Heavy meals in urban roadside soils, part 1: effect of particle size fractions on heavy metals partitioning

Urban roadside soils are important environmental media for assessing heavy metal concentrations in urban environment. However, among other things, heavy metal concentrations are controlled by soil particle grain size fractions. In this study, two roadside sites were chosen within the city of Xuzhou (China) to reflect differences in land use. Bulk soil samples were collected and then divided by particle diameter into five physical size fractions, 500–250, 250–125, 125–74, 74–45, < 45 μm. Concentrations of metals (Ti, Cr, Al, Ga, Pb, Ba, Cd, Co, Cu, Mn, Ni, V, Zn, Mo, As, Sb, Se, Hg, Bi, Ag) were determined for each individual fraction. These metals could be roughly classified into two groups: anthropogenic element (Pb, Ba, Cd, Cu, Zn, Mo, As, Sb, Se, Hg, Bi, Ag) and lithophile element (Ti, Cr, Al, Ga, Co, Mn, Ni, V) in terms of values of enrichment factor. As expected, higher concentrations of anthropogenic heavy metals (Cu, Zn, Mo, As, Hg, Bi, Ag) are observed in the finest particle grain size fraction (i.e. < 45 μm). However, heavy metals Se, Sb and Ba behave independently of selected grain size fractions. From the viewpoint of mass loading, more than 30% of the concentrations for all anthropogenic heavy metals are contributed by the particle grain size fractions of 45–74 μm at site 1 and more than 70% of the concentrations for all heavy metals are contributed by the particle grain size fractions of 45–74 and 74–125 μm at site 2. These results are important for transport of soil-bound heavy metals and pollution control by various remedial options.     

Geochemical factors controlling accumulation of major and trace elements in Greenland coastal and fjord sediments

 The major (Al, Ti, Ca, Mg, Fe, Mn, Si) and trace element (Cd, Cr, Cu, Hg, Li, Ni, Pb, V, Zn) concentrations in surficial (<20 cm) sediments from fjords and open coastal waters around Greenland have been determined. Regionally, high concentrations of Fe, Ti, Mg, Cr, Cu, Ni, and V occur in some west and east coast sediments, but they appear to be natural in origin, as there is no indication of anthropogenic influence. Chemical partition indicates that most of the heavy metals are structurally bound in various silicate, oxide, and sulfide minerals. These host minerals occur more or less equally in the coarse and fine sediment fractions (material >63 μm and <63 μm) and have accumulated at the same rate as other detrital clastic material. Provenance and glaciomarine deposition are the main factors controlling the abundance and distribution of the major and trace elements. The chemical composition reflects the mineralogical differences in the provenance of glacial marine material deposited by water and ice adjacent to Greenland. The main source of the sediments enriched in Ti, Fe, Mg, Cr, Cu, Ni, and V appears to be material derived from the volcanic rocks of the Mesozoic-Tertiary Provinces of Greenland by glacial erosion. Received: 26 June 1995 · Accepted: 11 August 1995     

Elemental chemistry and geochemical partitioning of heavy metals in road dust from Dhanbad and Bokaro regions,India

Road dust collected from India’s richest and oldest coal mining belt of Dhanbad and Bokaro regions was analysed for particle size characteristics and elemental composition. The particle size distribution pattern shows dominance of 500–250 μm and 250–125 μm size fractions, constituting 45–58% of the mass size spectrum. Si is the most dominant element and its concentration varied between 29.3 and 36.4% with the average value 34.3%. Fe, Ti and Mn are the dominant heavy metals followed by Zn, Cr, Pb, Cu, Ni and Co. No significant differences concentration of metals between sampling sites was apparent; however, some sites tend to accommodate relatively higher metals due to its proximity to industrial and mining sites. In general, finer fraction (<63 μm) tend to contain 1–3 times higher metals as compared with the bulk composition. Except Pb and Mn all the measured metals are generally lie below grade zero, suggesting that there is no pollution threat with respect to these metals in roadway dust from the studied sites. Geochemical speciation study shows that the lithogenic phase is the major sink for heavy metals. Fe–Mn oxide and organic are the major non-lithogenic phases and Pb and Zn are the major elements of the non-lithogenic phase.     

Status of anthropogenically induced metal pollution in the Kanpur-Unnao industrial region of the Ganga Plain, India

 The Ganga Plain is one of the most densely populated regions and one of the largest groundwater repositories of the Earth. For several decades, the drainage basin of the Ganga Plain has been used for the disposal of domestic and industrial wastes which has adversely affected the quality of water, sediments and agricultural soils of the plain. The concentrations of Al, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sn, Zn and organic carbon were determined in river sediments and soils of the Ganga Plain in the Kanpur-Unnao industrial region in 1994 and 1995 (pre-monsoon period of April–May). High contents (maximum values) of C-org (12.0 wt. %), Cr (3.40 wt. %), Sn (1.92 wt. %), Zn (4000 mg/kg), Pb (646 mg/kg), Cu (408 mg/kg), Ni (502 mg/kg) and Cd (9.8 mg/kg) in sediments (<20 μm fraction); and C-org (5.9 wt. %), Cr (2.16 wt. %), Sn (1.21 wt %), Zn (975 mg/kg) and Ni (482 mg/kg) in soils (<20 μm) in the pre-monsoon period of 1994 were found. From 1994 to 1995 the contents of Fe and Sn in sediments increase whereas those of C-org, Cd, Cu, Ni and Zn decrease. Considering the analytical errors, Al, Co, Cr, Mn and Pb do not show any change in their concentrations. In soils, the contents of Cd, Fe and Sn increase whereas those of Ni decrease from 1994 to 1995. Aluminium, Co, Cr, Cu, Mn, Pb and Zn do not show any change in their concentrations from 1994 to 1995. About 90% of the contents of Cd, Cr and Sn; 50–75% of C-org, Cu and Zn; and 25% of Co, Ni and Pb in sediments are derived from the anthropogenic input in relation to the natural background values, whereas in soils this is the case for about 90% of Cr and Sn; about 75% of Cd; and about 25% of C-org, Cu, Ni and Zn. The sediments of the study area show enrichment factors of 23.6 for Cr, 14.7 for Cd, 12.2 for Sn, 3.6 for C-org, 3.2 for Zn, 2.6 for Cu and 1.6 for Ni. The soils are enriched with factors of 10.7 for Cr, 9.0 for Sn, 3.6 for Cd, 1.8 for Ni and 1.5 for Cu and Zn, respectively. Received: 3 March 1998 · Accepted: 15 June 1998     

Grain size and geochemical partitioning of heavy metals in sediments of the Damodar River – a tributary of the lower Ganga, India

 The distribution of Si, Al, Fe, Mn, Cu, Zn, Ni and Cr in different grain-size fractions and geochemical association of Fe, Mn, Cu and Zn with <63-μm size fraction of bed sediments of Damodar River has been studied. In general, concentrations of heavy metals tend to increase as the size fractions get finer. However at two sites, near mining areas, the coarser particles show similar or even higher heavy metal concentrations than finer ones. The higher residence time and/or presence of coarser particles from mining wastes are possibly responsible for higher metal content in the coarser size fractions. The chemical fractionation study shows that lithogenic is the major chemical phase for heavy metals. Fe and Mn are the major elements of the lithogenic lattice, constituting 34–63% and 22–59%, respectively, of total concentrations. Fe-Mn oxide and organic bound fractions are significant phases in the non-lithogenic fraction. The carbonate fraction is less significant for heavy metal scavenging in the present environment and shows the following order of abundance Zn>Cu>Mn>Fe. The exchangeable fraction of the Damodar sediments contains very low amounts of heavy metals suggesting poor bioavailability of metals. Received: 18 August 1998 · Accepted: 1 December 1998     

Bed sediment-associated trace metals in an urban stream, Oahu, Hawaii

 Of the 117 stream and lake systems sampled nationwide, fish from Manoa Stream on Oahu, Hawaii, have consistently shown the highest Pb concentrations. Therefore a detailed study was conducted to examine total metal contents in bed sediments from a 5.8-km stretch of Manoa Stream. A total of 123 samples (<63 μm) were examined for 18 elements and 14 samples for 21 elements. Selected samples were also examined using different leach solutions to examine metal phase associations. All trace metal data, computations of enrichment ratios and the modified index of geoaccumulation point to mineralogical control for Cr and Ni; minor anthropogenic contamination for Ba, Cd, Cu, Hg and Zn; and a very strong contamination signal for Pb. Maximum Pb contents (up to 1080 mg kg⁻¹) were associated with anthropogenic material dumping in minor tributaries, storm sewer sediments and sediments in the “lower” section of the basin. Proportionally Pb had the highest non-residual component of elements examined; dominantly in the reducible phase associated with Mn and amorphous Fe oxyhydroxides. The contamination signal was typically lowest in the “undisturbed” headwater reach of the basin (above 5.1 km) with significant increases throughout the “residential” and “commercial-institutional” zones of the mid-basin. The spatial pattern of bed sediment contamination and evidence from storm sewer-outlet sediments strongly indicates that Pb, and to a lesser degree some other metals, is still being transported to the stream and the primary agent is soil erosion and transport of metals sorbed to sediments. The primary source of sediment-associated metals is considered to be the automobile, though other minor sources can not be ruled out. Received: 3 November 1998 · Accepted: 26 January 1999     

Distribution and immobilization of heavy metals in Pliocene aquifer sediments in Wadi El Natrun depression, Western Desert

The Pliocene aquifer receives inflow of Miocene and Pleistocene aquifer waters in Wadi El Natrun depression. The aquifer also receives inflow from the agricultural activity and septic tanks. Nine sediment samples were collected from the Pliocene aquifer in Wadi E1 Natrun. Heavy metal (Cu, Sr, Zn, Mn, Fe, Al, Ba, Cr, Ni, V, Cd, Co, Mo, and Pb) concentrations of Pliocene aquifer sediments were investigated in bulk, sand, and mud fractions. The determination of extractable trace metals (Cu, Zn, Fe, Mn, and Pb) in Pliocene aquifer sediments using sequential extraction procedure (four steps) has been performed in order to study environmental pathways (e.g., mobility of metals, bounding states). These employ a series of successively stronger chemical leaching reagents which nominally target the different compositional fractions. By analyzing the liquid leachates and the residual solid components, it is possible to determine not only the type and concentration of metals retained in each phase but also their potential ecological significance. Cu, Sr, Zn, Mn, Fe, and Al concentrations are higher in finer sediments than in coarser sediments, while Ba, Cr, Ni, V, Cd, Co, Mo, and Pb are enriched in the coarser fraction. The differences in relative concentrations are attributed to intense anthropogenic inputs from different sources. Heavy metal concentrations are higher than global average concentrations in sandstone, USEPA guidelines, and other local and international aquifer sediments. The order of trace elements in the bulk Pliocene aquifer sediments, from high to low concentrations, is Fe?>?Al?>?Mn?>?Cr?>?Zn?>?Cu?>?Ni?>?V?>?Sr?>?Ba?>?Pb?>?Mo?>?Cd?>?Co. The Pliocene aquifer sediments are highly contaminated for most toxic metals, except Pb and Co which have moderate contamination. The active soluble (F0) and exchangeable (F1) phases are represented by high concentrations of Cu, Zn, Fe, and Mn and relatively higher concentrations of Pb and Cd. This may be due to the increase of silt and clay fractions (mud) in sediments, which act as an adsorbent, retaining metals through ion exchange and other processes. The order of mobility of heavy metals in this phase is found to be Pb?>?Cd?>?Zn?>?Cu?>?Fe?>?Mn. The values of the active phase of most heavy metals are relatively high, indicating that Pliocene sediments are potentially a major sink for heavy metals characterized by high mobility and bioavailability. Fe–Mn oxyhydroxide phase is the most important fraction among labile fractions and represents 22% for Cd, 20% for Fe, 11% for Zn, 8% for Cu, 5% for Pb, and 3% for Mn. The organic matter-bound fraction contains 80% of Mn, 72% of Cu, 68% of Zn, 60% of Fe, 35% of Pb, and 30% of Cd (as mean). Summarizing the sequential extraction, a very good immobilization of the heavy metals by the organic matter-bound fraction is followed by the carbonate-exchangeable-bound fraction. The mobility of the Cd metal in the active and Fe–Mn oxyhydroxide phases is the highest, while the Mn metal had the lowest mobility.     

Trace element distributions in aquatic sediments of Danang – Hoian area, Vietnam

 Distribution of the trace elements Cr, Cu, Ni, Pb and Zn in surficial sediments of the river/sea environment in Danang – Hoian area (Vietnam) was investigated to examine the degree of metal pollution caused by anthropogenic activities. Point sources from domestic and industrial wastes are identified as dominant contributors of trace element accumulation. Surficial sediments of Hoian River show extremely high total concentrations of Cu (Average Concentration 295 μg/g), Ni (AC 112 μg/g), Pb (AC 396 μg/g) and Zn (AC 429 μg/g) that exceed assigned safety levels ER-M. Similarly, the sediments of Han River show high Pb (AC 188 μg/g) and Zn (AC 282 μg/g) contents. In marine sediments of Thanhbinh beach Pb is also enriched (138 μg/g) above guideline levels. In contrast the sediments of the Cude River are dominated by trace element concentrations close to background values. Received: 17 December 1998 · Accepted: 6 May 1999     

Heavy metals in Oka river sediments (Urdaibai National Biosphere Reserve, northern Spain): lithogenic and anthropogenic effects

 The Oka River basin is located in the Urdaibai National Biosphere Reserve, North Spain. In order to obtain a preliminary view of its environmental conditions, nitric acid extractable Fe, Mn, Zn, Pb, Cu, Cr, Ni and Co, organic matter content (L.O.I.), geochemical fractionation of heavy metals and mineralogical composition were analysed in surficial sediments (fraction <63 μm) collected in October 1991. Relatively high concentrations of metals occurred in a sampling site upstream, due to a local natural enrichment controlled by weathering of volcanic rocks. Geochemical fractionation confirmed the lithogenic origin of metals, which were mainly associated to the detrital phase. The significant increase of heavy metals found in some samples collected in the municipal area of Gernika suggested a pollution effect, related to anthropogenic wastes. Large amounts of metallic slags have been found mixed with the sediments upstream from this locality. Nevertheless, in view of their composition, it is unlikely that these slags constitute a significant source of heavy metals in the studied area. In a second sampling in October 1997 an apparent decreasing trend in some heavy metal levels was noted, particularly for Pb and Cu. Nowadays, enrichment factors relative to background values confirm moderate anthropogenic influence on Zn, Pb, Cu, Cr and Ni concentrations. However, heavy metal levels in the Oka river sediments are much lower than those detected in other major rivers of the Basque Country (Nervión, Urumea, Deba). Received: 7 July 1997 · Accepted: 4 July 1998     

Regional geochemistry of trace elements in Chesapeake Bay sediments

The concentrations of Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb in 177 surface sediment samples from throughout Chesapeake Bay are reported. Analyses were made of both unfractionated samples and the <63 μm fractions. Analytical uncertainty, always less than ±10%, controlled reproducibility in analyses of the <63 μm fractions, but sampling variance controlled reproducibility in the unfractionated samples, especially when coarse-grained sediments were being analyzed. Sediments in the northernmost part of the bay are enriched relative to average continental crust in all elements except Cr. This reflects the composition of dissolved and suspended material being delivered to that region by the Susquehanna River. The enriched sediments appear not to be transported south of Baltimore in significant quantily. Zinc, cadmium, and lead are enriched relative to average crust throughout the bay and in most other estuaries in the eastern United States.     

Heavy metal contamination of coastal lagoon sediments by anthropogenic activities: the case of Nador (East Morocco)

Nador lagoon sediments (East Morocco) are contaminated by industrial iron mine tailings, urban dumps and untreated wastewaters from surrounding cities. The lagoon is an ecosystem of biological, scientific and socio-economic interests but its balance is threatened by pollution already marked by biodiversity changes and a modification of foraminifera and ostracods shell structures. The aim of the study is to assess the heavy metal contamination level and mobility by identifying the trapping phases. The study includes analyses by ICP-AES and ICP-MS, of, respectively, major (Si, Al, Mg, Ca, Fe, Mn, Ti, Na, K, P) and trace elements (Sr, Ba, V, Ni, Co, Cr, Zn, Cu, As, Pb, Cd) in sediments and suspended matter, heavy metals enrichment factors calculations and sequential extractions. Results show that sediments contain Zn, Cu, Pb, V, Cr, Co, As, Ni with minimum and maximum concentrations, respectively, of 4–1190 μg/g, 4–466 μg/g, 11–297 μg/g, 11–194 μg/g, 9–139 μg/g, 1–120 μg/g, 4–76 μg/g, 2–62 μg/g. High concentrations in Zn are also present in suspended matter. The enrichment factors show contamination in Zn, Pb and As firstly induced by the mining industry and secondly by unauthorized dumps and untreated wastewaters. Cr and Ni are bound to clays, whereas V, Co, Cu and Zn are related to oxides. Thus, the risk in metal mobility is for the latter elements and lies in the oxidation–reduction-changing conditions of sediments.     

Adsorption of Lead (II) and Zinc (II) from Aqueous Solution by Bituminous coal

Activated carbons have been proven to be effective adsorbents for the removal of Pb (II) and Zn (II) dissolved in aqueous media. The study of adsorption of Pb (II) and Zn (II) on two different size fractions from a composite coal sample of Maghara coal mine, C₆₃ (63–125 μm) and C₂₅₀ (125–250 μm) is presented in this paper. C₆₃ and C₂₅₀ were treated in water solutions of 50 mM lead and zinc acetates. X-ray photoelectron spectroscopy (XPS) was used to characterize the starting and treated coal surfaces. The high surface area and surface functional groups (carboxy and phenolic) enable activated bituminous coal of Maghara to act as efficient adsorbents for removing dissolved Pb (II) and Zn (II) in alkaline medium.     

Trace elements contamination of agricultural soils affected by sulphide exploitation (Iberian Pyrite Belt,Sw Spain)

Agricultural soils of the Riotinto mining area (Iberian Pyrite Belt) have been studied to assess the degree of pollution by trace elements as a consequence of the extraction and treatment of sulphides. Fifteen soil samples were collected and analysed by ICP-OES and INAA for 51 elements. Chemical analyses showed an As–Cu–Pb–Zn association related with the mineralisation of the Iberian Pyrite Belt. Concentrations were 19–994 mg kg⁻¹ for As, 41–4,890 mg kg⁻¹ for Pb, 95–897 mg kg⁻¹ for Zn and of 27–1,160 mg kg⁻¹ for Cu. Most of the samples displayed concentrations of these elements higher than the 90th percentile of the corresponding geological dominium, which suggests an anthropogenic input besides the bedrock influence. Samples collected from sediments were more contaminated than leptosols because they were polluted by leachates or by mining spills coming from the waste rock piles. The weathering of the bedrock is responsible for high concentrations in Co, Cr and Ni, but an anthropogenic input, such as wind-blown dust, seems to be indicative of the high content of As, Cu, Pb and Zn in leptosols. The metal partitioning patterns show that most trace elements are associated with Fe amorphous oxy-hydroxides, or take part of the residual fraction. According to the results obtained, the following mobility sequence is proposed for major and minor elements: Mn, Pb, Cd, > Zn, Cu > Ni > As > Fe > Cr. The high mobility of Pb, Cu and Zn involve an environmental risk in this area, even in soils where the concentrations are not so high.     

Distribution of heavy metals in urban soils – a case study of Danang-Hoian Area (Vietnam)

 This work is part of a research study which is intended to study the degree of anthropogenic influences of the trace metal distribution of soils from Danang-Hoian area (Vietnam). Cu, Ni, Zn and Zr show significant effects in most of the cultivated soil categories, especially in the industrial soils. Extremely high levels of Pb (up to 742 μg/g) are observed in the industrial soil category, which shows an enrichment factor 114 as compared to rural soils. Cd shows only a relative local enrichment with the maximum level of 4.6 μg/g in urban soils. Sequential extraction was performed in selected samples to evaluate the geochemical trace metals. The result indicates that Zn and Cr are mainly found in the crystal and amorphous Fe oxide bounded forms. The contents of Cr in these fractions comprise more than 94% of total extractable Cr. In the case of Zn, 85% of total extractable Zn is in fractions F_V and F_VI. Cu is mainly found in the organic fraction at an average of 39.3% of total extractable content. On the other hand, heavy metal contents show an increasing tendency in the fine fraction (silt and clay). Received: 4 February 1998 · Accepted: 26 November 1998     

The effect of grain size on the Cu, Pb, Ni, Cd speciation and distribution in sediments: a case study of Dongping Lake, China

This paper examines the surface sediments collected from Dongping Lake in China for speciation and distribution of toxic heavy metals (Cu, Pb, Ni, Cd) in different grain size fractions, and for the factors that need to be considered in potential hazard of metals to the environment. Four grain size fractions (<63, 63–78, 78–163 and 163–280 μm), divided in wet condition, and bulk samples less than 280 μm in diameter were analyzed for their distribution, density and appearance. A three-stage extraction procedure following the BCR protocol was used to chemically fractionate metals into “acid soluble”, “reducible”, “oxidizable” and “residual” fractions. Correlation analysis was used to analyze the datasets. The results showed that <63 μm grain size part constitutes the major proportion of the sediments, but its density is the smallest among the four grain size fractions. In general, the metal content curve against grain size presents “S” distribution, and the highest concentrations do not exist in <63 μm grain size. Appearance observation indicates that the adsorbed substance increases gradually along with the decreasing grain size. The dominant speciation of elements and the extent of pollution are responsible for the metal distribution in different grain size sediments. While studying bioavailability and mobilization of metals, it is advisable to take metal speciation, grain size distribution and density into consideration.     

Chemodynamics of trace metal fractions in surface sediments of the Pandoh Lake,Lesser Himalaya,India

The seasonal variation in the trace metals’ concentrations (Cd, Co, Cu, Fe, Mn, Ni, Pb, and Zn) were investigated in surface sediments of the Pandoh Lake. The horizontal distribution of TC, TN, and TP reflects spatial and temporal differences in sedimentary organic production. The chemical sequential extraction of heavy metals was carried out by seven-step fractionation scheme (Leleyter and Probst in Int J Environ Chem 73:109–128, 1999). The significant concentrations of Ni and Cd were associated with “water soluble (Eua)” fraction in the monsoon and winter, respectively, while “exchangeable (Exch)” and “carbonate-bound (Carb)” fractions for Ni and Cd were abundant in winter and summer. The Cd, Cu, and Pb associated with “Exch” fraction in the summer season support their availability on exchange sites due to oxidized nature of surface sediments. Enrichment of Co, Fe, Mn, and Zn in “AFeO” fraction showed poor bioavailability, while Cd, Cu, and Mn in the monsoon, Co in the winter and summer, and Zn in the winter season showed significant “organically bound (Org)” fraction. The ANOVA was significant for chemical fractions of trace elements except “Carb” fraction of Pb and Zn and “CFeO” fraction of Pb. Factor analysis revealed that the “Eua”, “Exch”, and “Carb” fractions together control the metal enrichment of “MnO”, “AFeO”, and “CFeO” fractions in the summer season.     

Microscopic morphology and elemental composition of size distributed atmospheric particulate matter in Urumqi, China

Microscopic morphology and elemental composition of atmospheric particulate matter (PM) in 13 different size fractions from 0.01 to 10 μm were studied using a Field Emission Scanning Electron Microscope with Energy-Dispersive Spectrometer (FESEM–EDX). The relative mass fractions exhibited a bimodal distribution with a major mode in the fine range (0.18–1 μm) and a minor mode in the coarse range (>1 μm), suggesting that the major pollution of PM is fine particles in this area of Urumqi atmosphere. The PM could be classified as follows: aluminosilicate/silica mineral, Si–Al rich fly ash, Fe oxide particle, Ti dominant particle, sulfate/carbonate crystal, carbonaceous aerosols (including soot, organic carbon, tar ball and irregularly shaped carbon). The soot and organic carbon with anthropogenic sources are dominant types in fine range samples (<1 μm). The natural source minerals and secondary synthesized sulfate/carbonate crystals were accumulated in the coarse range (>1 μm). Elemental composition of various types of particles (0.056–5.6 μm) was also analyzed by EDX. C, S, O, N, Si, Al, Fe, Ca, Na, K, Mg, Cl, F, Hg were detected in most samples. Si, Al and Ca accumulated in coarse fractions, while S and Hg mainly accumulated in fine fractions. Concentrations of 15 metallic elements in size range from 0.1 μm to 5.6 μm were divided into three groups based on their possible sources. (1) The crustal elements (Al, Mg, Fe, Mn and V), mainly present in coarse particles (>1 μm); and (2) the anthropogenic source elements (Ca, Ni, As, Cu, Pb, Cd and Hg). The concentrations of Ca and Ni increased with increasing particle size, while As, Cu, Pb, Cd and Hg showed opposite trends. As, Cu, Pb, Cd and Hg accumulated mainly in fine fraction (<1 μm). (3) The multi sources elements (Cr, Co and Se) possibly come from both natural and anthropogenic sources. High levels of heavy metals, especially Hg in nanosize particles, may pose great risk to human health.     

Relationships between heavy metals and iron oxides,fulvic acids,particle size fractions in urban roadside soils

Urban roadside soils are the “recipients” of large amounts of heavy metals from a variety of sources including vehicle emissions, coal burning waste and other activities. The behavior of heavy metals in urban roadside soils depends on the occurrence as well as the total amount. Accordingly, knowledge of the interactions between heavy metals and other constituents in the soil is required to judge their environmental impact. In this study, correlations of heavy metal concentrations (Pb, Zn, Cu, Ag, Se, Ni, Cr and Ba) to iron extracted using dithionite–citrate–bicarbonate (DCB) buffer (Fe_DCB), fulvic acids and particle size fractions were examined from the Xuzhou urban roadside soils. Heavy metals except for Cr and fulvic acids had a positive significant correlation with Fe_DCB, indicating these metals and fulvic acids are principally associated with the surfaces of iron oxides of the soils. Significant positive correlations were also found between the contents of fulvic acids and heavy metals, showing these heavy metals (especially for Cu, Ni and Cr) form stable complexes with fulvic acids. Such finding is of importance with regard to the increased mobilization of heavy metals, e.g., into freshwater ecosystems. Ag, Se and Cr are independent of particle size fractions because of their low concentrations of Ag and Se in the studied soils. Pb, Zn, Cu, Ba and Ag are mainly enriched in the finer soil particles (especially <16 μm).     

Fe–Al–organic Colloids Control of Trace Elements in Peat Soil Solutions: Results of Ultrafiltration and Dialysis

Size fractionation of ~40 major and trace elements (TE) in peat soil solutions from the Tverskaya region (Russia) has been studied using frontal filtration and ultrafiltration through a progressively decreasing pore size (5, 2.5, 0.22 μm, 100, 10, 5, and 1 kD) and in situ dialysis through 6–8 and 1 kD membranes with subsequent analysis by ICP-MS. In (ultra) filter-passed permeates and dialysates of soil solutions, Fe, Al, and organic carbon (OC) are well correlated, indicating the presence of mixed organo-mineral colloids. All major anions and silica are present in “dissolved” forms passed through 1 kD membrane. According to their behavior during filtration and dialysis and association with mineral or organic components, three groups of elements can be distinguished: (i) species that are weakly affected by size separation operations and largely (>50–80%) present in the form of dissolved inorganic species (Ca, Mg, Li, Na, K, Sr, Ba, Rb, Cs, As, Mn) with some proportion of small (1–10 kD) organic complexes (Ca, Mg, Sr, Ba), (ii) biologically essential elements (Co, Ni, Zn, Cu, Cd) mainly present in the fraction smaller than 1 kD and known to form strong organic complexes with fulvic acids, and, (iii) elements strongly associated with aluminum, iron and OC in all ultrafiltrates and dialysates with 30–50% being concentrated in large (>10 kD) colloids (Ga, Y, REEs, Pb, Cd, V, Nb, Sn, Ti, Zr, Hf, Th, U). For most trace metals, the proportion in the colloidal fraction correlates with their first hydrolysis constant. This implies a strong control of negatively charged oxygen donors present in inorganic/organic colloids on TE distribution between aqueous solution and colloid particles. It is suggested that these colloids are formed during plant uptake of Al, Fe, and TE from mineral matrix of deep soil horizons and their subsequent release in surface horizons after litter degradation and oxygenation on redox or acid/base fronts. Dissolved organic matter stabilizes Al/Fe colloids and thus enhances trace elements transport in soil solutions.     

The chemical and physical characteristics of heavy metals in humus and till in the vicinity of the base metal smelter at Flin Flon, Manitoba, Canada

 Trace element geochemistry of humus (<0.425 mm) and till (<0.002 mm) collected in the Flin Flon-Snow Lake area, northern Manitoba and Saskatchewan, provides a regional context for assessing smelter contamination in the environment. The area includes a Cu-Zn smelter known to discharge As, Cd, Cu, Fe, Hg, Pb, and Zn. In this study, sequential extraction analyses, scanning electron microscopy and x-ray diffraction analyses were used on a suite of samples to determine: (1) the chemical and physical characteristics of heavy metals in surficial sediments related to distance from the smelter, (2) criteria for assessing the relative contribution of these metals from natural and anthropogenic sources, and (3) the potential of these metals for remobilization in the environment. Humus geochemistry reflects the anthropogenic and natural component of heavy metal concentrations. Smelter-related elements show anomalously high values adjacent to the smelter, decreasing with distance until background values are reached at 70–104 km, depending on the element. In humus, Zn is associated primarily with labile phases; Hg with non-labile phases. Adjacent to the smelter, high proportions and concentrations of Zn and Hg in non-labile phases, indicative of smelter-derived particulates, are confirmed by SEM examination. The particles occur as spheres, irregular grains, and with organics. With increasing distance from the smelter, the geochemical response to bedrock composition is more obvious than the anthropogenic input. Till geochemistry reflects the natural variation imposed by bedrock composition. At highly contaminated sites (<3 km from the smelter), increased percentages of smelter-related elements in labile phases suggests heavy metals are leached from humus to the underlying sediment. Received: 5 November 1996 · Accepted: 31 March 1997