Chemical Fractionation Of Metals Research Articles

Abundance and mobility of metal(loid)s in reservoir sediments of Singe Tsangpo and Yarlung Tsangpo in Tibet, China: Implications for ecological risk.

Geogenic arsenic enrichment in soil and river sediments of Tibet compared to its upper crustal abundance has been observed, raising the question whether other trace elements are also enriched and thus may pose ecological risks. Because human activities are limited, the reservoir sediments after the recent construction of the Shiquan dam on the Singe Tsangpo (ST) and the Zam dam on the Yarlung Tsangpo (YT) collect and thus represent material sourced from 14,870 km2 and 157,668 km2 of drainage areas, respectively. Bulk concentrations of the metalloid (As) and 13 metals (Li, Be, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Cs, and Pb) are analyzed for 123 samples from 9 mostly silty sediment cores (depth: 11-20cm) from the Shiquan Reservoir and for 250 samples from 13 mostly sandy sediment cores (depth: 9-28cm) from the Zam Reservoir. These elemental concentrations are normalized to the upper crustal Fe abundance of 3.9% to arrive at a regional sediment geochemical background value for each element. The regional background values of most elements in the ST drainage and the YT drainage are comparable with the upper crustal abundance. However, three elements (Li, As, and Cs) in both drainage basins display significant enrichment compared to their respective upper crustal abundance. Sequential leaching of a subset of sediment samples from the ST (n = 18) and YT (n = 29) drainages reveals that chemical fractions of metals and metalloids in these two reservoirs are similar, with most of the elements dominated by the residual fraction with low mobility. Taken together, the ecological risks of the most studied elements in the reservoir sediments are likely low pending further aquatic bioavailability investigations, except that As, Cu, Pb, and Be deserve more attention due to their elevated levels in mobile fractions.

Chemical Fractionation of Trace Elements in a Metal-Rich Amphibolite Soil Amended with Municipal Solid Waste Composts

The high concentrations of metals naturally present in soils developed on mafic and ultramafic rocks such as amphibolite could be mobilized in response to modification of soil physicochemical properties after compost amendment. However, so far, research with this type of soils is insufficient. With the objective of understanding the potential risk associated to trace elements in this case, we have studied the chemical distribution of trace metals in an amphibolite agricultural soil amended with several composts and incubated during 3 months in the laboratory. An agricultural acid soil developed on amphibolites was amended with 5% (dry weight) of five commercial composts (produced mainly from municipal solid wastes) and incubated in the laboratory during 90 days. Trace element potential mobility and bioavailability in the soils were studied by means of chemical analyses: extraction of immediately available trace elements with 0.01 N CaCl2 and the normalized BCR sequential extraction procedure. High concentrations of 0.01 N CaCl2 soluble metals occurred in the non-amended soil (especially Zn and Ni), that decreased after compost addition for Pb, Zn, Ni and Cd, with no effect on Cu and Cr. In general, composts had little effect on the BCR fractionation of the trace elements, because of their high native concentrations in the studied soil. Even so, the addition of the composts with the highest metal contents increased the oxidizable (organic matter-bound) and reducible (iron oxides-bound) fractions of soil Cu and the soluble and reducible fractions of soil Zn and Ni. None of the composts modified Pb fractionation, which was mostly found in the reducible fraction, nor that of Cr, present in more than 80% in the residual non-extractable fraction. This study showed that, in soils developed over metal-rich parent materials such as amphibolites, chemical fractionation of metals after compost amendment is more influenced by the nature of the metals previously present in soil than by the composition of the composts.

Chemical fractionation by sequential extraction of Cd, Pb, and Cu in Antarctic atmospheric particulate for the characterization of aerosol composition, sources, and summer evolution at Terra Nova Bay, Victoria Land

Insights in the knowledge of the Antarctic atmospheric composition of Cd, Pb, and Cu are obtained by chemical fractionation of metals in the aerosol to obtain water-soluble (soluble), dilute HCl-extractable (extractable), and inert fractions. The aim is to correlate chemical fractions to metal sources. A three-step sequential extraction and square wave anodic stripping voltammetry were applied to analyze aerosol samples (PM10) collected during summer near the “M. Zucchelli” Italian Station (Victoria Land). Metal mass fractions varied as follows (min–max, average, in μg g−1): Cd 1.4–38 (11), Pb 26–83 (47), and Cu 150–840 (490). In terms of atmospheric concentrations, the values were as follows (pg m−3): Cd 0.93–39 (9.5), Pb 17–60 (33), and Cu 88–480 (340). The soluble fraction relates to the marine contribution. The extractable fraction refers mainly to local human activity. The inert fraction is associated with the crustal dust. Soluble, extractable, and inert metal fractions changed very much during the Austral summer according to changes of source types and strengths. The observations on the temporal trends, the relationships with wind direction and speed, and the correlations between the same fractions of different metals, together with results of principal component analysis, agreed with the stated associations between chemical fractions and major sources. Fractionated data are among the first even published in Antarctic research.

Assessing the influence of technosol and biochar amendments combined with Brassica juncea L. on the fractionation of Cu, Ni, Pb and Zn in a polluted mine soil

Soil metal pollution is a widespread problem around the world and remediation of these soils is difficult. The objective of this study was to investigate the effect of two different strategies on the chemical fractions of metals in a soil of a depleted copper mine: (1) amending with a mixture of a technosol made of wastes and biochar and (2) amending combined with planting vegetation (Brassica juncea). A 3-month greenhouse experiment was carried out to evaluate the effects of organic amendments and vegetation on the metal fractionation of Cu, Ni, Pb and Zn in a mine soil of the depleted copper mine at Touro (Spain). We compared the influence of organic amendments alone (technosol + biochar) and combined with mustard plants (Brassica juncea L.). The results showed that amending with a technosol made of wastes promoted plant growth (from 0.7 to 2.9 g of biomass produced) and reduced the CaCl2-extractable metal concentration in soil, reduced the mobility factor of Cu from 18.3 to 1.6, Ni from 47.5 to 2.3 and Pb from 17.9 to 2.1, and also reduced the concentration of metals in the mobile soil fractions. It was not possible to grow up Brassica juncea plants in the untreated settling pond soil due to the extremely degraded conditions of that soil. However, the application of the used technosol increased the Pb and Zn pseudototal concentrations in the amended soils. We conclude that the combination of amending with wastes and planting B. juncea provides little additional benefit for remediating a metal-polluted soil compared with incorporation of wastes alone.

The build-up dynamic and chemical fractionation of Cu, Zn and Cd in road-deposited sediment

This study investigates the build-up dynamics of heavy metals on impervious urban surfaces with different antecedent dry-weather periods (ADPs) and land-use types. Solid-phase concentration (mg/kg), surface load (mg/m2), and chemical fractionation of Zn, Cu and Cd in bulk- and size-fractionated road-deposited sediment were determined. The inherent correlations among particle size distribution, ADP, land use, and chemical fractionation were analysed by hierarchical cluster analysis. Results show a clear build-up phenomenon of Cu and Zn at a city commercial centre and a highway area. Cd had complex build-up patterns. With regard to chemical fractionation, Zn and Cd could pose higher risks than Cu to aquatic biota after a longer ADP. Special attention should be paid to the significant risk in a rural area because of the high proportion of exchangeable chemical fractionation in terms of the unstable Cd component. Hierarchical cluster analysis indicates that ADP had a strong influence on build-up processes of sediments and associated metals. The metal contents were very dependent on the particle size distribution. However, the chemical fractionation of metals was dependent to a lesser extent on the land-use type.

Effect of biosolid application to Mollisol Chilean soils on the bioavailability of heavy metals (Cu, Cr, Ni, and Zn) as assessed by bioassays with sunflower (Helianthus annuus) and DGT measurements

This study assessed the effect of biosolid application on the bioavailable fraction of some trace elements (Cu, Cr, Ni, and Zn) using a bioassay with sunflower (Helianthus annuus) and a chemical assay, diffusion gradient in thin films (DGT). Five surface soil samples (0–20 cm) were collected from an agricultural zone in Central Chile where biosolids are likely to be applied. Municipal biosolids were mixed with the soil at concentrations of 0, 30, 90, and 200 Mg ha−1. The experiment to determine the bioavailability of metals in the soil using the bioassay was performed using sunflower. The DGT technique and Community Bureau of Reference (BCR) sequential extraction were used to determine the bioavailable fractions of the metals. The application of biosolids increased the phytoavailability of Zn, Ni, and Cr in most of the soils, as indicated by the increasing concentrations in sunflower plants as the biosolid application rate increased. In two of the soils, Codigua and Pelvin, this increase peaked at an application rate of 90 Mg ha−1. Decreases in the bioavailable fractions of Zn, Ni, and Cr were observed with higher biosolid application rates. The bioavailability of metals was estimated through multiple linear regression models between the metals in the sunflower plants and the different chemical fractions of metals in the soils treated with different biosolid rates, which displayed a positive contribution of the labile (water soluble, carbonate, and exchangeable), oxide, and organic metal forms in the soil, particularly with respect to Ni and Zn at application rates of 30 and 90 Mg ha−1. The bioavailable fraction of metals was determined in soils using the DGT technique. The effective concentration (C E) results were compared with those in sunflower plants. The DGT technique could effectively predict the bioavailable fractions of Cr, Ni, and Zn in the Taqueral soil but only that of Zn in the Polpaico soil. The application of biosolids significantly increased the labile fraction of most of the metals in the studied soils, particularly at the highest biosolid application rate. C E increased as the concentration of biosolids increased for most of the metals. The effectiveness of the DGT technique for predicting the bioavailability of metals was dependent on the soil type and the metal. However, the C E for soil Cu was not related to plant Cu for all soils studied.

Urbanization increased metal levels in lake surface sediment and catchment topsoil of waterscape parks

Lake surface sediment is mainly derived from topsoil in its catchment. We hypothesized that distribution of anthropogenic metals would be homogenous in lake surface sediment and the lake's catchment topsoil. Anthropogenic metal distributions (cadmium (Cd), copper (Cu), lead (Pb), and zinc (Zn)) in fourteen waterscape parks were investigated in surface sediments and catchment topsoils and possible source homogeneity was tested using stable Pb isotopic ratio analysis. The parks were located along an urbanization gradient consisting of suburban (SU), developing urban (DIU), developed urban (DDU), and central urban core (CUC) areas in Shanghai, China. Results indicated that surface lake sediments and catchment topsoils in the CUC parks were highly contaminated by the investigated anthropogenic metals. Total metal contents in surface sediment and topsoil gradually increased along the urbanization gradient from the SU to CUC areas. Generally, the surface sediments had greater total metal contents than their catchment topsoils. These results suggest that urbanization drives the anthropogenic metal enrichment in both surface sediment and its catchment topsoil in the waterscape parks. Soil fine particles (<63μm) and surface sediments had similar enrichment ratios of metals, suggesting that surface runoff might act as a carrier for metals transporting from catchment to lake. Stable Pb isotope ratio analysis revealed that the major anthropogenic Pb source in surface sediment was coal combustion as in the catchment topsoil. Urbanization also correlated with chemical fractionation of metals in both surface sediment and catchment topsoil. From the SU to the CUC parks, amounts of labile metal fractions increased while the residual fraction of those metals remained rather constant. In short, urbanization in Shanghai drives anthropogenic metal distribution in environmental matrices and the sources were homogenous.

Trace Metal Occurrence and Mobility Assessment in Stream Sediments near the Sungun Porphyry Copper Deposit in Northwest Iran

The Sungun porphyry copper deposit is located 100 km northeast of Tabriz in the Azarbaijan province of Iran. The total concentration and chemical fractionation of metals and metalloids (As, Se, Cd, Cr, Ni, Co, and Zn) in sediment downstream of the Sungun mine was investigated. The degree of contamination was evaluated using the sediment pollution index (SPI) and enrichment factor. The concentrations of As, Cd, Se, and Zn in the contaminated sediments were elevated due to anthropogenic activities. According to the SPI, surface sediments in the ephemeral rivers flowing in the vicinity of the Sungun porphyry copper deposit are classified as natural sediment with no ecological risk, while sediments that received contaminated effluents are classified as slightly polluted. Sequential extraction indicated that Co was principally associated with the iron and manganese oxide fraction, while other elements (As, Zn, Cr, Se, and Ni) were mainly distributed in residual phases. Cadmium is the only element that has a high potential for mobility and bioavailability in the sediments and, of the investigated elements, it poses the greatest potential risk to the local aquatic ecosystems. The chemical fractionation pattern of elements appears to be influenced by industrial effluents. Although the bioavailable fraction of most contaminant metals is low due to the freshness of the sediments, over time, the oxidation of sulfide minerals in these sediments could contribute contaminant elements in soluble form.

Chemical fractionation of metals in core sediments of Orogodo River, southern Nigeria

Sequential chemical extraction of metals (Cu, Ni, Mn, Fe, Pb, Cr, and Zn) from core sediments of the Orogodo River was carried out with a view of providing information on the phase distribution of these metals with respect to depths and seasons. The results indicate that copper was speciated into organic matter/sulfide, Fe–Mn oxides, and residual forms at 0–5 cm depth while at deeper sections copper was predominantly in the residual form. Nickel was speciated mainly into Fe–Mn oxides and residual forms. The average of lead in various particulate phases of the sediment are 0–100% for residual; 0–8% for carbonate; 0–16.2% for exchangeable; 0–10% for organic matter/sulfide form and 22–56% for Fe–Mn oxides bound metals. Manganese was speciated into exchangeable (10–36%) and Fe–Mn oxides bound (10–48%) at the surface layers of 0–20 cm depths and predominantly in the residual form in deeper sections implying partitioning into trioctahydral clay and/or well-defined crystalline oxides. Iron was predominantly in the Fe–Mn oxides and residual fractions, less than 8% in the organic fraction, and 24.4–37.3% in the exchangeable and carbonates fractions at the surface. The percentage contributions of iron in the exchangeable and carbonate fractions decreased to 3.2% at 55–60 cm depth. The amount of chromium in the exchangeable fraction ranged from 0% to 7% for exchangeable; 0–26.5% for organic matter/sulfide bound; 3.8–17.9% for Fe–Mn oxides; and 46.8–100% for residual fraction. The mobility factors of the metals indicated that these metals were relatively mobile at top sections as compared with deeper sections. The overall picture of metal mobility and availability indicates potential contamination risk by Fe, Zn, Mn, and Pb in the Orogodo River sediment system.

Relationships of Heavy Metals in Natural Lake Waters with Physico-chemical Characteristics of Waters and Different Chemical Fractions of Metals in Sediments

The relationships between heavy metal concentrations and physico-chemical properties of natural lake waters and also with chemical fractions of these metals in lake sediments were investigated in seven natural lakes of Kumaun region of Uttarakhand Province of India during 2003–2004 and 2004–2005. The concentrations of Cr, Mn, Fe, Ni, Cu, Zn, Cd and Pb in waters of different lakes ranged from 0.29–2.39, 10.3–38.3, 431–1407, 1.0–6.6, 5.3–12.1, 12.6–166.3, 0.7–2.7 and 3.9–27.1 μg l−1 and in sediments 14.3–21.5, 90.1–197.5, 5,265–6,428, 17.7–45.9, 13.4–32.0, 40.0–149.2, 11.1–14.6 and 88.9–167.4 μg g−1, respectively. The concentrations of all metals except Fe in waters were found well below the notified toxic limits. The concentrations of Cr, Mn, Ni, Cu, Zn, Cd and Pb were positively correlated with pH, electrical conductivity, biological oxygen demand, chemical oxygen demand and alkalinity of waters, but negatively correlated with dissolved oxygen. The concentrations of Cr, Ni, Zn, Cd and Pb in waters were positively correlated with water soluble + exchangeable fraction of these metals in lake sediments. The concentrations of Zn, Cd and Pb in waters were positively correlated with carbonate bound fraction of these metals in lake sediments. Except for Ni, Zn and Cd, the concentrations of rest of the heavy metals in waters were positively correlated with organically bound fraction of these metals in lake sediments. The concentrations of Cr, Mn, Ni, Cu and Zn in waters were positively correlated with reducible fraction of these metals in lake sediments. Except for Cd, the concentrations of rest of the metals in waters were positively correlated with residual fraction and total content of these heavy metals in lake sediments.

Metal/metalloid contamination and isotopic composition of lead in edible mushrooms and forest soils originating from a smelting area

High metal contents in edible mushrooms growing in severely contaminated industrial areas pose an important toxicological risk. In the presented study, trace element (Pb, Cd, Zn, Cu, Ag, As, Se) contents were determined in caps and stipes of three different edible mushroom species ( Boletus edulis Bull. Fr., Xerocomus badius Fr. Gilb., Xerocomus chrysenteron Bull. Quél.). Additionally, information about the chemical fractionation of metals in separate soil horizons and Pb isotopic data from soils and fruiting bodies allowed a more detailed insight on the uptake mechanisms of metals by the studied mushroom species. Total metal and metalloid concentrations in the organic soil horizons reached 36 234 mg Pb kg − 1 ; 11.9 mg Cd kg − 1 ; 519 mg Zn kg − 1 ; 488 mg Cu kg − 1 ; 25.1 mg Ag kg − 1 ; 120 mg As kg − 1 and 5.88 Se mg kg − 1 . In order to evaluate the accumulation capacity of the studied species, bioconcentration factors (BCF) were calculated for separate trace elements. For selected metals (Pb, Cd, Zn, Cu), a modified BCF calculation (using EDTA-extractable concentrations of metals in soil) was proposed. High contents of Pb (up to 165 mg kg − 1 ) and Cd (up to 55 mg kg − 1 ) exceeded all the regulatory limits in all the studied species. This was also the case for Se (up to 57 mg kg − 1 ) in B. edulis. Intensive consumption of this species grown in such polluted areas can therefore pose toxicological risks for human health. A novel finding was that X. badius can act as an Ag accumulating species when grown at polluted sites due to the high concentrations of Ag (up to 190 mg kg − 1 ) in caps. Pb isotopic data showed that Pb originating from the recent air pollution control residues is present mainly in the exchangeable/acid-extractable fraction of the organic horizons and is taken up by fruiting bodies; especially in the case of B. edulis, where fast Pb accumulation occurs. Due to the high species-dependent variations of metal contents, the studied mushrooms are not suitable as bioindicators of environmental pollution.

Chemical fractionation of metals in wetland sediments: Indiana Dunes National Lakeshore.

Tessier-type (1979) sequential extractions for heavy metals (Cd, Cr, Cu, Fe, Mn, Pb, and Zn) were conducted on sediments from two wetland sites, one inundated and the other drained, within the Indiana Dunes National Lakeshore (IDNL), NW Indiana, with the objective of (i) evaluating extraction techniques on organic-rich sediments, (ii) determining the geochemistry and mobility of potentially biotoxic trace metals in a contaminated environment, and (iii) considering the implications of different restoration strategies on the potential for heavy metal remobilization. Long and repeated extractions were needed to effectively degrade the organic-rich sediments (up to 75% of the sediment by mass). Analysis of sulfur fractionation revealed that it was predominantly sequestered along with the organically bound fraction (renamed oxidizable). Metal recovery was good with the sum of the extractant steps typically within 20% of the total metal concentration determined after total microwave digestion. Results showed metal fractionation to be both metal- and site-specific, The oxidizable fraction is dominant for Cu, Cr, and Fe (>65% of the nonresidual fraction for almost all samples) and overall is most important also for Cd and Pb. The iron/manganese oxide fraction is important for Pb, Mn, and Zn, particularly at the drained site. The carbonate bound fraction is relatively insignificant at both sites, except for Cd and Mn, although it is more important at the drained site. The exchangeable fraction is significant in the uppermost sediments at the drained site, particularly for Cd (3-24%), Pb (3-14%), and Zn (36-45%); whereas, for the inundated site, it ranged only from 0 to 1% Zn, with no detectable Cd or Pb. Chromium, Cu, and Fe exist in forms not likely to be remobilized, whereas Cd, Mn, Pb, and Zn are potentially mobile if drained wetland sites are reflooded (and pH and redox potential altered). Simple mass balance calculations illustrate the potential for the removal of approximately 84,375 kg of exchangeable Zn if currently drained sites across the IDNL are reflooded, with concentrations in water draining into Lake Michigan as high as 5 ppm.