Mobility and potential bioavailability of traffic-derived trace metals in a ‘wet–dry’ tropical region,Northern Australia

The aqueous mobility and potential bioavailability of metals and metalloids in road runoff in a ‘wet–dry’ tropical location were assessed by analysing metal and metalloid concentrations in particulate, total dissolved and labile dissolved phases in runoff waters. Road-derived Al, Cu, Pb, Sb and Zn concentrations were substantially elevated in runoff when compared to receiving creek waters. Median dissolved concentrations in road runoff exceeded those in creek waters by up to an order of magnitude. Leaching experiments of road sediments confirmed that several metals and metalloids were released in high concentrations from road sediments. Labile Zn and Cu concentrations measured by diffusion gradients in thin films (DGT) showed that almost all dissolved Zn and up to half of dissolved Cu in runoff waters and in road sediment leachate were potentially bioavailable. Comparisons of dissolved metal concentrations in receiving waters affected by road runoff with ecosystem guideline levels, indicated a risk of reaching toxic levels of Cu and Zn in the receiving waters in the absence of adequate treatment or dilution. Low dilution rates of road runoff are likely to occur during late ‘dry’ season/early ‘wet’ season storms which have the potential to produce high metal concentrations derived from long periods of accumulation of road sediment at a time when creek flow rates are at their annual minimum.     

Trace metal dynamics in a seasonally anoxic lake

Selected results are presented from a detailed 12-month study of trace metals in a seasonally anoxic lake. Dissolved concentrations of Fe, Mn, organic carbon, Cd, Cu, Pb, Zn, and pH were determined in the water column and the interstitial waters on 39 occasions. Trace metal concentrations remained low throughout the year in both water column and pore waters. There was evidence for some remobilization at the sediment-water interface but sediments deeper than 3 cm acted as a sink throughout the year. Variations in the water concentrations were largely associated with increased loading during periods of heavy rainfall. During the summer, concentrations of Cu and Zn in the waters overlying the sediments were enhanced by release from decomposing algal material. Similarly, enhanced concentrations of Cd, Cu, Pb, and Zn were observed during periods of much reduced mixing during ice-cover. Although there were large seasonal variations in the concentrations of dissolved and particulate Fe and Mn, there were no comparable changes in the concentrations of trace metals.     

Heavy metal trends in the Calabar River, Nigeria

. Heavy metal concentrations in sediments of the Calabar River: Pb (0.6–30 ppm); Ni (1.2–22.5 ppm); Cr (0.6–3.3 ppm); Cu (0.3–48 ppm); Zn (0.8–27 ppm); Fe (0.2–2,880 ppm) and V (0 ppm) are generally below levels that are known to be harmful to aquatic biota. Metal levels displayed marked seasonal, spatial and tidal variations, which are attributed to both anthropogenic influences and natural processes in the environment. Iron and Cr increased during the dry season (January), while Cu, Zn, Pb and Ni had their peak values in the wet season (September). High values of metals during the wet season indicate inputs through human activities mediated by rainfall. Relatively higher concentrations of metals are obtained during high tide compared to low tide regime. This is attributed to redox processes in the sediment and subsequent displacement of sediment pore water rich in metals by seawater intrusion during high tide. Higher values of Fe observed in the dry compared to the wet season may be attributed to oxidation and precipitation of soluble forms brought into the river during the wet season.     

Partitioning of copper and zinc in the sediments and porewaters of a high-elevation alkaline lake,east-central Arizona,U.S.A.

In Pacheta Lake, a high-elevation alkaline lake proximal to the smelting region of southern Arizona-New Mexico, concentrations of transition metal ions in pore waters and co-existing sediments were compared. Copper, Fe, Mn and Zn have been partitioned among operationally defined sediment solid phases (exchangeable sites, organic complexes, amorphous oxides, crystalline oxides, sulfides and residual silicates) and their concentrations in interstitial waters were measured. Concentrations are reported as a function of depth in the sediment column. The diagenetic environment is described and cycling mechanisms postulated for the above metals.Selective, sequential extraction of metals from lake sediments showed different binding mechanisms for Cu and Zn, the former most strongly associated with organic complexes, and the latter with iron oxyhydroxides. This difference has strong implications for selective metal remobilization under variable environmental conditions, both naturally and anthropogenically induced. Copper and zinc in porewaters were estimated to diffuse to overlying waters at 12.8 and 21.9 μg/cm²/a, respectively. These fluxes are large enough to account for observed concentrations of Cu and Zn in overlying waters. No sediment metal contamination was directly attributable to smelting activity. However, this study does document a flux from sediments, which have accumulated Cu and Zn, to overlying waters no longer receiving trace metal deposition from now inactive smelters.     

Assessment of trace metal contents in water and bottom sediments from Eğirdir Lake,Turkey

The concentration of metals (Pb, As, Co, Cu, Ni, Zn, Fe and Mn) was investigated in water and sediment samples of E?irdir Lake. The Lake is the second largest fresh water lake of Turkey and it is used as drinking water in the region. The anthropogenic pollutants are primary sources of trace metals which are negatively affected lake water quality. These negative effects were observed in both lake water and bottom sediments. According to obtained data, Pb, Cu, Ni, Fe and Zn have significant enrichment in sediments samples. In addition, the hydrodynamic model of the lake was determined as effectively for Pb, Co, Cu, Ni, Zn, Fe and Mn accumulations. Also, the effect of anthropogenic pollutants was found to be more dominant than geogenic effect in metal accumulation of the lake bottom sediments. Therefore, anthropogenic pollutants within the lake basin should be consistently controlled for the sustainable usage of the lake.     

Particulate metal speciation in surficial sediments from Loch Dee, southwest Scotland, U.K.

The geochemical partitioning of ten elements in stratified Holocene sediments from Loch Dee, southwest Scotland, has been established by use of a five-stage sequential extraction procedure. Samples from below 15 cm sediment depth show minimal evidence of modification by anthropogenic contamination or active diagenesis and hold Fe, Mg, Cu, Cd, Co, Pb, and Ni primarily in detrital silicates or organic complexes, while Mn, Ca, and Zn reside largely in adsorbed and reducible oxide phases. In the uppermost ca 15 cm of sediment, enhanced total concentrations of Zn, Cu, and Pb reflect increased atmospheric deposition during the postindustrial period. Of these metals, only Pb displays any notable adjustment of partitioning in the enriched zone, showing disproportionate accumulation in labile oxides and organic-Pb phases. The lack of Pb and Zn carbonates in the contaminated horizon may reflect inherent thermodynamic instability under the acid surface and pore-water conditions of Loch Dee. Increments to total Mn and Co in the surficial ca 5 cm of sediment are attributable to the accumulation of secondary oxides and adsorbed species, consistent with precipitation from the interstitial pore-waters across a sedimentary redox front. The presence of metals such as Zn and Cd in soluble or acid-volatile phases in the interfacial sediment has implications for the future management of the Loch Dee basin, with leaching into the overlying waters likely, given the continuation of current trends of lake acidification.     

Partitioning of heavy metals in surface Black Sea sediments

Bulk heavy metal (Fe, Mn, Co, Cr, Ni, Cu, Zn and Pb) distributions and their chemical partitioning, together with TOC and carbonate data, were studied in oxic to anoxic surface sediments (0–2 cm) obtained at 18 stations throughout the Black Sea. TOC and carbonate contents, and available hydrographic data, indicate biogenic organic matter produced in shallower waters is transported and buried in the deeper waters of the Black Sea. Bulk metal concentrations measured in the sediments can be related to their geochemical cycles and the geology of the surrounding Black Sea region. Somewhat high Cr and Ni contents in the sediments are interpreted to reflect, in part, the weathering of basic-ultrabasic rocks on the Turkish mainland. Maximum carbonate-free levels of Mn (4347 ppm), Ni (355 ppm) and Co (64 ppm) obtained for sediment from the shallow-water station (102 m) probably result from redox cycling at the socalled ‘Mn pump zone’ where scavenging-precipitation processes of Mn prevail. Chemical partitioning of the heavy metals revealed that Cu, Cr and Fe seem to be significantly bound to the detrital phases whereas carbonate phases tend to hold considerable amounts of Mn and Pb. The sequential extraction procedures used in this study also show that the metals Fe, Co, Ni, Cu, Zn and Pb associated with the ‘oxidizable phases’ are in far greater concentrations than the occurrences of these metals with detrital and carbonate phases. These results are in good agreement with the recent studies on suspended matter and thermodynamic calculations which have revealed that organic compounds and sulfides are the major metal carriers in the anoxic Black Sea basin, whereas Fe-Mn oxyhydroxides can also be important phases of other metals, especially at oxic sites. This study shows that, if used with a suitable combination of the various sequential extraction techniques, metal partitioning can provide important information on the varying geological sources and modes of occurrence and distribution of heavy metals in sediments, as well as, on the physical and chemical conditions prevailing in an anoxic marine environment.     

Impact of historical metalworks on the concentrations of major and trace elements in sediments: a case study in Finland

The concentrations of major and trace elements were determined (aqua regia leach and ICP-AES analyses) in stream, lake and dredged sediments downstream of the historical Antskog iron- and copperworks, S.Finland. The levels of Ag, Cd, Cu, Pb and Zn are highly elevated in all studied sediment types: roughly half of the studied lake-sediment samples contain >5 ppm Ag, >15 ppm Cd, >0.1% Cu, >0.1% Pb and >0.3% Zn. In the dredged sediment material located onshore, the concentrations of Ag, Cu and Pb are comparable to those in the polluted lake-sediment samples, while in stream sediments elevated metal concentrations are found especially in samples characterised by high concentrations of organic material. The source of the elevated metal concentrations is the historical metalworks at Antskog, mainly the copperworks of the 19th century. Compared to the limit values for contaminated soils in Finland, the concentrations of Cu, Pb and Zn are on average elevated by factors >10 in the polluted horizons of lake sediments, >5 in the dredged sediment located onshore and >2 at the most heavily contaminated site in the stream. Since the surface waters in the area are used for agricultural purposes and for various leisure activities, it is necessary to make further detailed investigations into the extent of the metal pollution and to determine species, mobility and bioavailability of the metals.     

Impact of tailings from the Kilembe copper mining district on Lake George, Uganda

The abandoned Kilembe copper mine in western Uganda is a source of contaminants, mobilised from mine tailings into R. Rukoki flowing through a belt of wetlands into Lake George. Water and sediments were investigated on the lakeshore and the lakebed. Metal associations in the sediments reflect the Kilembe sulphide mineralisation. Enrichment of metals was compared between lakebed sediments, both for wet and dry seasons. Total C in a lakebed core shows a general increment, while Cu and Co decrease with depth. The contaminants are predominant (> 65%) in the ≤ 63 μm sediment size range with elevated Cu and Zn (> 28%), while Ni, Pb and Co are low (< 18%) in all the fractions. Sequential extraction of Fe for lakeshore sediment samples reveals low Fe mobility. Relatively higher mobility and biological availability is seen for Co, Cu and S. Heavy metal contents in lake waters are not an immediate risk to the aquatic environment.     

Major and trace element geochemistry in Zeekoevlei, South Africa: A lacustrine record of present and past processes

This study reports a multi-parameter geochemical investigation in water and sediments of a shallow hyper-eutrophic urban freshwater coastal lake, Zeekoevlei, in South Africa. Zeekoevlei receives a greater fraction of dissolved major and trace elements from natural sources (e.g., chemical weathering and sea salt). Fertilizers, agricultural wastes, raw sewage effluents and road runoff in contrast, constitute the predominant anthropogenic sources, which supply As, Cd, Cu, Pb and Zn in this lake. The overall low dissolved metal load results from negligible industrial pollution, high pH and elevated metal uptake by phytoplankton. However, the surface sediments are highly polluted with Pb, Cd and Zn. Wind-induced sediment resuspension results in increased particulate and dissolved element concentrations in bottom waters. Low C/N ratio (10) indicates primarily an algal source for the sedimentary organic matter. Variation in sedimentary organic C content with depth indicates a change in primary productivity in response to historical events (e.g., seepage from wastewater treatment plant, dredging and urbanization). Primary productivity controls the enrichment of most of the metals in sediments, and elevated productivity with higher accumulation of planktonic debris (and siltation) results in increased element concentration in surface and deeper sediments. Aluminium, Fe and/or Mn oxy-hydroxides, clay minerals and calcareous sediments also play an important role in adsorbing metals in Zeekoevlei sediments.     

Heavy metals in the Derwent Estuary

Analyses of the concentrations of Cd, Cr, Co, Cu, Fe, Pb, Mn, Hg, Ni, and Zn in filtered waters, suspended particulates, sediments, shellfish, fish, airborne particulates, and sewage have confirmed work of other investigators showing that the Derwent Estuary is heavily contaminated, particularly withmercury, cadmium, lead, andzinc, and have added further information regarding the distribution of each metal. Apparently most of the contamination originated from the earlier operation of a zinc refining plant. A study of shellfish growing in variously contaminated regions found that more than 20 species could be listed in order of their respective abilities to accumulate each heavy metal. For example, the mussel (Mytilus edulis) was found to be a good indicator of cadmium and mercury contamination, but less valuable as an indicator of zinc. The surf barnacle, (Catophragmus polymerus) was found to be one of the most sensitive biological indicators of cadmium contamination. An indication of the steps by which a waste metal is eventually accumulated at high and even toxic concentrations in seafoods, may be seen from a comparison of the relative concentrations of cadmium, lead, mercury, and zinc found in mussels, sediments, suspended particulates, and filtered waters. The high concentrations recorded for metals include: 1,100 μg/g Hg, 10,000 μg/g Zn, and 862 μg/g Cd in dried sediments; 1,500 μg/g Cd in airborne dust fallout; 200 μg/g Cd and 100,000 μg/g Zn in dried oysters; and 16 μg/l Hg, 15 μg/l Cd and 1,500 μg/l Zn in filtered waters.     

Heavy metal distribution and accumulation in the <Emphasis Type="Italic">Spartina alterniflora</Emphasis> from the Andong tidal flat,Hangzhou Bay,China

In order to study the heavy metal accumulation and distribution in the roots, stems, and leaves of Spartina alterniflora, we collected S. alterniflora samples and the associated sediments along three transects at the Andong tidal flat, Hangzhou Bay. Co, Ni, Cd, Pb, Cu, and Zn were mainly accumulated in the aerial parts (stems and leaves) of the plants, and their distributions depended on their mobility and their roles during the metabolism processes of S. alterniflora. The concentrations of Cu, Zn, Cd, Hg, and Pb were significantly enhanced with the increasing of heavy metal concentrations in the sediments, while those of Co and Ni remained relatively constant. Bioaccumulation factors results showed that the serious heavy metal contamination in the sediments from the transect A may overwhelm the accumulation capability of the plants. In addition, the physicochemical properties of the sediments and the pore water therein also play a role in the heavy metal concentrations and accumulations in the plants, because they can influence the behaviors and bioavailabilities of heavy metals during nutrition and bioaccumulation processes of the plants. The sediments with vegetation did not show significantly decreased heavy metal concentration with respect to the unvegetated sediments, although the plants did absorb heavy metals from the sediments. Principal component analysis and correlation analyses indicated that Co–Ni, Cu–Cd–Hg behaved coherently during accumulation, which may be ascribed to their similar accumulation mechanisms. This work provided essential information on the heavy metal accumulation by plants in a tidal flat, which will be useful for the environmental control through phytoremediation at estuaries.     

Distribution of heavy metals in the clastic fine-grained sediments of Gavkhuni playa lake (Southeast of Isfahan,Iran)

The sedimentary basin of Gavkhuni playa lake includes two sedimentary environments of delta and playa lake. These environments consist of mud, sand and salt flats. There are potentials for concentration of heavy metals in the fine-grained sediments (silt and clay) of the playa due to existence of Pb/Zn ore deposits, industrial and agricultural regions in the water catchment of Zayandehrud River terminating to this area. In order to study the concentration of heavy metals and the controlling factors on their distribution in the fine-grained sediments, 13 samples were taken from the muddy facies and concentration of the heavy metals were determined. The results showed that the heavy metal concentrations range in the sediments (in ppm) are Mn (395.5–1,040), Sr (100.4–725.76), Pb (14.66–91.06), Zn (23.59–80.9), Ni (37–73.66), Cu (13.83–29.83), Co (5.73–13.78), Ag (3.03–4.76) and Cd (2.3–5.5) in their order of abundances. The concentration of Ag is noticeable in the sediments relative to the average concentration of this element in mud sediments. The amounts of Pb and Zn are relatively high in all the samples in comparison with the other elements. The concentration of Ni is relatively high in the oxidized samples. The distribution of Pb is directly related to organic matter content of the sediments. The concentrations of Zn, Sr, Cu, Co and Cd in the samples of the playa are lower than those in the delta. The amount of illite is another factor influencing Zn and Pb concentrations. Sr is more concentrated in the sediments with the high content of calcium carbonate. The distribution pattern of Cu, Co, Pb and Mn resembles to that of the clay content of the sediments. The clay content shows positive correlations with Co, Cu and Mn concentrations and negative correlation with Ag. The Sr and Ag concentrations are positively correlated with the amount of CaCO₃. The amounts of Co, Cu, Ni and Mn show negative correlations with the calcium carbonate content. Pb and Co are noticeably correlated with Mn.     

Heavy metal pollution of coastal river sediments, north-eastern New South Wales, Australia: lead isotope and chemical evidence

 Heavy metal and metalloid concentrations within stream-estuary sediments (<180-μm size fraction) in north-eastern New South Wales largely represent natural background values. However, element concentrations (Ag, As, Cd, Cr, Cu, Hg, Ni, Pb, Sb, Zn) of Hunter River sediments within the heavily industrialized and urbanized Newcastle region exceed upstream background values by up to one order of magnitude. High element concentrations have been found within sediments of the Newcastle Harbour and Throsby Creek which drains into urbanized and light industry areas. Observed Pb enrichments and low ²⁰⁸Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁶Pb/²⁰⁴Pb ratios are likely caused by atmospheric deposition of Pb additives from petrol and subsequent Pb transport by road run-off waters into the local drainage system. Sediments of the Richmond River and lower Manning, Macleay, Clarence, Brunswick and Tweed River generally display no evidence for anthropogenic heavy metal and metalloid contamination (Ag, As, Cd, Cr, Cu, Hg, Ni, Pb, Sb, Zn). However, the rivers and their tributaries possess localized sedimentary traps with elevated heavy metal concentrations (Cu, Pb, Zn). Lead isotope data indicate that anthropogenic Pb provides a detectable contribution to investigated sediments. Such contributions are evident at sample sites close to sewage outlets and in the vicinity of the Pacific Highway. In addition, As concentrations of Richmond River sediments gradually increase downstream. This geochemical trend may be the result of As mobilization from numerous cattle-dip sites within the region into the drainage system and subsequent accumulation of As in downstream river and estuary sediments. Received: 5 September 1997 · Accepted: 4 November 1997     

The environmental impact of Aguilar mine on the heavy metal concentrations of the Yacoraite River,Jujuy Province,NW Argentina

The Yacoraite River and its tributaries run down the eastern slope of the Aguilar Range. It is one of the tributaries of the Rio Grande, located in Quebrada de Humahuaca, a UNESCO World Heritage site. The Aguilar underground mine (Pb–Ag–Zn) is located in the upper reaches of the Yacoraite River drainage basin. The aim of this work is to characterize the presence of heavy metals in water and sediments of the Yacoraite River and to identify their sources. The analysis shows the seasonal variation of heavy metals concentration in water and their relation with the World Health Organization (WHO) limits established for human consumption. The Yacoraite basin is naturally anomalous in some metals and some elements, such as As which is controlled by the chemical composition of regional lithology. During the wet season, Al, Co, Mo and Pb concentrations in water samples are higher than during the dry season; in addition, these metals are also higher than WHO limit values. High enrichment factors for Ba, Mo, Pb, Zn and Cd were found in Casa Grande stream, indicating the direct influence of the mining activities. Cd, Pb and Zn are present in the Aguilar ore minerals, such as sphalerite and galena. Sediments collected during the dry season show a drastic increase in the concentration of As, Pb, Ba, Zn, Cd and Mn. The Müller geo-accumulation index in Casa Grande indicates that it is a highly polluted stream. The concentrations of As, Pb, Ba, Zn, Cd are also high in Yacoraite River: Security Quality Guidelines indicates toxicity. A decrease in enrichment factors and geo-accumulation indices observed in sediments indicates the occurrence of precipitation/adsorption processes in the river to restore the equilibrium composition. Strict environmental controls in Aguilar Mine are necessary to avoid the uncontrolled input of toxic metals in Casa Grande stream and Yacoraite River.     

Concentrations and contamination trends of heavy metals in the sediment cores of Taihu Lake,East China,and their relationship with historical eutrophication

To assess the contamination trends and potential bio-availability of sediment-bound heavy metals, concentrations of heavy metals in acid-leaching fraction and in bulk sediments from the two typical bays (the Meiliang Bay and Xuhu Bay) of the Taihu Lake, East China, were studied. Pb and Zn showed elevated concentrations in the sediments from both areas, although sedimentation history and degree of pollution are different between the two bays. In the Meiliang Bay, both Pb and Zn pollutions started in the late 1970’s, the same time as the beginning of eutrophication of the lake, while the in the Xuhu Bay the metal contamination started since recent 10 years. The concentrations of acid-leachable Pb in the sediments from the Meiliang Bay are correlated with the historical eutrophication process. Before the eutrophication and heavy metal pollution, the chemical properties of the lake sediments were the same as the source compositions of the Xiashu loess. Both Pb and Zn in the sediments mainly occur in leachable forms by nitric or hydrochloric acid, whilst most of Cu is in residual fraction. The results indicate that both Pb and Zn may have higher mobility and bioavailability in water and biology than Cu.     

Distribution of cadmium, chromium, copper, lead and zinc in marine sediments in Hong Kong waters

Partitioning of heavy metals (Cd, Cr, Cu, Pb, Zn) in marine sediments collected from various sites in Hong Kong waters were determined using sequential extraction method. Sediments from Kellette Bank, located in Victoria Harbour, had higher metal concentrations especially Cu and Zn than most other sites. Slightly over 20% of total Cu and Cr existed as readily available forms in Peng Chau and Kellette Bank. At most sampling sites, over 15% of the Cu existed as the exchangeable form indicating that Cu could be readily released into the aqueous phase from sediments. A significantly higher percentage of Pb and Zn was associated with the three non-residual fractions. Hence, there is a greater environmental concern for remobilization of Pb and Zn compared with Cr. The high amount of residual Cd (>50%) and the relatively lower Cd content indicate that little environmental concern is warranted for the remobilization of Cd. Distribution of metals in sediments collected from different depth at Kellette Bank shows that metal concentrations decreased with profile depth. The levels of Pb and Zn associated with the two readily available fractions increased sharply in the surface sediment. These metals represented the pollutants, which were introduced into the area in the mid-eighties through early nineties as a result of rapid economic and industrial development in the territory. As significant portions of these metals were bound to the readily available phases in the surface sediments, metal remobilization could be a concern. An erratum to this article can be found at     

Heavy metal partitioning in river sediments severely polluted by acid mine drainage in the Iberian Pyrite Belt

This study provides a geochemical partitioning pattern of Fe, Mn and potentially toxic trace elements (As, Cd, Cr, Cu, Ni, Pb, Zn) in sediments historically contaminated with acid mine drainage, as determined by using a 4-step sequential extraction scheme. At the upperstream, the sediments occur as ochreous precipitates consisting of amorphous or poorly crystalline oxy-hydroxides of Fe, and locally jarosite, whereas the estuarine sediments are composed mainly of detrital quartz, illite, kaolinite, feldspars, carbonates and heavy minerals, with minor authigenic phases (gypsum, vivianite, halite, pyrite). The sediments are severely contaminated with As, Cd, Cu, Pb and Zn, especially in the vicinity of the mining pollution sources and some sites of the estuary, where the metal concentrations are several orders of magnitude above background levels. Although a significant proportion of Zn, Cd and Cu is present in a readily soluble form, the majority of heavy metals are bonded to reducible phases, suggesting that Fe oxy-hydroxides have a dominant role in the metal accumulation. In the estuary, the sediments are potentially less reactive than in the riverine environment, because relevant concentrations of heavy metals are immobilised in the crystalline structure of minerals.     

Surface metal enrichment and partitioning of metals in a dated sediment core from a Norwegian fjord

A 24-cm long sediment core from an oxic fjord basin in Ranafjord, Northern Norway, was sliced in 2 cm sections and analysed for As, Co, Cu, Ni, Hg, Pb, Zn, Mn, Fe, ignition loss and Pb-210. Partitioning of metals between silicate, non-silicate and non-detrital phases was assessed by leaching experiments, in an attempt to understand the mechanisms of surface metal enrichment in sediments. Relative to metal concentrations in sediments deposited in the 19th century, metals in near surface sediments were enriched in the following order: Pb > Mn > Hg > Zn > Cu > As > Fe. Cobalt and Ni showed no enrichment. The non-detrital fraction of Cu, Pb, Mn and Zn was significantly higher in the upper 10 cm than at greater depth in the core. This corresponds to sediments deposited since 1900, when mining activities started in the area. The enrichment of Cu, Pb and Zn is assumed to be mainly a result of mining, while Mn is apparently enriched in the surface due to migration of dissolved Mn and precipitation in the oxic surface layer. Elevated concentrations of As and Fe in the upper 4 cm are presumably due to discharges from a coke plant and an iron works respectively. The excess Hg present in the near surface sediments is tightly bound, either in coal particles or ore dust introduced by local industry, or via long distance transport of atmospheric particles. Calculations of metal flux to the sediments indicate an anthropogenic flux of Zn equal to its natural flux, while the flux of Pb shows a threefold increase above natural input.     

Spatial variations and ecological risk assessment of heavy metals in surface sediments on the upper reaches of Hun River, Northeast China

The distribution, accumulation, and ecological risk of heavy metals (Cu, Cd, Pb, Zn, Ni, Cr, and As) in the surface sediment were investigated in the upper reaches of Hunhe River, Northeast China. Sediment samples from 51 points throughout the upper reaches of Hunhe River were collected and measured for heavy metal concentrations, TN content, and TP content. Results showed that heavy metal concentrations at the vicinity of mines and towns were higher than those at other locations. According to sediment quality guidelines (SQGs), Cd and Zn were enriched in the sediments. The correlation analysis and principal component analysis (PCA) were conducted to assess the heavy metal sources. Close correlations between metal distribution and TP indicated that the sediments may be affected by application of phosphate fertilizer. Elements, Cu, Cd, Pb, Zn, and As, were grouped together, reflecting they were released from the same sources. PCA suggested that their primary sources were anthropogenic, namely mining and extensive use of fertilizers. Therefore, heavy metal pollution due to mining and agricultural intensification in the upper Hunhe River basin should be taken into account during the formation of regional management strategies for the water environment.