Geochemistry of trace metals associated with reduced sulfur in freshwater sediments

Porewater concentration profiles were determined for Fe, trace elements (As, Cd, Co, Cu, Mn, Ni, Pb, Zn), sulfide, SO₄ and pH in two Canadian Shield lakes (Chevreuil and Clearwater). Profiles of pyrite, sedimentary trace elements associated with pyrite and AVS were also obtained at the same sites. Thermodynamic calculations are used, for the anoxic porewaters where sulfide was measured, to characterize diagenetic processes involving sulfide and trace elements and to illustrate the importance of sulfide, and possibly polysulfides and thiols, in binding trace elements. The ion activity products (IAP) of Fe sulfide agree with the solubility products (K_s) of greigite or mackinawite. For Co, Ni and Zn, IAP values are close to the K_S values of their sulfide precipitates; for Cu and Pb, IAP/K_s indicate large oversaturations, which can be explained by the presence of other ligands (not measured) such as polysulfides (Cu) and thiols (Pb). Cobalt, Cu, Ni and Zn porewater profiles generally display a decrease in concentration with increasing ΣH₂S, as expected for transition metals, whereas Cd, Pb and Zn show an increase (mobilisation). The results suggest that removal of trace elements from anoxic porewaters occurs by coprecipitation (As and Mn) with FeS(s) and/or adsorption (As and Mn) on FeS(s), and by formation of discrete solid sulfides (Cd, Cu, Ni, Pb, Zn and Co). Reactive Fe is extensively sulfidized (51–65%) in both lakes, mostly as pyrite, but also as AVS. Similarities between As, Co, Cu and Ni to Fe ratios in pyrite and their corresponding mean diffusive flux ratios suggest that pyrite is an important sink at depth for these trace elements. High molar ratios of trace elements to Fe in pyrite from Clearwater Lake correspond chronologically to the onset of smelting activities. AVS can be an important reservoir of reactive As, Cd and Ni and, to a lesser extent, of Co, Cu and Pb. Overall, the trace elements most extensively sulfidized were Ni, Cd and As (maximum of 100%, 81% and 49% of the reactive fraction, respectively), whereas Co, Cu, Mn, Pb and Zn were only moderately sulfidized (11–16%).     

Partitioning of manganese,iron, copper,zinc, lead,cobalt, and nickel in black coatings on stream boulders in the vicinity of the Magruder mine,Lincoln Co., Georgia

Sequential digestions of Fe-Mn oxide coated boulders collected upstream and downstream from the Magruder mine, Lincoln Co., Georgia, indicate probable partitioning relationships for Zn, Cu, Pb, Co, and Ni with respect to Mn and Fe. Initial digestion with 0.1M hydroxylamine hydrochloride (Hxl) in 0.01M HNO₃ selectively dissolyes Mn oxides, whereas subsequent digestion with 1:4 HCl dissolves remaining Fe oxides.The results indicate that partitioning is not constant, but varies systematically with respect to the location of metal-rich waters derived from sulfide mineralization. Upstream from the mineralized zone Zn and Ni are distinctly partitioned to the Fe oxide component and Co and Cu are partitioned to the Mn oxide component. Immediately downstream from the mineralized zone, Mn oxides become relatively more enriched in Zn, whereas Fe oxides are relatively more enriched in Cu, Co, and Ni. Analytical precision for Pb is poor, but available data suggests it is more closely associated with Fe oxides.For routine geochemical surveys utilizing coated surfaces, a one-step digestion method is probably adequate. Parameters useful for detecting sulfide mineralization are metal concentrations normalized to surface area or various ratios (e.g. Zn/(Mn + Fe), Cu/Mn, Pb/Fe). Ratios can be obtained much faster, and at lower analytical costs than conventional analysis of stream sediment.     

Heavy metals contamination in road dust in Delhi city,India

Road dust samples were collected from four different areas having different landuse patterns: industrial, heavy traffic, residential and mixed use in Delhi city of India. The samples were analyzed for Ba, Co, Cr, Cu Fe, Mn, Ni, Pb and Zn by ICP-AES. Results indicate high levels of Co, Cr, Cu, Mn and Ni in samples collected from industrial area. Ba, Pb and Zn showed higher concentration levels in heavy traffic area while Fe did not show any discernible variation between the localities. The concentrations of Fe, Mn, Ba, Zn, Cr, Cu, Pb, Ni and Co showed a decreasing trend. The content of heavy metals was comparable to those in other cities in the world. A multivariate statistical approach which includes Pearson’s correlations and principal component analysis was used to identify the possible sources of metals in the road dust. Enrichment factors were estimated for further confirming the sources of contamination. Significant positively correlations between road dust metals Cu–Mn–Co–Cr–Ni suggest that major common source of origin is industrial activities. A meaningful correlation between Ba and Zn, and a moderate positive correlation between Pb and Ba indicate the influence of traffic activities. Enrichment factors calculation indicated that Pb, Cu, Cr and Zn are moderately enriched whereas Co, Ni and Mn are less enriched while Ba exhibited very low enrichment in the dust samples. The results indicate that industrial and vehicular traffic are the two major sources. Traffic appears to be responsible for the high levels of Zn, Cu and Ba. High concentration of Co, Cr, Cu and Mn may be due to industrial sources.     

Partitioning and transport of metals across the O2H2S interface in a permanently anoxic basin: Framvaren Fjord,Norway

The geochemical processes operating on metals in anoxic marine waters influence metal mobility and mode of transport to the sediments in a manner different from that observed in oxic regimes. In order to better understand these processes, dissolved and particulate Mn, Fe, Co, Ni, Cu, Zn, and Cd concentrations were determined in the water column of a permanently anoxic basin, Framvaren Fjord, Norway. Class specific behavior determines the degree to which these metals are involved in the processes of redox cycling at the $\text{O}{}_2\text{H}{}_2\text{S}$ interface and metal sulfide precipitation in the sulfidic water. Metal sulfide precipitation influences the magnitude of metal enrichment in the sediments. The transition metals, Mn, Fe, and Co, show active involvement in redox cycling, characterized by dissolved maxima just below the $\text{O}{}_2\text{H}{}_2\text{S}$ interface. Nickel concentrations appear unaffected by processes influencing the profiles of the other metals. The metals, Cu, Zn, and Cd, display a dramatic solubility decrease across the interface, are not involved in redox cycling, and are enriched in the sediments relative to a lithogenic component by factors of 11, 105, and 420, respectively. Ion activity products of the metals and sulfide provide evidence that chemical equilibria with a pure metal sulfide solid phase is not the dominant process controlling dissolved metal concentrations in the sulfide containing waters.     

Early diagenesis of trace metals (Cd, Cu, Co, Ni, U, Mo, and V) in the freshwater reaches of a macrotidal estuary

Vertical profiles from the water column, including the maximum turbidity zone (MTZ) to the consolidated sediment were sampled in September 2000 in the freshwater reaches of the Gironde Estuary during a complete neap tide-spring tide cycle. The vertical distributions of dissolved major redox parameters and metals (Mn, Fe, Cd, Cu, V, Co, Ni, Mo, and U) were determined. Reactive particulate metal fractions were also determined from selective leaching. The studied system is characterized by density layers functioning at different time-scales, consisting of two mobile layers, i.e., the liquid (LM) and the soft mud (SM), overlying consolidated sediments (CS). This results in a three-zone diagenetic regime where (1) O₂ dynamics are fast enough to show depletion in the rapidly mixed LM sequence (tidal time-scale), (2) denitrification occurs on the weekly time-scale mixing SM sequence, and (3) the Mn, Fe, and sulfate cycling occurs in the CS layer (annual time-scale). The studied trace metals show differential behavior during early diagenesis: (1) Cd, Cu, and V are released into pore water preferentially from organic matter in the SM, (2) Co, Ni, and U are released in the CS from Mn and Fe oxides during reductive dissolution, and (3) Mo from both processes. Transient conditions (i.e., oscillations of redox fronts and reoxidation processes), due to the dynamics of the mobile layers, strongly influence the trace metal distributions as inducing resolubilization (Cd, Cu, and Mo). In the CS, authigenic metal phases accumulate, either by direct precipitation with sulfides (Cu, Cd) or co-precipitation with Fe-sulfides (Mo). Microbially mediated reduction of Fe oxides is proposed to control U removal from pore water by reduction of U(VI) to U(IV) at depth. However, a significant fraction of the trace metals is trapped in the sediment in exchangeable forms, and therefore is susceptible to be mobilized due to resuspension of estuarine sediment during strong river flood periods and/or dredging activities.     

Heavy metal relationships in a Pennsylvania soil

Soils of loamy sand on weathered, sandy dolomite were cored from six holes up to 70 ft beneath a municipal waste landfill in central Pennsylvania. Mn, Fe, Ni, Co, Cu, Zn, Cd, Pb, and Ag were determined in exchangeable and non-exchangeable forms in total and < 15 μm soil samples. Most of these metals were bound in Mn oxides, non-exchangeable with 0.5 M CaCl₂. The Mn oxides (often X-ray amorphous) identified when crystalline as todorokite occurred chiefly as coatings on quartz grains.Somewhat higher amounts of acid leachable trace metals were found in the < 15 μm size fraction than in the total soil samples; however, trace metal/Mn ratios were similar in both. In general, the initial mild soil leaching, which dissolved chiefly Mn oxides, gave MnFeX>Co>Ni>Pb>Zn> Cu>Cd>Ag. The final leaching, which dissolved chiefly ferric oxides, gave Fe>Mn>Ni>Zn>Co> Cu>Pb>Cd>Ag. Samples taken from an unpolluted site and from the same soils affected for seven years by leachate from the refuse had similar metal contents.Soil extractable Co, Ni, Cu, and Zn could be predicted from the Mn extracted. Based in part on factor analysis of the data, Mn-rich oxides had at least tenfold higher heavy metal percentages than Fe-rich oxides (crystalline component goethite), reflecting their greater coprecipitation potential. Because of this potential and because of the generally higher solubility of Mn than Fe oxides, more heavy metals may be released from Mn-rich than from Fe-rich soils by disposal of organic-bearing wastes. However, leaching of the moisture-unsaturated soils in situ is rarely severe enough to completely dissolve both Mn and Fe oxides. Based on the Mn content, Cd, Cu, and Pb were depleted in soil moisture beneath the landfill relative to their amounts in the soil. This depletion may reflect factors including heterogeneity in metal content of the soil oxides; preferential resorption of these metals; and removal of the Cd, Cu, and Pb as organic precipitates or as inorganic precipitates such as carbonates.     

Chemical influences on trace metal-sulfide interactions in anoxic sediments

Interactions of trace metals with sulfide in anoxic environments are important in determining their chemical form and potential toxicity to organisms. In recent years, a considerable body of observational data has accumulated that indicates very different behavior for various trace metals in sulfidic sediments. These differences in behavior cannot be entirely attributed to thermodynamic relationships, but also reflect differences in ligand exchange reaction kinetics, and redox reaction pathways.Pb, Zn, and Cd, which are generally pyritized to only a few percent of the “reactive” fraction, have faster water exchange reaction kinetics than Fe²⁺, resulting in MeS phases precipitating prior to FeS formation and subsequent pyrite formation, whereas, Co and Ni, which have slower H₂O exchange kinetics than Fe²⁺, are incorporated into pyrite. Although Hg and Cu have faster reaction kinetics than Fe²⁺, both are incorporated into pyrite or leached from the pyrite fraction with nitric acid. Hg undergoes significant chloride complexation, which can retard reaction with sulfide, but can also replace Fe in FeS to form HgS, which can only be dissolved in the pyrite fraction. Cu²⁺ is reduced by sulfide and forms a variety of sulfides with and without Fe that can only be dissolved with nitric acid. Mn²⁺ does not form a MnS phase easily and is incorporated into pyrite at high iron degrees of pyritization (DOP).Oxyanions of Mo and As are first reduced by sulfide. These reduced forms may then react with sulfides resulting in incorporation into pyrite. However, the oxyanion of Cr is reduced to Cr³⁺, which is kinetically inert to reaction with sulfide and, therefore, not incorporated into pyrite.     

Transport and sediment–water partitioning of trace metals in acid mine drainage: an example from the abandoned Kwangyang Au–Ag mine area, South Korea

Transport and sediment–water partitioning of trace metals (Cr, Co, Fe, Pb, Cu, Ni, Zn, Cd) in acid mine drainage were studied in two creeks in the Kwangyang Au–Ag mine area, southern part of Korea. Chemical analysis of stream waters and the weak acid (0.1 N HCl) extraction, strong acid (HF–HNO₃–HClO₄) extraction, and sequential extraction of stream sediments were performed. Heavy metal pollution of sediments was higher in Chonam-ri creek than in Sagok-ri creek, because there is a larger source of base metal sulfides in the ores and waste dump upstream of Chonam-ri creek. The sediment–water distribution coefficients (K _d) for metals in both creeks were dependent on the water pH and decreased in the order Pb ≈ Al > Cu > Mn > Zn > Co > Ni ≈ Cd. K _d values for Al, Cu and Zn were very sensitive to changes in pH. The results of sequential extraction indicated that among non-residual fractions, Fe–Mn oxides are most important for retaining trace metals in the sediments. Therefore, the precipitation of Fe(–Mn) oxides due to pH increase in downstream sites plays an important role in regulating the concentrations of dissolved trace metals in both creeks. For Al, Co, Cu, Mn, Pb and Zn, the metal concentrations determined by 0.1 N HCl extraction (Korean Standard Method for Soil Pollution) were almost identical to the cumulative concentrations determined for the first three weakly-bound fractions (exchangeable + bound to carbonates + bound to Fe–Mn oxides) in the sequential extraction procedure. This suggests that 0.1 N HCl extraction can be effectively used to assess the environmentally available and/or bioavailable forms of trace metals in natural stream sediments.     

Mechanism of enrichment of trace metals on fine sludges collected from filtration plants

Fine sludges were collected from five filtration plants, and the partitioning of ten metals (Ag, Cd, Mn, Zn, Pb, Cu, Sn, Co, Ni, and Fe) in them was determined by selective leaching techniques. (1) The available amounts, which shows the total of each metal leached between 1 M CH₃COONH₄ and 30 percent H₂O₂, for Ag, Cd and Mn, ranged from 51 to 98 percent for five sludges. (2) The available amounts for Zn, Pb, Cu, and Sn were 47–92 percent for five sludges. (3) The most important fraction for Co, Ni, and Fe, except the Inagawa sludge, which is markedly polluted by organic matter, was the crystalline particle. Therefore, the above metals, except Co, Ni, and Fe, are thought to be enriched on ion-exchangeable sites, organic matter, hydrous Fe/Mn oxides, and sulfides in fine sludges.     

A comparison of the early diagenetic environment in intertidal sands and muds of the Manukau Harbour,New Zealand

The early diagenetic environment of intertidal sandy sediments (sands) and muddy sediments (muds) is described and compared from two cores taken from an unpolluted part of the Manukau Harbour, New Zealand. Extraction techniques characterized the form of the trace elements (Fe, Mn, S, C, Pb, Zn, Cu) at different depths in the sediment. Dissolved forms of Fe, Mn, and S were measured in interstitial water. Nonresidual metal concentrations, humic acid, FeS, and FeS₂ are an order of magnitude higher in the muds than in the sands because of dilution by unreactive sand particles. Muds contain a larger proportion of metals in the mobile fractions; exchangeable (Mn), carbonate (Mn, Fe, Zn), and easily-reducible oxide (Fe, Mn, Zn, Pb). This is due to greater surface area (for Mn adsorption); the favorable conditions for MnCO₃, FeCO₃, and FeS precipitation; and higher concentrations of easily reducible iron oxide and humic acid. Therefore, compared to the sands, muds are more important as reservoirs for toxic metals, both in terms of quantity and availability. At either site there was very little difference between the forms of Zn, Pb or Cu identified by sequential extraction as sediments changed from oxic to anoxic conditions. One reason for this is that the amounts and proportions of some of the important components that bind metals, viz., amorphous iron hydrous oxides, humic acids, and FeS₂, do not change much. Other components that do change with redox conditions, for example, manganese phases and FeS, are only minor components of the sediment. Redox conditions, then, have relatively little effect on trace-metal partitioning in the sediment matrix of these unpolluted sediments.     

Trace metal speciation in sea and pore water of the Gotland Deep,Baltic Sea, 1994

Studies on the speciation (particulate, colloidal, anionic and cationic forms) of trace metals (Cd, Co, Cu, Fe, Mn, Mo, Ni, Pb, Zn) in the water column and in pore waters of the Gotland Deep following the 1993/94 salt-water inflows showed dramatic changes in the total “dissolved” metal concentrations and in the ratios between different metal species in the freshly re-oxygenated waters below 125 m. Changes in concentrations were greatest for those metals for which the solubility differs with the redox state (Fe, Mn, Co) but were also noted for those metals which form insoluble sulphides (Cd, Pb, Cu, Zn) and/or stable complexes with natural ligands (Cu). Pore water data from segmented surface muds (0–200 mm) indicated that significant redox and related metal speciation changes took place in the surface sediments only a few weeks after the inflow of the oxygenated sea water into the Gotland Deep.     

High-resolution profiles of trace metals assessed by DGT techniques in lake sediment porewaters

The technique of diffusive gradients in thin films (DGT) was applied to obtain high-resolution vertical profiles of trace metals in sediment porewater of a eutrophic lake, Lake Chaohu. All sampling sediments were under anaerobic conditions with Eh values below 0, the redox potential profile in M4 was relatively stable, and higher Eh values in M4 than that in M1 were observed due to hydrodynamic effects. Fe, Mn and As exhibited closely corresponding profiles due to the co-release of Fe and Mn oxides and the reduction of As. Higher Fe and Mn concentrations and lower As concentrations were observed in M1 of the western half-lake than those in M4 of the eastern half-lake due to different sources and metal contamination levels in the two regions. Cu and Zn showed increasing concentrations similar to Mn and Fe at 1–2 cm depth of sediments, while DGT measured Co, Ni, Cd and Pb concentrations decreased down to 3–4 cm in the profiles. Co, Ni, Cu, Zn, Cd and Pb showed insignificant regional concentration variances in the western and eastern half-lakes. According to the R(C _DGT/C _{centrifugation}) values, the rank order of metal labilities decrease as follows: Fe (>1) > Cu, Pb, Zn (>0.9) > Co, Ni, Cd (>0.3) > Mn, As (>0.1).     

Seasonal Dynamics of Dissolved Trace Metals in the Scheldt Estuary: Relationship with Redox Conditions and Phytoplankton Activity

Seasonal dynamics of dissolved trace metals (Cd, Co, Cu, Ni and Zn) and its relationship with redox conditions and phytoplankton activity has been studied in the Scheldt estuary, during nine surveys carried out between May 1995 and June 1996. Seasonal profiles of dissolved trace metals and general estuarine water quality variables are compared, to identify the geochemical and biological processes responsible for the observed trace metal distributions. In keeping with previous studies, the behavior of dissolved Cd, Cu, and Zn can be explained by the presence of anoxic headwaters and the restoration of dissolved oxygen within the estuary. In the river water, the concentration of dissolved Cu and Zn is generally low, except during winter when dissolved oxygen is present in the water column, although highly undersaturated. Mobilization of particle-bound Cd, Cu, and Zn occurs as dissolved oxygen increases with increasing salinity, possibly because of oxidation of metal sulfides in the suspended matter. The geochemistry of dissolved Co is also related to the redox conditions but in an opposite way. Dissolved Co is mobilized in the anoxic upper estuary, along with the reduction in Mn (hydro) oxides, and subsequently coprecipitated with Mn (hydro) oxides when dissolved oxygen is restored. Conservative behavior is observed for dissolved Ni within the estuary. In the middle estuary, Cd and Zn are readsorbed during phytoplankton blooms, as suggested by the low concentrations of these metals during the most productive periods in spring and early summer. The removal may be caused by direct biological uptake and/or increased adsorption to suspended matter because of the pH increase associated with algae blooms. In the lower estuary, chemical gradients are much weaker and dilution with seawater is the dominant process.     

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.     

粤北大宝山铜多金属矿区黄铁矿与磁黄铁矿EPMA和LA-ICP-MS原位微区组分特征及其对矿床成因机制约束

粤北大宝山铜多金属矿床一直存在燕山期岩浆热液成因和海西期火山喷流成因之争,争议的焦点在于块状、似层状硫化物矿体的成因。本文在全面开展矿区地质调查和钻探查证的基础上,对块状、似层状和脉状硫化物矿石中的黄铁矿和磁黄铁矿开展EPMA和LA-ICP-MS原位分析。测试结果表明,不同产状黄铁矿的平均分子式相似,分别为FeS_(1.98)、FeS_(1.99)和FeS_(1.98),似层状和脉状硫化物中磁黄铁矿的平均化学式为Fe_(0.886)S和Fe_(0.874)S,属形成温度相对较低单斜磁黄铁矿。与花岗岩岩浆热液标型黄铁矿相比,不同产状的黄铁矿和磁黄铁矿中Co、Ni、Mn、Se和Ge等元素以类质同象形式赋存,它们含量较低但稳定,Cu、Pb、Zn、Ag、Bi和Tl及Ga主要以微细矿物子晶形式存在,其含量丰富,但变化明显。从块状、似层状到脉状硫化物矿体,黄铁矿和磁黄铁矿中Co、Zn和Se的含量及Co/Ni值降低,而Cu、Pb、Ag、Bi等元素的含量明显升高。结合矿区次英安斑岩的产状和含矿性特征表明,大宝山矿床块状、似层状和脉状硫化物矿体都是次英安斑岩深部岩浆房产出的含矿流体在不同赋矿环境中的产物。     

Distribution and enrichment of heavy metals in a sediment core from the Pearl River Estuary

A sediment core collected from coastal zone near the Qiao Island in the Pearl River Estuary was analyzed for total metal concentrations, chemical partitioning, and physico-chemical properties. Three vertical distribution patterns of the heavy metals in the sediment core were identified, respectively. The dominant binding phases for Cu, Pb, Cr, and Zn were the residual and Fe/Mn oxides fractions. Cd in all sediments was mainly associated with exchangeable fraction. Influences of total organic carbon content and cation exchange capacity on the total concentrations and fractions of almost all the metals were not evident, whereas sand content might play an important role in the distributions of residual phases of Cr, Cu, Pb, and Zn. In addition, sediment pH had also an important influence on the Fe/Mn oxides, organic/sulfide and residual fractions of Cr, Cu, and Zn. Contamination assessment on the heavy metals in the sediment core adopting Index of Geoaccumulation showed that Cr, V, Be, Se, Sn, and Tl were unpolluted, while Cu, Ni, Pb, Zn, Cd, and Co were polluted in different degrees throughout the core. It was remarkable that the various pollution levels of the metals from moderate (for Cu, Pb, and Zn) to strong (for Cd) were observed in the top 45 cm of the profiles. The relative decrease of the residual fraction in the upper 45 cm of the core is striking, especially for Zn and Cu, and, also for Pb, and Cr. The change in fraction distribution in the upper 45 cm, which is very much contrasting to the one at larger depths, confirms that the residual fraction is related to the natural origin of these metals, whereas in the upper part, the non-residual fractions (mainly the Fe/Mn oxides fraction) are increased due to pollution in the last decade. The possible sources for Cu, Pb, Zn, and Cd contaminations were attributed to the increasing municipal and industrial wastewater discharges, agricultural runoff, atmospheric inputs, and runoff from upstream mining or smelting activities, which may be associated with an accelerating growth of economy in the Pearl River Delta region in the past decade.     

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.     

Geochemical features of heavy metals in core sediments of northwestern Taihu Lake, China

Sequential core sediments from northwestern Taihu Lake in China were analyzed for grain size, organic carbon and heavy metal content. The sediments are composed of organic-poor clayey-fine silts. The chemical speciations of Cu, Fe, Mn, Ni, Pb, and Zn were also analyzed using the BCR sequential extraction procedure. Cu, Fe, Ni, and Zn are mainly associated with the residue fraction; Mn is concentrated mainly in exchangeable/carbonate fraction and residue fraction; and Pb mainly in Fe/Mn oxide fraction and organic/sulfide fraction. The exchangeable/carbonate fractions of Cu, Fe, Ni, Zn and Pb are lower. The fractions of Ni, Pb and Zn bound to the Fe/Mn oxide have significant correlations with reducible Mn; the organic/sulfide fractions of Cu, Mn, Ni, Pb, and Zn have significant correlations with TOC. The extractable fractions of Cu, Mn, Ni, Pb, and Zn are high at the top 4 cm of the core sediments as compared to those in the deeper layers, showing the anthropogenic input of heavy metals is due to rapid industrial development. The heavy metal pollution history of the sediments has been recorded since the late 1970s, determined by the result of ^137Cs dating.     

New Data on the Concentrations of Dissolved Trace Elements in Waters of Russian Arctic Rivers

Doklady Earth Sciences - Published data and research results from the authors on the concentrations of dissolved trace elements (P, Si, Li, Rb, Cs, Sr, Ba, Mn, Fe, Co, Ni, Cu, Zn, Cd, Tl, Pb, Al,...