumulation. Cd and Cu in hepatic and renal cytosol were present mostly in metallothionein fractions (MTs), whereas Zn was fractionated into MTs and high-molecular-weight-substances (HMWS). The comparison with the results of other investigations on individuals of the same species collected in different marine areas shows good agreement relatively to essential metals. For Cd our data are comparable with those encountered in specimens from the Mediterranean Sea (Cyprus) confirming the homogeneity of the area comprising the south-eastern basin of the Mediterranean Sea from an ecological point of view.     

Removal of Pb(II), Cd(II), Cu(II), and Zn(II) by hematite nanoparticles: effect of sorbent concentration, pH, temperature, and exhaustion

Nanoparticles offer the potential to improve environmental treatment technologies due to their unique properties. Adsorption of metal ions (Pb(II), Cd(II), Cu(II), Zn(II)) to nanohematite was examined as a function of sorbent concentration, pH, temperature, and exhaustion. Adsorption experiments were conducted with 0.05, 0.1, and 0.5 g/L nanoparticles in a pH 8 solution and in spiked San Antonio tap water. The adsorption data showed the ability of nanohematite to remove Pb, Cd, Cu, and Zn species from solution with adsorption increasing as the nanoparticle concentration increased. At 0.5 g/L nanohematite, 100 % Pb species adsorbed, 94 % Cd species adsorbed, 89 % Cu species adsorbed and 100 % Zn species adsorbed. Adsorption kinetics for all metals tested was described by a pseudo second-order rate equation with lead having the fastest rate of adsorption. The effect of temperature on adsorption showed that Pb(II), Cu(II), and Cd(II) underwent an endothermic reaction, while Zn(II) underwent an exothermic reaction. The nanoparticles were able to simultaneously remove multiple metals species (Zn, Cd, Pb, and Cu) from both a pH 8 solution and spiked San Antonio tap water. Exhaustion experiments showed that at pH 8, exhaustion did not occur for the nanoparticles but adsorption does decrease for Cd, Cu, and Zn species but not Pb species. The strong adsorption coupled with the ability to simultaneously remove multiple metal ions offers a potential remediation method for the removal of metals from water.     

Challenges with tracing the fate and speciation of mine-derived metals in turbid river systems: implications for bioavailability

The fast-flowing and highly turbid Lagaip River (0.5–10 g/L suspended solids) in the central highlands of Papua New Guinea receives mine-derived metal inputs in both dissolved and particulate forms. Nearest the mine, metal concentrations in suspended solids were 360, 9, 90, 740 and 1,300 mg/kg for As, Cd, Cu, Pb and Zn, while dissolved concentrations were 2.7, 0.6, 3.1, 0.1 and 25 μg/L, respectively. This creates a significant metal exposure source for organisms nearer the mine. However, because the Lagaip River is diluted by a large number of tributaries, the extent to which mine-derived metals may affect biota in the lower catchments is uncertain. To improve our understanding of the forms of potentially bioavailable metals entering the lower river system, we studied the partitioning and speciation of metals within the Lagaip River system. Dissolved and particulate metal concentrations decreased rapidly downstream of the mine due to dilution from tributaries. As a portion of the particulate metal concentrations, the more labile dilute acid-extractable forms typically comprised 10–30 % for As and Pb, 50–75 % for Cu and Zn, and 50–100 % for Cd. Only dissolved Cd, Cu and Zn remained elevated relative to the non-mine-impacted tributaries (<0.03, 0.5 and 0.3 μg/L), but the concentrations did not appreciably change with increasing dilution downriver. This indicated that release of Cd, Cu and Zn was likely occurring from the more labile metal phases of the mine-derived particulates. Chelex-labile metal analyses and speciation modelling indicated that dissolved copper and lead were largely non-labile and likely complexed by naturally occurring organic ligands, while dissolved cadmium and zinc were predominantly present in labile forms. The study confirmed that mine-derived particulates may represent a significant source of dissolved metals in the lower river system; however, comparison with water quality guidelines indicates the low concentrations would not adversely affect aquatic life.     

Dry atmospheric inputs of trace metals at the Mediterranean coast of Israel (SE Mediterranean): sources and fluxes

This study presents the first detailed data on aerosol concentrations of trace metals (Cd, Pb, Cu, Zn, Cr, Mn, Fe and Al) at the SE Mediterranean coast of Israel, and assesses their sources and fluxes. Aerosol samples were collected at two sampling stations (Tel-Shikmona and Maagan Michael) along the coast between 1994 and 1997. Two broad categories of aerosol trace metal sources were defined; anthropogenic (Cd, Cu, Pb and Zn) and naturally derived elements (Al, Fe, Mn and Cr). The extent of the anthropogenic contribution was estimated by the degree of enrichment of these elements compared to the average crustal composition (EF_crust). High values (median >100) were calculated for Cd, Pb and Zn, minor values for Cu and relatively low values (<10) for Fe, Mn and Cr. The crustal-derived elements exhibited a statistically significant seasonal pattern of higher concentrations during spring and autumn (e.g. Al concentrations in some cases during these periods were observed to be in excess of 1500 ng m⁻³). In the eastern Mediterranean basin crustal-dominated elements are enriched by 2–3 times while others (Cd and Pb) are comparable to the northwestern Mediterranean. The Pb : Cd ratios of ∼150 are higher than in coastal European sites (60–116) or emission materials (∼50). It is speculated that these differences are attributed mainly to the mixing of crustal material with local and European emissions. At present, it is impossible to quantify the latter two fractions. Back trajectory analysis and the subsequent categorization of two main aerosol populations, ‘European’ and ‘North Africa–Arabian’, exhibited a significantly different geochemical imprint on the aerosol chemical composition. ‘European’-derived air masses indicated significantly higher EF_crust values for Cd and Pb due to the greater anthropogenic character of the aerosol population, with a dilution by crustal material of this population leading to comparatively lower EF_crust values associated with the North African–Arabian air masses.     

Elemental analysis of the edible fruit of Carpobrotus dimidiatus (from Kwazulu-Natal,South Africa) and the influence of soil quality on its elemental uptake

Abstract

Carpobrotus dimidiatus is an indigenous South African medicinal plant species from the Aizoaceae family that bears edible fruit that is consumed for nutritional value. In this study, the elemental distribution in C. dimidiatus fruit and growth soil from fifteen sites in KwaZulu-Natal (South Africa) was determined along with soil pH, soil organic matter and cation exchange capacity, to assess for nutritional value and the effect of soil quality on elemental uptake. The results showed elemental concentrations in fruit to be in decreasing order of Ca (6235–32755?mg kg^?1) > Mg (2250–5262?mg kg^?1) > Fe?>?Mn?>?Zn (20.9–50.6?mg kg^?1) > Cu (3.83–20.6?mg kg^?1) > Pb?>?Cr?>?Cd?>?As?～?Co?～?Ni?～?Se and no potential health risk due to metal toxicity from average consumption. For sites that had high levels of Cd and Pb, bioaccumulation occurred from atmospheric deposition. Concentrations of elements in soil were found to be in decreasing order of Fe (1059–63747?mg kg^?1) > Ca (1048–41475?mg kg^?1) > Mg?>?Mn (9.76–174?mg kg^?1) > Cr (1.55–135?mg kg^?1) > Zn (0.76–58.2?mg kg^?1) > Se?>?Cu?>?Ni?>?Pb?>?Co?>?As?～?Cd with no evidence of heavy metal contamination. This study revealed that the plant inherently controlled uptake of essential elements according to physiological needs and that the concentrations of essential elements in the fruit could contribute positively to the diet.