Leaching potential of heavy metals (Cd, Ni, Pb, Cu and Zn) from acidic sandy soil amended with dolomite phosphate rock (DPR) fertilizers

There is an increasing concern on heavy metal leaching from the soils amended with sewage sludge. A column study was conducted to examine the extent of leaching of five important heavy metals (Cd, Ni, Pb, Cu and Zn) from an acidic sandy soil amended with different dolomite phosphate rock (DPR) fertilizers (an application rate of 1% fertilizers) developed from DPR and N-Viro (consisting of biosolids and fly ash) at 0%, 10%, 20%, 30%, 40%, 50% and 100% DPR. Ten leaching events were carried out with each event done at an interval of 7 days and with total leaching volume of 1183mm, which is equivalent to the mean annual rainfall of this region during the period of 2001-2003. Leachate was collected after each leaching event and analyzed for heavy metals. The maximum leachate concentrations of Cd, Ni, Pb, Cu and Zn were all below drinking water quality guidance limits set by Florida Department of Environmental Protection and World Health Organization, suggesting that the application of DPR fertilizers may not pose a threat to water quality by leaching. Most of leachate concentrations of Cd, Ni and Pb were below their detection limits and there were no significant differences between the control and the treatments with different DPR fertilizers. By contrast, there were higher leachate concentrations of Cu and Zn (ranging from 0.7 to 37.1mug Cu/l and 5.1 to 205.6mug Zn/l for all treatments) due to their higher contents in both the soil and different DPR fertilizers compared with Cd, Ni and Pb. The leachate concentrations of Cu and Zn for each treatment decreased with increasing leaching events. The differences in leachate concentrations of Cu and Zn between the control and the treatments with different DPR fertilizers containing N-Viro were significant, especially in the first several leaching events and, moreover, they increased with increasing proportion of N-Viro in the DPR fertilizers. There were similar trends in total losses of Cu and Zn after ten leaching events. Greater differences in both leachate concentrations and total losses of Zn between the control and the treatments containing N-Viro were noted. Total losses of Zn for the treatments containing N-Viro were 3.0-5.1 times higher than those for the control compared with 1.4-2.2 times higher for total losses of Cu, suggesting that greater proportions of Zn losses came from the DPR fertilizers due to the greater mobility of Zn in the DPR fertilizers compared with Cu.     

Tolerance and hyperaccumulation of a mixture of heavy metals (Cu,Pb, Hg,and Zn) by four aquatic macrophytes

In the present investigation, four macrophytes, namely Typha latifolia (L.), Lemna minor (L.), Eichhornia crassipes (Mart.) Solms-Laubach, and Myriophyllum aquaticum (Vell.) Verdc, were evaluated for their heavy metal (Cu, Pb, Hg, and Zn) hyperaccumulation potential under laboratory conditions. Tolerance analyses were performed for 7 days of exposure at five different treatments of the metals mixture (Cu⁺², Hg⁺², Pb⁺², and Zn⁺²). The production of chlorophyll and carotenoids was determined at the end of each treatment. L. minor revealed to be sensitive, because it did not survive in all the tested concentrations after 72 hours of exposure. E. crassipes and M. aquaticum displayed the highest tolerance to the metals mixture. For the most tolerant species of aquatic macrophytes, The removal kinetics of E. crassipes and M. aquaticum was carried out, using the following mixture of metals: Cu (0.5 mg/L) and Hg, Pb, and Zn 0.25 mg/L. The obtained results revealed that E. crassipes can remove 99.80% of Cu, 97.88% of Pb, 99.53% of Hg, and 94.37% of Zn. M. aquaticum withdraws 95.2% of Cu, 94.28% of Pb, 99.19% of Hg, and 91.91% of Zn. The obtained results suggest that these two species of macrophytes could be used for the phytoremediation of this mixture of heavy metals from the polluted water bodies.     

Heavy metals (Cd, Pb, Zn, Ni, Cu and Cr(III)) removal from water in Malaysia: post treatment by high quality limestone

This paper presents the results of research on heavy metals removal from water by filtration using low cost coarse media which could be used as an alternative approach to remove heavy metals from water or selected wastewater. A series of batch studies were conducted using different particle media (particle size 2.36-4.75 mm) shaken with different heavy metal solutions at various pH values to see the removal behaviour for each metal. Each solution of cadmium (Cd), lead (Pb), zinc (Zn), nickel (Ni), copper (Cu) and chromium (Cr(III)) with a concentration of 2 mg/L was shaken with the media. At a final pH of 8.5, limestone has significantly removed more than 90% of most metals followed by 80% and 65% removals using crushed bricks and gravel, respectively. The removal by aeration and settlement methods without solid media was less than 30%. Results indicated that the removal of heavy metals was influenced by the media and not directly by the pH. Investigations on the removal behaviour of these metals indicated that rough solid media with the presence of carbonate were beneficial for the removal process. Adsorption and precipitation as metals oxide and probably as metals carbonate were among the two mechanisms that contributed to the removal of metals from solution.     

Effects of Cu,Pb and Zn on two Potamogeton species grown under field conditions

Two common macrophyte species, Potamogeton perfoliatus L. and Potamogeton pectinatus L. were grown for 12 weeks at shallow depths in sediments contaminated with 1250 or 2500 g Pb or Cu and/or Zn (gDW sediment)^-1. Control experiments were run at background levels of 4, 13, and 38 g Pb, Cu and Zn (gDW sediment)^-1, respectively. Effects of heavy metals on biomass production and metal uptake and distribution in plants are presented in relation to total amount and plant-available fraction of metals in the sediment.All three studied metals gave reduced biomass production, and the toxicity of the metals decreased in the order Zn>Cu>Pb. The root/shoot biomass ratio increased for P. pectinatus, but decreased for P. perfoliatus with metal treatment. The content of any single metal was higher in shoots than in roots of plants grown on sediments not contaminated with that specific metal, but addition of that metal increased the proportion in roots. The uptake by plants of any of the heavy metals increased with increased metal addition. The magnitude of the plant-available fraction of metals of untreated sediment was Zn>Cu>Pb, and increased in contaminated sediments. Addition of Cu decreased both the plant-available fraction and the total concentration of Zn in the sediment, while increased the uptake of Zn by the plants. The opposite was found for Cu when Zn was added. P. pectinatus accumulated about twice as much Cu as P. perfoliatus. On the other hand, the concentration of Pb was higher in P. perfoliatus than in P. pectinatus, and was negligible in P. pectinatus when cultivated in untreated sediments.     

Ecological risk assessment of heavy metals (Zn,Cr, Pb,As and Cu) in sediments of Dohezar River,North of Iran,Tonekabon city

Sediments of the Dohezar River in Tonekabon contain high levels of heavy metals and therefore, they were chemically analyzed to determine concentrations of these elements. In fact, this research intended to evaluate the ecological risks of the heavy metals As, Pb, Cr, Zn, and Cu in the river sediments. Contamination indices such as enrichment factor and contamination factor, potential ecological risk index for each heavy metal (Ei), and potential ecological risk index (RI) were evaluated. Considering the average concentrations of the heavy metals at all of the Stations, the maximum average for the elements was zinc and the minimum was copper. Therefore, the averages of changes in the concentrations of the elements are Zn > Cr > Pb > As > Cu. Considering calculation of the enrichment factors for the heavy metals according to the EF classification table, the maximum number of Stations (43.02%) with respect to contamination with As were in class 4(moderately severe enrichment). With respect to enrichment of Pb, Zn, Cr, and copper, the rest of the stations with 83.72, 77.91, 86.05, and 69.77%, respectively, were in class 2 (minor enrichment). Considering the high concentrations of the studied elements in the sediments of the region compared to the background value, and based on calculations related to contamination factor, arsenic with the average of 11.9 exceeded the most from the standard limit. It was followed by Pb with 2.2, zinc with 2, Cr with 1.8, and Cu with1.6 (copper exceeding the least from the standard limit). With respect to Ei (the potential ecological risk index for each heavy metal), arsenic was the element with the highest environmental risk. Moreover, with respect to RI (potential ecological risk index), most Stations were in the low-grade range (low environmental risk). This research used statistical studies on correlation coefficients and cluster analysis to find the origin of the heavy metals in the sediments of the region. The low correlation between the heavy metals in the soil can indicate they probably did not have the same source. Moreover, these elements have different geochemical behaviors due to their low correlation. Finally, the kriging method was employed to extract interpolation maps of the spatial distribution for each of the heavy metals.     

Bioaccumulation of alkaline soil metals (Ca,Mg) and heavy metals (Cd,Ni, Pb) patterns expressed by freshwater species of Ulva (Wielkopolska,Poland)

The paper includes results of the first study on the accumulation of selected metals in freshwater populations of Ulva taxa at 16 sites in Poland. The thalli examined contained very high concentrations of Ca and Mg, owing to well‐developed surface incrustations of carbonate. Among the heavy metals investigated, the most significant concentration in the thalli was Ni, whereas the lowest was Pb. The median concentrations of Ni and Cd in the freshwater Ulva thalli were significantly higher than those reported in the available literature for marine taxa of the same genus. Several statistically significant correlations were found when the concentrations of different metals in the thalli and the water were analysed (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Flow of heavy metals (Ni and Cu) in the catchment area of a subarctic lake

This paper considers methodological approaches to estimating the flow, balance, and accumulation of heavy metals (HMs) in a lake under conditions of long-term air pollution. Using the example of Chunozero Lake in the Lapland State Biospheric Reserve in Murmansk region, the accumulation of HMs in sediments is estimated for over a 70-year period of activity of a metallurgical mining enterprise (GMK Severonikel). The thickness of polluted sediments in a greater part of the lake water area averages 2 cm, and the average sedimentation rate for the last 20 years is 1 mm/year. Metals accumulated in lake sediments can indicate a danger of pollution in the future, particularly if processes of lake eutrophication develop. Due to the peculiar properties of substance flow to the Chunozero, the running type of water-mass movement, and the elongated form of the lake, only about 3% of HMs that enter the catchment area accumulate in sediments, in contrast to Imandra Lake (which has the largest area), where the accumulation of HMs reaches 55% owing to the fact that they enter mainly in the composition of wastewater and the low velocities of water flow.     

Heavy Metals (Cd,Cu, Ni,Pb, and Zn) Fractionation in River Sediments,Hamedan, Western Iran

Five heavy metals (Cd, Cu, Ni, Pb, and Zn) in river sediments from Abshineh River, Hamedan, western Iran, were fractionated by a sequential extraction procedure. Cu, Ni, Pb, and Zn existed in sediments mainly in residual fraction (mean 92%, 86%, 77%, and 65%, respectively), whereas Cd occurred mostly as organic matter (mean 41%) and exchangeable (mean 25%) fractions. The mean percent of mobile fraction of Cd, Cu, Ni, Pb, and Zn in contaminated sediments was 25, 13, 4, 24, and 10, respectively, which suggests that the mobility and bioavailability of the five metals in sediments probably decline in the following order: Cd = Pb > Cu > Zn > Ni. The metal levels were also evaluated according to the contamination factor, which revealed significant anthropogenic pollution of Cd and Pb.     

Effect of heavy metals (Cu,Cd and Pb) on aspartate and alanine aminotransferase in Ruditapes philippinarum (Mollusca: Bivalvia)

The accumulation of cadmium, copper and lead and their effects on aspartate and alanine aminotransferases in digestive gland, gills, foot and soft body in the clam Ruditapes philippinarum were examined. The animals were exposed to different concentrations: Cd (200–600 μg·l⁻¹), Pb (350–700 μg·l⁻¹) and Cu (10–20 μg·l⁻¹) for 7 days. The highest concentrations were found in digestive gland for cadmium and copper, and in gills for lead, and the lowest values were observed in the foot. Aspartate aminotransferase activity (AST), in general, was not inhibited by cadmium, lead or copper during the exposure. Only in clams exposed to cadmium (600 μg·l⁻¹, 7 days) and copper (20 μg·l⁻¹, 5 days) were observed significant differences (P<0.05) in foot and gills, respectively, with respect to control. In the case of alanine aminotransferase activity (ALT), significant differences were observed for cadmium and lead in treated animals with respect to control. With regard to copper, a decrease in ALT was observed in gills and foot exposed to 20 μg·l⁻¹. A significant correlation (P<0.05) was observed between ALT and metal accumulation for cadmium, copper and lead in gills. In the case of soft body, only cadmium and lead showed a significant correlation. In summary, R. philippinarum can be considered a bioindicator species for cadmium and lead accumulation and ALT could be useful as biomarker of sublethal stress for these metals in soft tissues and gills. Only gills can be considered an adequate target tissue for copper.     

二球悬铃木不同器官对空气中Cu、Ni、Pb和Zn的累积作用

以交通繁忙区(污染点)和相对清洁区(对照点)道路两侧的二球悬铃木〔Platanus acerifolia ( Ait.) Willd.〕为研究对象,测定了不同器官(包括主干、老树皮、2年生枝条、1年生枝条、腋芽、叶片和果实)中Cu、Ni、Pb和Zn的含量,并对污染点二球悬铃木各器官中4种重金属元素的累积量和污染指数及二者的分布比例进行分析。结果表明：二球悬铃木体内重金属元素的含量因样点、器官及元素的不同而呈现不同的变化规律,污染点4种重金属元素的累积量及其分布比例、污染指数及其分布比例则因器官和元素的不同而有明显差异。总体上看,污染点各器官的Cu、Ni、Pb和Zn的含量均高于对照点且差异显著(P<0.05);4种重金属元素相比较,均以Zn含量最高,Cu含量次之,而Ni和Pb含量则较低;在不同器官中同一重金属元素的含量也有明显差异,其中,Cu、Ni和Zn含量均在腋芽中最高,Pb含量在2年生枝条中最高。4种重金属元素的累积量及其分布比例均在叶片中最高,在老树皮中次之,在1年生枝条、2年生枝条和腋芽中均较低;而4种重金属元素的污染指数及其分布比例则在老树皮中最高,在叶片中次之。研究结果显示：二球悬铃木各器官对空气中的重金属元素均有一定的吸滞能力,并且叶片和老树皮的吸滞能力明显优于其他器官。     

Trace Metals (Cd,Co, Cr,Cu, Hg,Ni, Pb,and Zn) in Food Supplements of Marine Origin

We determined the concentrations of Cd, Co, Cr, Cu, Hg, Ni, Pb, and Zn in dietary supplements of marine origin. Four supplement categories were studied; algae, coral, krill, and shark cartilage. A direct mercury analyzer was used for Hg determinations while acid digestions and ICP-AES were used for Cr analysis and ICP-MS for the other trace metals. Algae are the supplements showing the highest concentrations of Pb, Cr, and Ni with respective means of 1.6 mg Pb/kg dry weight (d.w.), 3.2 Cr mg/kg d.w., and 8.0 mg Ni/kg d.w. Krill supplements have the highest levels of Cd, Cu, and Zn with 0.65 mg Cd/kg d.w., 63 mg Cu/kg d.w., and 50 mg Zn/kg d.w., respectively. Shark cartilage supplements show the highest levels of Hg and Co with mean concentrations of 160 μg Hg/kg d.w. and 73 ± 51 μg Co/kg d.w., respectively. No samples in our study exceeded the provisional tolerable daily intakes set by Health Canada, the joint committee of the World Health Organization/Food and Agricultural Organization, or the U.S. Environmental Protection Agency. Nevertheless, Ni and Pb in algae and Hg in shark cartilage may end up contributing to a very significant portion of the allowable daily intake—leaving little room for normal intake through food consumption and other exposure pathways.     

Sequential extraction and speciation of Ba,Cu, Ni,Pb and Zn in soil contaminated with automotive industry waste

Abstract

Sequential extraction or fractionation of heavy metals in the solid phase and their speciation in soil solution are important tools for assessing changes resulting from land use and/or pollution. The distribution of the various forms of Ba, Cu, Ni, Pb and Zn was evaluated in soil samples taken from a polluted area, and the speciation of cations and anions in a soil solution contaminated with automotive industry waste. We evaluated the sequential extraction and speciation of Ba, Cu, Ni, Pb and Zn in a Leptosol associated with a Cambisol and contaminated with automotive industry waste. Soil samples were collected at 0-0.2 m (a mix of soil and waste); 0.2-0.4 m (waste only), and 0.4-0.6 m (soil only) both in the polluted area and in two contiguous unpolluted areas: a sugarcane plantation and a forest fragment. Total concentrations of metals in the polluted area were above limits for intervention established by European Community regulations. Cu was mostly distributed in the residual and in the oxide-bonded fractions, except for the waste-only sample, in which the carbonate-bonded fraction was significant. Zn was concentrated in the residual and carbonate-bonded fractions, while Ba, Ni and Pb predominated in the residual fraction of the contaminated samples. Metals in the soil solution were predominantly in the hydroxyl forms, except for Ba, which was mostly in the ionic form (Ba²⁺).     

The interaction of 5-fluoroorotic acid with transition metals: synthesis and characterisation of Ni(II), Cu(II) and Zn(II) complexes

5-Fluoroorotic acid (H(3)FOro) is a potent inhibitor for some metalloproteins such as dihydroorotase and dihydroorotate dehydrogenase and for thymidylate synthase (nonmetalloprotein) in the human malaria parasite Plasmodium falciparum. To study the coordination chemistry of H(3)Foro, the ammonium salt [NH(4)(+)][H(2)FOro(-)].1H(2)O (1) and the first coordination compounds of H(3)FOro with transition metals [Ni(HFOro(2-))(H(2)O)(4)].1H(2)O (2), [Cu(HFOro(2-))(NH(3))(H(2)O)](n) (3) and [Cu(3)(FOro(3-))(2)(NH(3))(6)(H(2)O)(2)] (4) have been synthesised and characterised by single-crystal X-ray diffraction, IR spectroscopy and by thermogravimetry. Three different coordination modes of 5-fluoroorotic acid have been established. In all cases the ligand is chelated to the metal via an amido-nitrogen and a carboxylate-oxygen but for (3), there is also a carboxylate oxygen from another HFOro(2-) ligand resulting in a polymeric structure and for (4), the second amido-nitrogen in the ororotic acid ring coordinates to give a trinuclear complex. The metal coordination polyhedra are octahedral in (2), square-pyramidal in (3) and square-planar and approximately square-pyramidal in (4). An octahedral coordination geometry including a N(1)/O(61)-chelating HFOro(2-) ligand with four aqua ligands is proposed for the Zn complex [Zn(HFOro(2-)) (H(2)O)(4)].0.5H(2)O (5), based on IR and thermogravimetric data. Extensive hydrogen bonded networks and some ring-ring stacking interactions are observed in each of the structures.     

Element content (Cu, Fe, Mn, Ni, Pb, and Zn) of the ruderal plant Verbascum olympicum Boiss. from East Mediterranean

In this study, heavy metal content (Cu, Fe, Mn, Ni, Pb, Zn) was determined in soils and different organs of Verbascum olympicum Boiss. This species is endemic to Uluda? and spreads on destroyed areas such as: roadsides, developed building areas, ski lift stations and sheep folds. Soils and different organs (roots, stems, leaves and flowers) of plant samples were analyzed using an atomic absorption spectrophotometer for determining the element content. Heavy metal contents in soils and different organs in this species were highly correlated (P < 0.05). However, the contribution of plant organs to the accumulation capacity varied according to the metal. These results suggest that this species may be useful as a bioindicator for heavy metals.     

Heavy metals (Cu,Zn, Pb,Cd) in sediment,zooplankton and epibenthic invertebrates from the area of the continental slope of the Banc d'Arguin (Mauritania)

The concentrations of copper, zinc, lead and cadmium in the surface sediment (upper 5 mm) were generally higher in the silt fraction than in the bulk sediment. No significant geographical trend in the metal concentrations of the surface sediments was found, nor a correlation between concentrations in bulk sediment as well as in the silt fraction and the % silt could be established. In general, the metal concentrations in both bulk sediment and silt are lower, when compared to marine environments in other climatological regions.In zooplankton, the metal concentrations were relatively high: expressed in µg g^–1 on a dry weight (D.W.) basis, they ranged from 15–90 for copper, 70–580 for zinc, 12–55 for lead and 4–10 for cadmium.In epibenthic invertebrate species, both in crustaceans and bivalve molluscs, the concentrations of copper, zinc, and lead were in the same order of magnitude as compared to corresponding species from other geographical latitudes. Cadmium concentrations were relatively low, ranging from 0.13–0.42 µg g^–1 D.W. in the bivalve molluscs Pitaria tumens and from 0.04–0.27 µg g^–1 D.W. in the shrimp Processa elegantula. Also in the crab species Ilia spinosa, Inachus sp. and Pagurus sp., the cadmium concentrations were low, varying between 0.1 and 0.2 µg g^–1 D.W.No significant relation between the metal concentration in whole-body samples and sediment (either bulk or silt) was present. Also no gradient was apparent in concentrations in organisms sampled at different depths (5 to 200 m) along two off-shore transects perpendicular to the Banc d'Arguin. Data indicated lower metal concentration in epibenthic organisms from sampling stations along a northern transect (southwest of Cap Blanc) than in organisms from the southern transect, off Cap Timiris.Evidence was obtained for a considerable atmospheric input of heavy metals, in particular zinc and lead, in a certain area along the continental slope of the Banc d'Arguin.     

污染条件下VAM玉米元素积累和分布与根际重金属形态变化的关系

为了了解重金属Cu、Zn、Pb、Cd在土壤－根际－植物系统中的行为,揭示VAM植物减弱土壤中过量重金属对植物生理毒的抗性机理,采用原子吸收光谱测定Cu、Zn、Pb、Cd在污灌土壤中生长的VA菌根玉米和无菌根玉米中的积累和分布,并用连接形态分析技术分析了菌根际中Cu、Zn、Pb、Cd的形态分布和变化趋势,结果表明,Cu、Zn、Pb、Cd在菌根玉米中的积累量比非攻根中积累量分别减少10％、18％和29％,Cd积累量没有改变,生长7周后,菌根玉米是非菌根玉米生物量的1．5倍,与对照土壤相比,根际中除Cu交换态显著增加外,Zn、Pb、Cd各形态相对改变量显著大于非菌根,且菌根根际上中Cu、Zn、Pb有机结合态增加量显著大于非根际土,说明菌根际金属向稳定状态转移的程度显著大于非菌根际,同时,讨论了根际金属形态对金属有效性的影响,及其与菌根植物金属抗性机理的关系。     

Cu、Pb和丁草胺污染对土壤呼吸强度的影响

采用室内碱液吸收法研究了重金属Cu 、Pb 和丁草胺及其复合污染对土壤呼吸强度的影响及其随时间的动态变化.重金属Cu 、Pb 和丁草胺单一污染对土壤呼吸强度的影响,随污染物的浓度和培养时间而变化,DMRT 法检验表明,在后期各处理与对照间的呼吸强度都存在显著差异,前期则差异不显著.复合污染中,丁草胺与Cu 复合污染对土壤呼吸强度的影响在培养后期存在明显的交互作用,而丁草胺与Pb 复合污染对土壤呼吸强度的影响在培养前期存在一定的的交互作用,Cu 与丁草胺复合污染及Pb 与丁草胺的复合污染对土壤呼吸强度变化率的影响大于单一污染对土壤呼吸强度变化率的影响,复合污染对土壤呼吸强度变化率的影响表现为:丁草胺与Cu 复合污染>丁草胺与Pb 复合污染.