Distribution and chemical fractionation of some heavy metals in bottom sediments of Lake Nasser

Distribution and phase association of Cd, Cr, Cu, Fe, Mn, Ni,Pb, Zn and organic matter in Nile sediments taken from LakeNasser (Aswan, Egypt) were investigated. The sediment sampleswere subjected to selective chemical extraction proceduresdesigned to fractionate the particulate heavy metals into sixfractions: (A) ammonium acetate-extractable metals; (B) sodiumacetate-extractable metals; (C) acid oxalate-extractablemetals; (D) hydroxylamine HCl-extractable metals; (E) aquaregia-extractable metals and (F) total metals (HF/HCl/HNO₃destruction). Exchangeable metals which can be extracted byammonium acetate solution are generally considered readilybioavailable as they are weakly bound and may equilibrateeasily with the aqueous phases. In the present study very smallconcentrations of all heavy metals considered were found inthis phase. Between this phase and the metal phases which arenot bioavailable (those exist in highly resistant phases) thereexist several geochemical phases (fractions B, C & D) that maypotentially release their associated metals under changingenvironmental conditions, such as pH and redox potential in thewater sediment interface. This revised version was published online in July 2006 with corrections to the Cover Date.     

Distribution of extractable heavy metals in different soil fractions

Abstract

Due to the difficulties of precisely characterizing environmentally contaminated soil, the effects of heavy metals on plants are studied using uncontaminated soil spiked with known quantities of heavy metals. One problem in using spiked soils is how accurately the distribution of metals mimics stabilized natural soils. We studied the distribution of cadmium, chromium, copper, lead, nickel, and zinc in soil fractions after application in soluble form. The soil samples included a control (an uncontaminated Typic Argiudoll) and two samples spiked with either a moderate or high heavy metal concentration). After application of the salts the soils were subjected to wet/dry cycles over the course of three months. The soils were fractionated using a sequential chemical extraction procedure employing: (1) CaCl₂,(2) NaOH, (3) Na₂EDTA and (4) HNO₃, HCl, and HF. Soil physical separation was carried out by ultrasonic dispersion. The heavy metal levels were determined using ICP-AES. Each heavy metal displayed a unique behavior when added to soil in the form of soluble salts. Cadmium and zinc remained in the soluble fraction, indicating that no equilibrium was attained, while nickel primarily appeared in the insoluble fraction. Chromium, copper and lead were distributed among various soil chemical fractions. The highest levels of all metals appeared in the clay fraction except lead which was mainly present in the silt fraction.     

Heavy metals uptake by vegetables growing in sewage irrigated soil: relationship with heavy metal fractionation in soil

Abstract

Concentrations of the heavy metals Cd, Ni, Cr, Zn, Mn, Co and Cu in soils and vegetable samples (i.e. green chili and gourd) taken from six vegetable fields in the vicinity of Lahore, Pakistan were measured. These soils have been irrigated for a long time with untreated sewage effluents. A control site was selected that has history of fresh canal water irrigation. The sequential extraction procedure developed by Tessier was adopted to demarcate five metal fractions: exchangeable, acid soluble, reducible, oxidizable and residual. The extractants and digests were analysed by atomic absorption spectrometry. The fractionation procedure showed that all the metals were dominant (>50%) in the residual phase in control as well as in waste waster irrigated soils. The concentrations of all the metals in edible parts of the vegetables collected from wastewater irrigated soils, were above critical levels. The total metal concentrations in wastewater irrigated soils followed the order Mn> Co> Zn> Cr> Ni> Cu> Cd, while in control soils the ord er was Mn> Zn> Ni> Co> Cr> Cu> Cd. In order to understand the uptake of metals from soil to vegetables, correlation analyses were performed between metal concentrations in different fractions of soil and their concentrations in vegetables. Correlation analysis was performed at 95% and 99% confidence level. The meaningful significant negative correlation was observed between Cd_F5–Cd_chili,Cr_Total–Cr_gourd,Mn_F5–Mn_Chili,Gourd, Co_F5, _Total–Co_chili, Cu_Total–Cu_Chili which indicate the non availability of total content and residual fraction to studied vegetables. The positive correlation was observed between Cd_Fl-Cd_ChiU, Cd_Fl–Cd_gourd, Ni_{Fi, F3}–Ni_Gourd, Cr_{Fi, F3}, _F4–Cr_ChiU, Cr_F2–Cr_Gourd, Zn_{Fi, F2}–Zn_Gourd, Mn_F3–Mn_Chili, Mn_Fi–Mn_Gourd, Co_F2–Co_Chili, Cu_Fi–Cu_Chili. The positive correlation, especially for the first (exchangeable) second (acid soluble) and for the third (reducible) extraction steps, was obtained which indicate the bioavailability of these metal fractions to plant.     

Olive oil waste as a biosorbent for heavy metals

The sourcing of novel, inexpensive biowastes such as olive mill waste (OMW) from the two-decanter olive-oil-production system offers potential for the removal of metal ions by biosorption. OMW can be used in repeated regeneration cycles for the adsorption of heavy metals from aqueous solutions. The metal ions sequestered can be released in an acid solution until the concentration of these metal ions reaches a level where conventional methods can be used to provide economic metal recovery and potential revenue generation. The ability of this biomass to adsorb more than one metal ion from solution may increase its potential for application in the wastewater industry since the majority of industrial effluents contain more than one metallic species. Metal ion adsorption was found to increase with the speed of agitation and at an optimum pH value of between 4 and 7.     

Geochemical distribution and fractionation of heavy metals in sediments of a freshwater reservoir of India

Abstract

Sediments of a polluted reservoir were evaluated for total contents of Cd, Cr, Cu, Ni, Pb and Zn along with their different geochemical forms (exchangeable, carbonate, Fe–Mn, organic matter and residual). Mineralogy of the sediments and physico-chemical parameters i.e. pH, OC and percentage of sand, silt and clay were also evaluated to see the dependency of heavy metals concentration on these parameters. The total concentration of heavy metals in the sediments varied according to sites and seasons. Except for station H1 which had moderately higher concentration of Cu (45.5 mg kg^-1), concentrations of all other metals at all the sites under study were below the standard shale value. Maximum proportions of all metals were associated with the carbonate and residual fractions. The Risk Assessment Code showed a low risk for Cr, Ni and Zn, and a medium risk for Cu at station H3 and H4. On the basis of freshwater sediment quality guidelines, there is a strong possibility of Cr and Cu toxicity for aquatic biota of the reservoir. The data were further processed using Pearson’s correlation and factor analysis to obtain more accurate information about the behaviour of these metals. A positive relationship among the metals confirmed the anthropogenic sources of pollution in the reservoir. Significant positive relationships of heavy metals with the texture of the sediment were also obtained.     

Chemical mobility and bioavailabity of sediment-bound heavy metals influenced by salinity

The transfer of metals from contaminated sediments to algal cell walls (Scenedesmus quadricauda) and organisms from various trophic levels (euryhaline osmoconform hydroid Cordylophora caspia and algae Brachiomonas submarina) was studied with a multichamber device. The system consists of a central chamber which contained the mud suspension and six external chambers containing the different biological indicators. The solids in the central and external chambers are separated by 0.45 m-diameter membranes which allow diffusion of the mobilized, dissolved metal compounds. Experiments were performed with dredged sediments at various salinities (0.5, 1.0, 1.5, and 2.0 percent, respectively) and the kinetic of re-adsorption was obtained by taking samples after different time intervals. High enrichment of Cd was found in the living alga Brachiomonas submarina, but on the other side only a weak influence of salinity on re-adsorption could be observed. Model experiments with ionic Cd showed a clear dependency on Cd-sorption on the algae, Cd-concentration in solution, and salinity. These results indicate that the transfer of metals mainly depends on the specific surface properties of the substrates and on the specific chemical form of the dissolved mobilized metal.     

Metal contents and fractionation in contaminated soil after column leaching using [S,S]-EDDS

Abstract

Column leaching using [S, S]-ethylene diamine disuccinate ([S, S]-EDDS) on copper tailing soils was carried out to investigate metal content and fractionation after leaching. The soil column was divided into four layers after leaching. Fractionation of Cu, Pb, Zn, and Mn in soil was analyzed using a modified BCR sequential extraction method. Metal contents (Cu, Pb, Ca, Mn) in soil layers increased with the depth of the soil column after leaching in the [S, S]-EDDS treatment. The cumulative extraction efficiency was approximately 43.1% for Cu, 26.8% for Zn, 19.5% for Pb, 10.5% for Ca, 2.07% for Mg, 58.5% for Mn, and 7.92% for Fe. The removal of the reducible fractions of Cu and Mn and the exchangeable fraction of Zn was the most significant in the treatment with [S, S]-EDDS. The exchangeable fraction of Pb was the main fraction that was affected by leaching using [S, S]-EDDS. Distribution of Cu and Mn were severely modified by leaching with [S, S]-EDDS. Percentages of residual fractions of the tested heavy metals in the treatment with [S, S]-EDDS after leaching were much higher than that in the control. Although column leaching using [S, S]-EDDS could remove target metals effectively and impaired their availability, it also dissolved large amounts of major elements and modified the distribution of Mn appreciably.     

重金属污染土壤植物修复基本原理及强化措施探讨

阐述了植物修复的基本概念及主要作用方式 ,并从土壤中重金属存在形态 ,植物对重金属吸收、排泄和积累以及植物生物学特性与植物修复的关系等方面讨论了重金属污染土壤植物修复的基本原理及局限性和限制性因素 ,从超富集植物性能强化和技术强化两方面探讨了植物修复的强化措施 ,并指出与现代化农业技术相结合是植物修复重金属污染土壤大规模商业应用的一条捷径     

Genotoxic effects of heavy metals in rat hepatocytes

The genotoxic interaction of metals, which are common environmental contaminants, was studied in cultured hepatocytes. Freshly isolated rat hepatocytes were exposed to concentrations of cadmium, copper, silver and lead salts ranging from non-cytotoxic to moderately cytotoxic (as determined by LDH release), and the incorporation of [³H]thymidine into the DNA, as a measure of repair synthesis, was followed. In addition, the uptake of metals by the nuclear fraction was determined using Inductively Coupled Plasma/Mass Spectrometry or atomic absorption spectrophotometry. The evaluation of binding of ¹⁰⁹Cd to the DNA in situ was also attempted. It was observed that after a 20 h exposure period, all the metals investigated were found in the nuclear fraction of hepatocytes, with Ag apparently being accumulated less efficiently. In parallel, Cd (0.18 to 1.8 µM) and Cu (7.9 to 78.5 µM) consistently produced a statistically significant stimulation of [³H]thymidine incorporation into the DNA, in the presence or absence of hydroxyurea while Ag was active only at the highest concentration tested (18.5 µM). In contrast, Pb failed to induce a UDS response at the levels used. Moreover, exposure of hepatocytes to 1.8 µM ¹⁰⁹CdCl₂ for 20 h led to a DNA binding ratio of 0.98 ± 0.23 ng Cd/ µg DNA. The present results support the view that the nucleus may be an important target organelle for metal toxicity.Abbreviations 2-AAF 2-acetylaminofluorene - Cd cadmium - HU hydroxyurea - lCP/MS inductively coupled plasma/mass spectrometry - Hg mercury - Ni nickel - UDS unscheduled DNA synthesis     

A feasibility test to estimate the duration of phytoextraction of heavy metals from polluted soils

The practical applicability of heavy metal (HM) phytoextraction depends heavily on its duration. Phytoextraction duration is the main cost factorfor phytoextraction, both referring to recurring economic costs during phytoextraction and to the cost of the soil having no economic value during phytoextraction. An experiment is described here, which is meant as a preliminary feasibility test before starting a phytoextraction scheme in practice, to obtain a more realistic estimate of the phytoextraction duration of a specific HM-polluted soil. In the experiment, HM-polluted soil is mixed at different ratios with unpolluted soil of comparable composition to mimic the gradual decrease of the HM content in the target HM-polluted soil during phytoextraction. After equilibrating the soil mixtures, one cropping cycle is carried out with the plant species of interest. At harvest, the adsorbed HM contents in the soil and the HM contents in the plant shoots are determined. The adsorbed HM contents in the soil are then related to the HM contents in the plant shoots by a log-log linear relationship that can then be used to estimate the phytoextraction duration of a specific HM-polluted soil. This article describes and evaluates the merits of such a feasibility experiment. Potential drawbacks regarding the accuracy of the described approach are discussed and a greenhouse-field extrapolation procedure is proposed.     

Source identification and availability of heavy metals in peri-urban vegetable soils: A case study from China

The purpose of this study was to investigate the total and available concentrations of Pb, Cr, Cu, Ni, and Zn in the vegetable soils from the outskirts of a heavy industry city, Northeast China, and to assess the sources of heavy metals and their availability. The average concentrations of Pb, Cu, and Zn were significantly higher than their background values of Changchun topsoil. Principal component analysis, cluster analysis, and geostatistical analysis results suggested that Pb, Cu, and Zn were consistently from anthropogenic sources, while Cr and Ni were from natural sources with low concentrations. Kriging results showed that several hotspots of high metal concentration were identified by the geochemical maps and caused by different environmental factors. Although the available (ethylene-diamine-tetraacetic acid-extractable) fractions showed much lower values than total concentrations of metals, Pb and Cu had relatively high AR^a (average availability ratio of metals) values. Our findings show that most of the studied metals had accumulated to some extent in vegetable soils and several hotspots of high metal concentration appeared at the peri-urban of Changchun. The concentrations of some metals in peri-urban vegetable soils have been largely affected by anthropogenic activities. Appropriate measures should be taken to effectively control heavy metal levels in vegetable soils and thus protect human health.     

西安城市路边土壤重金属来源与潜在风险

应用X-Ray荧光光谱仪对西安城市路边土壤重金属含量进行测定,运用相关分析、主成分分析和聚类分析探讨了路边土壤的重金属来源,并利用潜在生态风险指数法评价了其生态风险.结果表明:西安城市路边土壤中Co、Cr、Cu、Mn、N、iPb和Zn的平均含量均高于陕西土壤背景值.路边土壤中As、Mn和N i主要来自于自然源和交通源,Cu、Pb和Zn主要来自交通源,Co和Cr主要来源于工业源.潜在生态风险评价结果显示,西安城市路边土壤中重金属元素属于中等污染程度,具有中等潜在生态风险.     

Total concentrations and fractionation of heavy metals in road-deposited sediments collected from different land use zones in a large city (Nanjing), China

Abstract

In order to investigate heavy metal contamination in an urban environment during urbanization and economic development, 35 road-deposited sediment samples were collected from seven different land-use zones (commercial, residential, traffic, scenic park, educational, industrial and peri-urban) in Nanjing, a large city in P.R. China. The ranges of total metal concentrations found were: 28.7–272 mg kg^?1 for Cu; 24.8–268 mg kg^?1 for Ni; 37.3–204 mg kg^?1 for Pb; 140–798 mg kg^?1 for Zn; 0.44–2.19mg kg^?1 for Cd; and 60.6–250 mg kg^?1 for Cr. Metal fractionation was carried out using a modified three-step European Bureau of References (BCR) sequential extraction procedure. Cadmium and Zn were found predominantly associated with the acid extractable fractions; Ni and Cr were dominant in the residual fraction; Pb was predominantly associated with the residual and reducible fractions; Cu was dominant in the oxidizable and residual metal fractions. Based on the sum of the acid-extractable, reducible, and oxidizable fractions, Cd, Zn and Pb are potentially the most toxic metals in the road-deposited sediment in Nanjing. No significant differences, except for Zn, were found in the metal fractionation pattern for Cu, Ni, Pb, Cd, and Cr in different land use zones.     

The determination of heavy metals in water,suspended materials and sediments from Langat River,Malaysia

The distributions of heavy metals in the Langat River were studied for a period of six months between September 1984 and February 1985. Heavy metals such as arsenic, cadmium, cerium, cobalt, chromium, caesium, lanthanum, rubidium, antimony, scandium, thorium and zinc were determined in water, suspended materials and sediment samples from the Langat River by neutron activation and atomic absorption spectrometry. The concentrations of arsenic, cadmium, cerium, cobalt, scandium, antimony, and zinc were generally highest in the suspended materials, whereas the concentrations of chromium, rubidium and thorium were always highest in the sediments: Arsenic concentrations in the river were slightly higher than the natural concentration, while other elements were generally at their natural concentration levels. The use of arsenical herbicides in plantations along the river could be a source of arsenic pollution.     

Chemical speciation distribution characteristics and ecological risk assessment of heavy metals in soil from Sunan mining area,Anhui Province,China

In this study, the content characteristics, comprehensive pollution assessment, and morphological distribution characteristics of heavy metals (Mn, Cd, Cr, Pb, Ni, Zn, and Cu) were researched based on the processes of field investigation, sample collection, and experimental analysis. Results showed that the mean concentrations of Mn, Pb, Cr, Cu, Cd, Zn, and Ni in surface soils were 522.77, 22.56, 55.10, 25.41, 0.25, 57.02, and 48.47 mg kg^?1, respectively. The surface soil from Sunan mining area was contaminated by Cu, Cd, and Ni in different degrees, and high CV values of Cd, Zn, Pb, and Ni were influenced by local human activities possibly. The evaluation results suggested that the mean I_geo values were in the sequence of Cd (0.657) > Ni (0.052) > Cu (?0.293) > Mn (?0.626) > Zn (?0.761) > Cr (?0.884) > Pb (?0.899). Besides, Cd was the most significant potential risk factor among all elements. Nevertheless, the Cd of bioavailable speciations with higher proportion had stronger migration and toxicity, and was more easier to be absorbed and enriched than other elements by some crops (e.g., vegetables, rice), and being at a relatively higher potential ecological risk in soil.     

Speciation of heavy metals in soils based on charge separation

Summary An experimental approach to the speciation of heavy metals in soil extracts has been developed. The proposed methodology differentiates between differently charged metal species in water and ammonium acetate soil extracts. Furthermore a distinction has been made between labile and stable metal species by using a Chelex 100 chelating ion exchange resin.Significant differences in heavy metal speciation were found between an untreated soil and the same soil treated with 100 ppm Zn-ions and 100 ppm Zn-EDTA-ions.     

Migration of heavy metals in two Japanese soils

Summary The migration of common bio-toxic heavy metals in two typical soils of Japan under the influence of various leaching solutions was investigated.The results of the present study have indicated that the Pb and Cu ions were less mobile than those on Zn and Cd. Thus, the former two ions have largely been concentrated in the surface horizon while the latter two have been localised in the sub-surface layers. Ni has exhibited greater mobility than other heavy metals under all the leaching stress in both the soils. It is clear from the present study that Ni, Cd and Zn might pose a greater threat of ground water pollution than Cu and Pb. The specific migration properties of each metal ion varied depending on the nature of the ion and leaching solutions. The major soil factors governing the mobility of heavy metals in the soils have been discussed in the light of the results of the present investigation.     

Accumulative phases for heavy metals in limnic sediments

Data from mechanical concentrates of recent sediments indicate that clay minerals, clay-rich aggregates and heavy minerals are the major carriers of heavy metals in detrital sediment fractions. Hydrous Fe/Mn oxides and carbonates and sulfides, in their specific environments, are the predominant accumulative phases for heavy metals in autochthonous fractions. Sequential chemical extraction techniques permit the estimation of characteristic heavy metal bonding forms: exchangeable metal cations, easily reducible, moderately reducible, organic and residual metal fractions, whereby both diagenetic processes and the potential availability of toxic compounds can be studied. The data from lakes affected by acid precipitation indicate that zinc, cobalt and nickel are mainly released from the easily reducible sediment fractions and cadmium from organic phases. In contrast at pH 4.4, neither lead nor copper seem to be remobilized to any significant extent. Immobilization by carbonate precipitation seems to provide an effective mechanism for the reduction of dissolved inputs 9f metals such as zinc and cadmium in pH-buffered, hard water systems.     

Pesticides and heavy metals in Danish streambed sediment

The role of streambed sediment as a sink for pesticides and heavy metals was investigated in 30 Danish lowland streams. The investigated streams drain catchments varying in hydrology, topography, soil type and land use. The <250 m newly accumulated fraction of the uppermost 1–2 cm layer of streambed sediment was analysed for 19 old and modern pesticides and 9 heavy metals. DDE was present in the sediment of all the streams. Of the herbicides, fungicides and insecticides currently in use, the most frequently detected was diuron (50.0%), fenpropimorph (66.7%) and lambda-cyhalothrin (6.7%), respectively. The pesticides detected in the highest concentration were fenpropimorph (1700 ng g^–1), propiconazole (130 ng g^–1) and isoproturon (110 ng g^–1). The heavy metals are listed in order of increasing median concentration: Cd (0.80 g g^–1), Co (9.1 g g^–1), As (12.0 g g^–1), Ni (19.0 g g^–1), Cr (19.2 g g^–1), Pb (19.7 g g^–1), Cu (20.1 g g^–1), V (28.5 g g^–1), Zn (103 g g^–1). The average number of pesticides detected in the 27 streams draining predominantly agricultural catchments was (3.7±2.0) being higher (p=0.077) than in the three streams draining non-agricultural catchments (1.7±0.6). Pesticides were significantly related to catchment size, soil type and hydrological regime. Several heavy metals (Cr, Cu, Pb, V and Zn) were related to urban activity and soil type.     

Inhibition of photosynthesis by heavy metals

Inhibition of photosynthesis by heavy metals is well documented. In this review the results are compared between in vitro experiments on isolated systems (chloroplasts, enzymes ­.), experiments on excised leaves and intact plants and algae in vivo. In vitro experiments suggest potential sites of heavy metal interaction with photosynthesis at several levels of organisation, which are not necessarily confirmed in vivo. Analytical data on subcellular heavy metal level are generally missing to discuss their mechanism of action in the intact organism. In the field factors such as soil characteristics and air pollution have to be taken into account for assessing the mechanism of action of heavy metals on photosynthesis in plants, growing in a polluted erea.paper presented at the FESPP meeting in Strasbourg (1984)