Adsorption of chromium and zinc ions from aqueous solutions by cellulosic graft copolymers

Cellulosic graft copolymers were prepared by the reaction of bast fibers of the kenaf plant (Hibiscus cannabinus) with acrylonitrile and methacrylonitrile monomers in aqueous media initiated by the ceric ion-toluene redox pair. The cellulose-polyacrylonitrile (Cell-PAN) and cellulose-polymethacrylonitrile (Cell-PMAN) graft copolymers were used for the removal of Zn(II) and Cr(III) ions from aqueous solutions at 30°C. Zn(II) ion was more sorbed than Cr(III) ion by both copolymers by an average factor of 1.80 ± 0.40. For each metal ion, the Cell-PAN graft copolymer was a more effective sorbent than the Cell-PMAN derivative. The amount of ion sorbed decreased with an increase in percentage graft and over the range 38–149% of the graft the amounts of Zn(II) and Cr(III) ions sorbed by Cell-PAN decreased by 44% and 56%, respectively.     

Heavy metal bioaccumulation by the organs of Phragmites australis (common reed) and their potential use as contamination indicators

The concentrations of heavy metals in the roots, rhizomes, stems and leaves of the aquatic macrophyte Phragmites australis (common reed), and in the corresponding water and sediment samples from the mouth area of the Imera Meridionale River (Sicily, Italy), were investigated to ascertain whether plant organs are characterized by differential accumulation, and to test the suitability of the various organs for heavy metal biomonitoring of water and soil. Heavy metals considered were Cd, Cr, Cu, Hg, Mn, Ni, Pb, Zn. Results showed that belowground organs were the primary areas of metal accumulation. In particular, metal concentrations in plant organs decreased in the order of root > rhizome ≥ leaf > stem. All four organs showed significant differences in concentration for Cr, Hg, Mn, Zn, thus suggesting low mobility from roots to rhizomes and to aboveground organs. Although the organs followed different decreasing trends of metal concentration, the trend Mn > Zn > Pb > Cu was found in each plant organ. Mn showed the highest concentrations in all organs whereas the lowest concentrations regarded Cd and Cr in the belowground and aboveground organs, respectively. The toxic threshold was exceeded by Cr in roots, rhizomes and leaves, Mn in roots and leaves, Ni in roots. The highest average concentrations were found as follows: Cd, Hg, Pb, Zn in root, Cr, Mn, Ni in sediment, Cu in water. Positive linear relationships were found between heavy metal concentrations in all plant organs and those in water and sediment, thus indicating the potential use of such organs for pollution monitoring of water and sediment. Advantages of using plant species as biomonitors, especially Phragmites australis, were also discussed.     

Effect of the presence of lead on the biosorption of copper,cadmium and nickel by anaerobic biomass

Heavy metals are toxic pollutants released into the environment as a result of industrial, mining and agricultural activities. The biosorption of Pb, Cu, Cd, and Ni from single and binary metal systems were studied in equilibrium systems and in a flow-through column packed with a calcium-saturated anaerobic sludge biosorbent, respectively. The single-metal sorption uptake capacity of the biomass for Pb was slightly inhibited by the presence of Cu and Cd cations (by 6%) and by the presence of nickel (by 11%). The affinity order of anaerobic biomass for the four metals was established as: Pb > Cu > Ni > Cd. Factors such as hydration effects, hydrolysis effects and covalent binding of the metal ions may contribute to this result. By studying the breakthrough curves obtained from a fixed bed column fed with an equimolar mixture of Pb, Cd, Cu, and Ni, it was determined that lead was the last metal to break through the column at the 150 bed volume mark compared to 4, 15, 30 bed volume marks for Ni, Cd, and Cu, respectively.     

Physiologically based extraction of heavy metals in compost: Preliminary results

A physiologically based extraction test (PBET) was run for the extraction of six metals (Cu, Zn, Cd, Cr, Ni and Pb) in four composts containing high concentrations of heavy metals. An aqueous solution of pepsin plus citric, acetic, and malic acids buffered to pH 2 was used to simulate the gastric mixture, and an extraction of 1 h at 37 °C was run with a solid:liquid ratio of 1:100. The results were compared to those obtained using water and CaCl₂–DTPA solution. The PBET extracted far more metals than water, but less than CaCl₂–DTPA for Cu, Pb and Cr, while giving similar or slightly lower results for Cd, Zn, and Ni.     

Metal complexes of crosslinked chitosans: Correlations between metal ion complexation values and thermal properties

A series of heavy metal complexes of crosslinked chitosans were evaluated by thermogravimetric studies. The metal complexes with Cu, Cd and Hg ions exhibiting the highest complexing ability to chitosans (Hg 354–364, Cu 100–112, and Cd 121–160, in mg/g chitosan), had the lowest onset of degradation temperatures (range 194–210 °C) and the lowest final degradation temperatures (generally less than 294–304 °C for Hg, 296–338 °C for Cu, and 305–368 °C for Cd complexes). Mn ion, with the lowest binding to chitosans (Mn 5–7 mg/g), showed the reverse behavior, having onset (240–248 °C) and final degradation temperatures (range 300–368 °C). Zn (binding 74–87 mg/g) and Pb (binding 39–62 mg/g) ions have a binding ability intermediate to Cu/Cd/Hg and Mn extremes, and therefore the effects on onset and final degradation temperatures are intermediate to these values.     

A ratiometric fluorescent detection of Zn(II) in aqueous solutions using pyrene-appended histidine

A fluorescent chemosensor, Py-His, based on histidine was easily synthesized in solid phase synthesis. Py-His displayed a highly sensitive ratiometric response to Zn(II) with potent binding affinity (K_a = 1.17 × 10¹³ M^?2) in aqueous solutions. The detection limit of Py-His for Zn(II) was calculated as 80.8 nM. Moreover, Py-His distinguished Zn(II) and Hg(II) by different ratiometric response type; the chemosensor showed a more enhanced increase of excimer emission intensity to Zn(II) than Hg(II). Upon addition of Ag(I) and Cu(II), Py-His showed a turn-off response mainly due to the quenching effect of these metal ions. The binding stoichiometry (2:1 or 1:1) of Py-His to target metal ions played a critical role in the fluorescent response type (ratiometric and turn off response) to target metal ions. The role of imidazole group of Py-His for ratiometric detection of Zn(II) was proposed by pH titration experiments.     

Geochemical baseline establishment and ecological risk evaluation of heavy metals in greenhouse soils from Dongtai,China

Currently, heavy metal (HM) contamination in greenhouse soils is a significant concern due to the rapid expansion of greenhouse agriculture. However, it is difficult to accurately assess HM pollution in greenhouse soils in China due to the lack of local geochemical baseline concentrations (GBCs) or corresponding background values. In the present study, the GBCs of HMs in Dongtai, a representative greenhouse area of China, were established from subsoils using cumulative frequency distribution (CFD) curves. The pollution levels of HMs and potential ecological risks were investigated using different quantitative indices, such as geo-accumulation index (I_geo), pollution index (PI), pollution load index (PLI) and ecological risk index (RI), based on these regional GBCs. The total concentrations of six metals (Cd, Cr, Cu, Ni, Pb and Zn) in surface soils were determined and shown to be lower than the concentrations reported in other greenhouse regions of China. The GBCs of Cd, Cr, Cu, Ni, Pb and Zn were 0.059–0.092, 39.20–54.50, 12.52–15.57, 20.63–23.26, 13.43–16.62 and 43.02–52.65 mg kg⁻¹, respectively. Based on this baseline criterion, Cd, Pb and Zn accumulated in the surface soils because they were present at concentrations higher than their baseline values. The soils were moderately polluted by Cd according to the I_geo values, and the PI results indicated that moderate Cd contamination was present in this area. The large variation of I_geo value of Cd revealed that Cd in this area was likely influenced by agricultural activities. The PLI showed that most of the study area was moderately polluted. However, an analysis of the RI showed that the investigated HMs had low ecological risks. Correlation analysis and principle component analysis suggested that the Cd, Pb and Zn in the greenhouse soils mainly originated from anthropogenic sources (agricultural activities, atmospheric deposition etc.), while Cr, Cu, and Ni originated from natural sources. The findings of this study illustrated the necessity of GBC establishment at the local scale to facilitate more accurate HM evaluation of greenhouse soils. It is advisable to pay more attention to Cd, which could cause environmental problems in the greenhouse system.     

Copper flotation waste from KGHM as potential sorbent for heavy metal removal from aqueous solutions

Sorption affinity of copper flotation waste from KGHM toward Cd(II), Cr(III), Cu(II), and Pb(II) ions was investigated in this work. Batch sorption studies, using single-element synthetic aqueous solutions at various pH (2–12), contact time (10–300 min), initial concentration (100–5000 mg dm^?3; 1–100 mg dm^?3 for Cd(II)) and adsorbent dose (25–200 g dm^?3), were performed. Bonding strength of adsorbed metals was tested from the degree of desorption. The maximum metal removal was observed at pH 5–8, ≥120 min reaction time, and 25 g dm^?3 adsorbent dose. Maximum sorption capacities of studied material were 41.6, 58.8, and 83.8 mg g^?1 for Cr(III), Cu(II), and Pb(II), respectively, for 5000 mg dm^?3 initial concentration, and 0.86 mg g^?1 for Cd(II) for initial concentration of 50 mg dm^?3. Sorption isotherms were very well fitted to Langmuir (Cd, Cr, Pb) and Freundlich (Cu) models. Sorption kinetics was nearly ideally fitted to pseudo-second-order kinetic model. Desorption studies showed that most of Cr(III) (98.5%) and Pb(II) (67.3%) ions remained bound to the surface, indicating that the chemisorption dominated as a controlling process. On the other hand, mostly desorbed were Cd(II) (98.5%) and Cu(II) (90.3%) ions, which indicated that processes like physisorption or precipitation were prevailing.     

Copper and zinc in Elodea canadensis from rivers with various pollution levels

The anthropogenic impact of xenobiotics contributes to environmental risk for the aquatic environment and thus, must be controlled. Elodea canadensis, a cosmopolitan aquatic macrophyte with an important role in the ecology of many littoral zones, may provide an integrated record of pollution. Therefore, it was interesting to investigate the accumulation of Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn in this species and in water and bottom sediments collected from rivers with various levels of contamination. Of these rivers one control and one polluted was selected for the collection of E. canadensis for an experiment to compare the ability of this species to accumulate Cu and Zn. These elements were supplemented at concentrations (mg L⁻¹) of 0.01, 0.02, 0.03, 0.05, 0.08 and 0.14 as CuSO₄·5H₂O, and 0.4, 0.6, 0.9, 1.4, 2.03 and 3.04 as ZnSO₄·7H₂O and in a mixture containing (mg L⁻¹) 0.01Cu + 0.4Zn, 0.02Cu + 0.6Zn, 0.03Cu + 0.9Zn, 0.05Cu + 1.4Zn, 0.08Cu + 2.03Zn and 0.14Cu + 3.04Zn. After the experiment, E. canadensis from the polluted river contained significantly higher Cu and Zn concentrations when applied separately and also significantly higher Cu and Zn concentrations when applied as a mixture compared to the control river. These higher concentrations in E. canadensis from the polluted river were found in all combinations in the experiment. Thus, E. canadensis habituated in polluted sites to the exposure, and long-term influence of elevated metal levels appeared to be better adapted, and it also exhibited a higher increase in biomass than plants from the control river in all the experimental Cu and Zn solutions. Younger leaves of E. canadensis were more resistant to the effects of Cu and Zn than older leaves. Both Cu and Zn negatively affected the cell structure of older leaves, although the influence of Cu on plasma membrane integrity and chloroplast distribution was stronger than that of Zn. The influence of the Cu + Zn mixture on E. canadensis resulted in less pronounced cell disintegration than the influence of Cu added separately.The explanation of differences in the E. canadensis biomass increase and metal concentrations under the binary Cu and Zn impact needs further examination.     

Heavy metals in wetland soils along a wetland-forming chronosequence in the Yellow River Delta of China: Levels,sources and toxic risks

Surface soil (0–20 cm) samples were collected from four chronological sequences of wetlands (i.e., >50-yr-old wetlands, 40-yr-old wetlands, 30-yr-old wetlands and 10-yr-old wetlands) in the Yellow River Delta of China in May and June of 2007. Total contents of Al, As, Cd, Cr, Cu, Ni, Pb and Zn were determined using inductively coupled plasma atomic absorption spectrometry (ICP-AAS) to investigate the levels, sources and toxic risks of heavy metals in these wetlands. Our results showed an increasing trend for Pb, Cu and Zn along the wetland-forming chronosequence although their pollution levels were low. Both As and Cd exhibited significant enrichment due to their high enrichment factor (EF) values (EF > 5), especially in older wetlands (i.e., >50-yr-old and 40-yr-old wetlands), whereas other heavy metals were minimally or moderately enriched in this region. The results of principal component analysis showed that 83.09% of total variance based on eigenvalues (eigenvalue > 1) could be explained by three principal components (PCs) in four wetlands. The source of Al, Cu, Pb and Zn was different from Cd, Cr and Ni. According to the sediment quality guidelines (SQGs) of China, soil samples in the younger wetlands, especially the 10-yr-old wetlands, were moderately polluted by As, Cd and Ni. According to the SQGs of US EPA, all soil samples were heavily polluted by As and moderately polluted by Ni and soil samples in the older wetlands were moderately polluted by Cr. However, with the exception of As and Ni, the contents of other heavy metals in the four wetlands did not exceed the probable effect level (PEL) values. As, Cd and Ni were identified as heavy metals of primary concerns in four wetlands, Cr were of moderate concern in older wetlands, and Pb, Cu and Zn should be paid more attention in younger wetland (i.e., 10-yr-old and 30-yr-old wetlands). A new and sensitive toxic risk index (TRI) is developed for the accurate assessment of toxic risk for heavy metals in wetland soils compared with the sum of the toxic units (∑TUs), and As, Cr, Ni and Cd showed higher contributions to TRI.     

A new peptidyl fluorescent chemosensors for the selective detection of mercury ions based on tetrapeptide

A novel peptidyl chemosensor (PySO₂-His-Gly-Gly-Lys(PySO₂)-NH₂, 1) was synthesized by incorporation of two pyrene (Py) fluorophores into the tetrapeptide using sulfonamide group. Compound 1 exhibited selective fluorescence response towards Hg(II) over the other metal ions in aqueous buffered solutions. Furthermore, 1 with the potent binding affinity (K_d = 120 nM) for Hg(II) detected Hg(II) without interference of other metal ions such as Ag(I), Cu(II), Cd(II), and Pb(II). The binding mode of 1 with Hg(II) was investigated by UV absorbance spectroscopy, ¹H NMR titration experiment, and pH titration experiment. The addition of Hg(II) induced a significant decrease in both excimer and monomer emissions of the pyrene fluorescence. Hg(II) interacted with the sulfonamide groups and the imidazole group of His in the peptidyl chemosensor and then two pyrene fluorophores were close to each other in the peptide. The decrease of both excimer and monomer emission was mainly due to the excimer/monomer emission change by dimerization of two pyrene fluorophores and a quenching effect of Hg(II).     

Lead,zinc, cadmium hyperaccumulation and growth stimulation in Arabis paniculata Franch

Metal hyperaccumulation is of great interest in recent years because of its potential application for phytoremediation of heavy metal contaminated soils. In this study, a field survey and a hydroponic experiment were conducted to study the accumulation characteristics of lead (Pb), zinc (Zn) and cadmium (Cd) in Arabis paniculata Franch., which was found in Yunnan Province, China. The field survey showed that the wild population of A. paniculata was hyper-tolerant to extremely high concentrations of Pb, Zn and Cd, and could accumulate in shoots an average level of 2300 mg kg^?1 dry weight (DW) Pb, 20,800 mg kg^?1 Zn and 434 mg kg^?1 Cd, with their translocation factors (TFs) all above one. Under the hydroponic culture, stimulatory effects of Pb, Zn and Cd on shoot dry biomass were noted from 24 to 193 μM Pb, 9 to 178 μM Cd and all Zn supply levels in nutrient solution, while the effects were not obvious in the roots. Chlorophyll concentrations in Pb, Zn and Cd treatments showed an inverted U-shaped pattern, consistent with the change of plant biomass. Pb, Zn and Cd concentrations in the shoots and roots increased sharply with increasing Pb, Zn and Cd supply levels. They reached > 1000 mg kg^?1 Pb, 10,000 mg kg^?1 Zn and 100 mg kg^?1 Cd DW in the 24 μM Pb, 1223 μM Zn and 9 μM Cd treatment, respectively, in which the plants grew healthy and did not show any symptoms of phytotoxicity. The TFs of Zn were basically higher than one and the amount of Zn taken by shoots ranged from 78.7 to 90.4% of the total Zn. However, the TFs of Pb and Cd were well below one, and 55.0–67.5% of total Pb and 57.8–83.5% of total Cd was accumulated in the shoots. These results indicate that A. paniculata has a strong ability to tolerate and hyperaccumulate Pb, Zn and Cd. Meanwhile, suitable levels of Pb, Zn and Cd could stimulate the biomass production and chlorophyll concentrations of A. paniculata. Thus, it provides a new plant material for understanding the mechanisms of stimulatory effect and co-hyperaccumulation of multiple heavy metals.     

Removal of Zn(II) ions from aqueous solution using Moringa oleifera Lam. (horseradish tree) biomass

The removal of Zn(II) ions from aqueous solution using pure and chemically pretreated biomass of Moringa oleifera was investigated at 30 ± 1 °C in this study. The experimental results explored that the maximum pH (pH_max) for efficient sorption of Zn(II) was 7 ± 0.1 at which evaluated biosorbent dosage and biosorbent particle size, were 0.5 g/L, <0.255 mm, respectively. The cellular Zn(II) concentration increased with the concentrations of Zn(II) in solution. Pretreatment of M. oleifera biomass affected the sorption process and the uptake capacity (mg/g) of biomass for Zn(II) uptake was in following order: NaOH (45.76) > H₂SO₄ (45.00) > CTAB (42.80) > Ca(OH)₂ (42.60) > Triton X-100 (42.06) > H₃PO₄ (41.22) > Al(OH)₃ (41.06) > SDS (40.41) > HCl (37.00) > non-treated biomass (36.07). There was significant increase in uptake capacity of M. oleifera biomass, which suggested that affinity between metal and sorbent can be increased after some sort of pretreatment. Both Langmuir and Freundlich isotherm model fitted well to data of Zn(II) biosorption as represented by high value of their correlation coefficient (i.e. R² ≈ 1). Kinetic studies revealed that Zn(II) uptake was fast with 90% or more of uptake occurring with in 40 min of contact time and the equilibrium was reached in 50 min of contact time. The sorption rates were better described by a second order expression than by a more commonly applied Lagergren equation. Finally it was concluded that pretreatment of M. oleifera biomass can achieve superior Zn(II) uptake capacity in comparison to non-pretreated biomass.     

Biochemical responses of the aquatic moss Fontinalis antipyretica to Cd,Cu, Pb and Zn determined by chlorophyll fluorescence and protein levels

Biochemical reactions to Cu, Cd, Zn and Pb in the aquatic moss Fontinalis antipyretica were studied in order to characterize the physiological background of the metal response. Chlorophyll fluorescence and intracellular metal localization and stress protein levels were measured. Exposure to 25 or 100 μM Cu over a 7-day period resulted in a decline of chlorophyll fluorescence to about 70% and 52%, respectively. Up to 100 μM Cd caused a decrease in chlorophyll fluorescence to 75%. With all metals used at 25–100 μM concentrations, the intracellular uptake increased. For all metals investigated at 25–100 μM, the intracellular uptake increased. Maximum values were reached at 100 μM Cu, Pb, Zn or Cd exposure. As shown by analytical electron microscopy (EDX, EELS) moss material treated with 50 μM Cu exhibited reduced sulphur levels in the cytoplasm and an increase in phosphate in vacuolar dense particles. EEL-spectra indicated that Cu is chelated in the cytoplasm by SH-groups and coprecipitated with orthophosphate in vacuoles. To monitor the stress response at the protein level, heavy metal induced heat shock protein 70 (hsp70) was measured. An antibody was raised against conserved plant metallothionein p2 motifs derived from Brassica juncea. In all metal-treated samples the antibody bound to proteins of about 8 kDa. However, sequencing failed to reveal significant homologies to known proteins. These experiments provide for the first time results on protein level after heavy metal stress in the aquatic bioindicator moss.     

Distribution and enrichment of heavy metals among sediments,water body and plants in Hengshuihu Wetland of Northern China

In this study, a survey for the spatial distribution of heavy metals in Hengshuihu Wetland of China was conducted. Samples were collected from three compartments, water, sediment, and reed (Phragmites communis Trin), at different sites, and their contents of heavy metals, including mercury (Hg), arsenic (As), chromium (Cr), lead (Pb), copper (Cu), zinc (Zn), and cadmium (Cd), were analyzed. The results showed heavy metals in the sediments distributed in the Buffer Zone and Wangkou Sluice area at concentrations relatively higher than those in other areas, while concentrations in the Core Zone were lower. The heavy metal concentrations of water bodies in all areas, except those for Hg and Pb, were lower than the cutoff values for the first-grade water quality that was set as the highest standard to protect the national nature reserves. The heavy metal distributions among the three compartments were significantly different, with the following order: sediment > plant > water. In the reeds, accumulated amounts of different heavy metals varied in the following order: Hg > Zn > As > Cu > Cr. Concentrations of heavy metals only showed weak correlations between the water bodies and the sediments. Concentrations of heavy metals (except Hg and Cr) had no corrections between the sediments and the reeds. The distribution of mercury indicated that it enters the lake mainly from the atmosphere and outside water bodies. The concentrations of As, Hg, Cr, Cu and Zn in different parts of the reeds were detected and their abundances were ranked in the following order: root > leaf > stem.     

Tolerance,accumulation and distribution of zinc and cadmium in hyperaccumulator Potentilla griffithii

In this study, zinc (Zn) and cadmium (Cd) tolerance, accumulation and distribution was conducted in Potentilla griffithii H., which has been identified as a new Zn hyperaccumulator found in China. Plants were grown hydroponically with different levels of Zn²⁺ (20, 40, 80 and 160 mg L^?1) and Cd²⁺ (5, 10, 20 and 40 mg L^?1) for 60 days. All plants grew healthy and attained more biomass than the control, except 40 mg L^?1 Cd treatment. Zn or Cd concentration in plants increased steadily with the increasing addition of Zn or Cd in solution. The maximum metal concentrations in roots, petioles and leaves were 14,060, 19,600 and 11,400 mg kg^?1 Zn dry weight (DW) at 160 mg L^?1 Zn treatment, and 9098, 3077 and 852 mg kg^?1 Cd DW at 40 mg L^?1 Cd treatment, respectively. These results suggest that P. griffithii has a high ability to tolerate and accumulate Cd and Zn, and it can be considered not only as Zn but also as a potential cadmium hyperaccumulator. Light microscope (LM) with histochemical method, scanning electron microscope combined with energy dispersive spectrometry (SEM-EDS) and transmission electron microscope (TEM) were used to determine the distribution of Zn and Cd in P. griffithii at tissue and cellular levels. In roots, SEM-EDS confirmed that the highest Zn concentration was found in xylem parenchyma cells and epidermal cells, while for Cd, a gradient was observed with the highest Cd concentration in rhizodermal and cortex cells, followed by central cylinder. LM results showed that Zn and Cd distributed mainly along the walls of epidermis, cortex, endodermis and some xylem parenchyma. In leaves, Zn and Cd shared the similar distribution pattern, and both were mostly accumulated in epidermis and bundle sheath. However, in leaves of 40 mg L^?1 Cd treatment, which caused the phytotoxicity, Cd was also found in the mesophyll cells. The major storage site for Zn and Cd in leaves of P. griffithii was vacuoles, to a lesser extent cell wall or cytosol. The present study demonstrates that the predominant sequestration of Zn and Cd in cell walls of roots and in vacuoles of epidermis and bundle sheath of leaves may play a major role in strong tolerance and hyperaccumulation of Zn and Cd in P. griffithii.     

Copper,Lead, Cadmium,and Zinc Sorption By Waterlogged and Air-Dry Soil

Competitive sorption of copper (Cu), lead (Pb), cadmium (Cd), and zinc (Zn) was studied in three soils of contrasting chemical and physical properties under air-dry and waterlogged conditions. Competitive sorption was determined using the standard batch technique using six solutions, each with Cu, Pb, Cd, and Zn concentrations of approximately 0, 2.5, 5, 10, 20, and 50?mg L^?1Waterlogged soils tended to sorb higher amounts of added Cu, Pb, Zn and Cd relative to soils in the air-dry condition; however, this increase in sorption was generally not statistically (p<0.05) significant. The magnitude of sorption under both waterlogged and air-dry conditions was affected by the type and amount of soil materials involved in metal sorption processes, and competition between other metals for the sorption sites. Metal sorption was closely correlated with soil properties such as cation exchange capacity, organic carbon, and Fe and Mn hydrous oxides. Exchangeable Al may have markedly reduced metal sorption due to its strong affinity for the sorption sites, while increases in exchangeable Mn may have enhanced Zn and Cd sorption. Heavy metal sorption was best described as a combination of both specific and nonspecific interactions. The extractability of Cu, Pb, Cd, and Zn under waterlogged and air-dry conditions was also studied. Three solutions containing these metals were mixed with each soil to achieve a final concentration of 0, 50, and 500?mg kg^?1. Each soil was extracted every 7 days using 1?M MgCl₂ (pH 7) to determine metal extractability. Metal extractability initially decreased then increased due to waterlogging. The increased extractability of added metals was closely related to increased solubility of Fe and Mn suggesting that dissolution of Fe and Mn, oxides under reducing conditions caused a release of previously sorbed Cu, Pb, Cd, and Zn.     

Trace elements accumulation and temporal trends in leaves of urban deciduous trees (Aesculus hippocastanum and Tilia spp.)

Leaves of common deciduous trees: Aesculus hippocastanum and Tilia spp. from three parks within the urban area of Belgrade (Serbia) were studied as biomonitors of trace elements (Cr, Fe, Ni, Cu, Zn, and Pb) atmospheric pollution. The seasonal trace elements accumulation (September/May) in the leaves, and their temporal trends, were assayed in a multy-year period (2002–2006). Significant seasonal accumulation was evident in samples of A. hippocastanum for: Cr, Fe, Ni, Zn, and Pb, as well as in Tilia spp. leaves, except for Zn. For Cu, no regular seasonal accumulation was observed in leaves of the studied species. Decreasing temporal trend in leaf tissue concentrations were evident for Pb in A. hippocastanum (16.0 μg g^?1 in September of 2002 to 4.6 μg g^?1 in September of 2006) which is in accordance with the bulk atmospheric deposition measurements. The leaf Cu concentrations were the highest at one of the studied sites, also marked previously with extremely high atmospheric Cu loadings by some other monitoring (bulk deposition, particulate matter, moss) surveys. Decreasing Cu concentrations temporal trend at that site in the leaves of A. hippocastanum was evident through the studied years and also confirmed with the bulk deposition measurements. The Cr, Fe, Ni, and Zn leaf tissue concentrations remained at about the same level in the studied species throughout the experiment and no agreement was observed with the bulk deposition data. Comparing the studied biomonitors, the leaves of A. hippocastanum showed significantly higher elements accumulation and more consistency than Tilia spp., so it may be considered as more suitable species for assessment of Pb and Cu atmospheric pollution.     

Toxic and essential elements in children's blood (<6 years) from Kinshasa,DRC (the Democratic Republic of Congo)

In this study we determined the concentration of 9 trace elements (As, Cd, Cu, Hg, Mn, Mo, Pb, Se and Zn) in whole blood of children (n = 100, 64 girls, 36 boys and median age: 36 months) using inductively coupled plasma mass spectrometry (ICP-MS). The proportion of children potentially deficient in essential elements or poisoned by toxic elements was evaluated. The aging effects on the concentration of these elements were also investigated. The median values were 3.17 μg/L (As), 0.15 μg/L (Cd), 1.1 mg/L (Cu), 2.1 μg/L (Hg), 10.4 μg/L (Mn), 17.7 μg/L (Mo), 8.7 μg/dL (Pb), 10.7 μg/L (Se) and 5.0 mg/L (Zn). The concentration of many elements (As, Cd, Hg, Mn, Pb and Zn) showed significant age variations but not sex influence. Regarding levels of the essential elements (Cu, Mn, Mo, Se and Zn), B-Cu, B-Mn, B-Se and B-Zn were in the normal range, whereas exceeded levels were observed for B-Mo. None of these children was deficient in essential elements. Except B-Cd, all toxic elements showed exceeded blood levels. The proportion of children potentially poisoned by toxic elements varies from 10% (n = 10) to 95% (n = 95) and depends on toxic element: 95% for As, 10% for Hg and 35% for Pb. The main health concerns emerging from this study are the high As, Hg and Pb exposures of the Kinshasan children requiring further documentation, corrective actions and the implementation of appropriate regulations.