Partitioning of transition metals in oxidised and reduced zones of sulphide-bearing fine-grained sediments

Distribution and forms of transition metals (Ti, Zn, Ni, Co, Mn, Fe, Cu, V and Cr) were investigated in oxidised, partly oxidised and reduced zones of sulphide-bearing fine-grained sediments located in the coastal areas of western Finland. Samples for the analysis and study of vertical distribution of elements were taken from each vertical 10 cm section in pits ranging in depth between 2 and 3 metres, while bulk samples for characterisation of species and forms of metals were taken from 3 zones in each pit: the acid sulphate soil (characterised by acid and oxidising conditions), transition zone (characterised by a steep pH gradient and partly oxidising conditions) and the reduced zone (pH >6). The former samples were digested in aqua regia (3:1:2 HCl:HNO₃:H₂O), while the latter were digested in aqua regia and hot concentrated acids (HClO₄–HNO₃–HCl–HF) and were subjected to extractions with acid ammonium acetate, H₂O₂ and acid ammonium oxalate. Each leachate was analysed for metals with ICP–AES.The vertical variation in the concentrations of Ti were small at all the studied sites indicating that the sediments are homogeneous and that the total losses of other elements from the soil profiles (acid sulphate soil+transition zone) are not extensive. Field observations, extractions with ammonium oxalate, and concentration–variation patterns indicated that Fe-oxide is largely precipitated and retained also in these acid soils. There are, however, indications of redistribution of Fe within the soil profiles. The results also demonstrated that Mn, Ni, Zn, Co and Cu have been lost in considerable amounts from the acid sulphate soils. However, whereas Mn in general has been lost throughout the soil profile, part of the Zn, Ni and Co released in the acid sulphate soils have migrated downward and been reimmobilised in the transition zone immediately above the reduced zone. Also Cu has been lost from the acid sulphate soil, but generally in smaller proportions than Mn, Zn, Ni and Co. Dissolved metal sulphides seem to be major sources of the mobilised metal fractions. A main part of the V and Cr in the sediments are associated with weathering-resistant minerals. These metals are therefore, like Ti, only to a limited extent mobilised by the oxidation of the sulphide-bearing sediments.     

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.     

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.     

Evaluation of elemental enrichments in surface sediments off southwestern Taiwan

Surface slices of 20 sediment cores, off southwestern Taiwan, and bed sediment of River Kaoping were measured for major and trace elements (Al, As, Ca, Cd, Cl, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, P, Pb, S, Si, Ti, V, and Zn) to evaluate the geochemical processes responsible for their distribution, including elemental contamination. Major element/Al ratio and mean grain size indicate quartz-dominated, coarse grained sediments that likely derived from sedimentary rocks of Taiwan and upper crust of Yangtze Craton. Bi-plot of SiO₂ versus Fe₂O₃^T suggests the possible iron enrichment in sediments of slag dumping sites. Highest concentrations of Cr, Mn, P, S, and Zn found in sediments of dumping sites support this. Correlation analysis shows dual associations, detrital and organic carbon, for Cr, P, S, and V with the latter association typical for sediments in dumping sites. Normalization of trace elements to Al indicates high enrichment factors (>2) for As, Cd, Pb, and Zn, revealing contamination. Factor analysis extracted four geochemical associations with the principal factor accounted for 25.1% of the total variance and identifies the combined effects of dumped iron and steel slag-induced C–S–Fe relationship owing to authigenic precipitation of Fe–Mn oxyhydroxides and/or metal sulfides, and organic matter complexation of Fe, Mn, Ca, Cr, P, and V. Factors 2, 3, and 4 reveal detrital association (Ti, Al, Ni, Pb, Cu, and V), effect of sea salt (Cl, Mg, Na, and K) and anthropogenic component (As and Zn)-carbonate link, respectively, in the investigated sediments.     

Abundance, Sources and Speciation of Trace Elements in Humus-Rich Streams Affected by Acid Sulphate Soils

The behaviour of trace elements (Al, As, Cd, Co, Cr,Cu, Fe, Mn, Ni, V, Zn) was studied in five humus-richstreams (dissolved organic carbon = 14–40 mg/L)impacted by acid sulphate soils developed in marinesulphide-bearing fine-grained sediments. During heavyrainfalls in autumn, on which the study focusses, themetals Al, Cd, Co, Cu, Mn, Ni and Zn are extensivelyleached from these acidic soils (pH = 2.5–4.5), whileAs, Cr, Fe and V are not leached more strongly fromthis soil type than from areas of till and peat. Aspeciation experiment, based on anion and cationexchange of the stream waters in the field, showedthat (1) the metals Al, Cd, Co, Mn, Ni and Zn aretransported in the streams mainly as inorganiccations, (2) Cu exists mainly in cationic form but isalso to a significant extent associated with dissolvedhumic substances, (3) Fe occurs mainly in the anionicfraction explained by organic coating on colloidal Feoxyhydoxides and (4) the hydrochemistry of As, Cr andV is complex as these elements may exist in severalunquantified anionic fractions and to a minor extentin cationic species/forms. Whereas the proportion ofacid sulphate soils in the catchments had a largeimpact on concentrations levels of several elements inthe stream waters, these soils did not have a largeaffect on the speciation of elements in water.     

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.     

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     

Trace-element distribution and ore formation in vein-metasomatised peridotite at Kalskaret,near Tafjord,South Norway

The concentration profiles of the trace elements, S, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Sr, and Y have been determined across a metasomatic vein in peridotite. The introduced elements Ti, V, Sr, and Y show specific enrichment in particular silicate phases in accordance with the availability of suitable lattice sites. In contrast, the other introduced trace elements (Cu and S) behave more like the redistributed elements, Cr, Ni, Mn, and Co which do not show concentration ‘fronts’ that can be simply related to the silicate minerals. Concentration of pentlandite, chalcopyrite, and Cr-magnetite near the boundary between the enstatite and anthophyllite zones gives rise to maxima in the Ni, Cu, S, and Cr distributions, while in the chlorite zone significant concentrations of Cr and Ni occur in the chlorite itself. Control of the distribution of Ni, Cu, and Cr is ascribed to the oxidation/reduction reactions involved in the formation of pentlandite, chalcopyrite and Cr-magnetite, together with the critical role of Al in limiting chlorite formation during metasomatism.     

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     

太平洋北部铁锰结核富集区沉积物的元素地球化学特征

本文对太平洋北部铁锰结核富集区沉积物的元素地球化学作了较为详细的研究。因子分析提供的信息表明,元素的分布主要受三个因子控制:（1）粘土及Fe、Mn氧化物水化物胶体的吸附作用;（2）生物化学作用过程有关的自生沉积作用;（3）海底页岩风化及附近海区的火山喷发作用。元素的来源:（1）Fe、Mn、Cu、Co、Ni、Zn、Cr、Cr、Mg、Al、Ti、K共生,主要来自粘土吸附;（2）C_有机、N、Sr、Na及Si、Ca、Sr主要来自生物化学过程沉积;（3）Pb主要来源于岩石碎屑（火山喷发碎屑）。     

Heavy metals in freshly deposited sediments of the Gomati River (a tributary of the Ganga River): effects of human activities

 The concentrations of various metals (Cr, Cu, Co, Fe, Mn, Ni, Pb, Zn, and Cd) were determined in recently deposited surface sediments of the Gomati River in the Lucknow urban area. Markedly elevated concentrations (milligrams per kilogram) of some of the metals, Cd (0.26–3.62), Cu (33–147), Ni (45–86), Pb (25–77), and Zn (90–389) were observed. Profiles of these metals across the Lucknow urban stretch show a progressive downstream increase due to additions from 4 major drainage networks discharging the urban effluents into the river. The degree of metal contamination is compared with the local background and global standards. The geoaccumulation index order for the river sediments is Cd>Zn>Cu>Cr>Pb. Significant correlations were observed between Cr and Zn, Cr and Cu, Cu and Zn and total sediment carbon with Cr and Zn. This study reveals that the urbanization process is associated with higher concentrations of heavy metals such as Cd, Cu, Cr, Pb, and Zn in the Gomati River sediments. To keep the river clean for the future, it is strongly recommended that urban effluents should not be overlooked before their discharge into the river. Received: 16 February 1996 · Accepted: 29 February 1996     

Vertical distribution and water solubility of phosphorus and heavy metals in sediments of the St. Lucie Estuary, South Florida, USA

Accumulation and distribution of heavy metals and phosphorus in sediments impact water quality. There has been an increasing concern regarding fish health in the St. Lucie Estuary, which is related to increased inputs of nutrients and metals in recent decades. To investigate vertical changes of contaminants (P, Cd, Cr, Co, Cu, Ni, Pb, Zn, and Mn) in sediments of the St. Lucie Estuary in South Florida, 117 layer samples from six of the 210 to 420 cm depth cores were analyzed for their total and water-soluble P and heavy metals, clay, total Fe, Al, K, Ca, Mg, Na, and pH. Principal component analysis (PCA) was used in two sets of analytical data (total and water-soluble contaminant concentrations) to document changes of contaminants in each core of sediments. The PCA of total contaminants and minerals resulted in two factors (principal components). The first and second factors accounted for 61.7 and 17.2 % of the total variation in all variables, and contrast indicators associated with contaminants of P, Cd, Co, Cr, Ni, Pb, Zn, and Mn and accumulation of Fe and Al oxides, respectively. The first factor could be used for overall assessment of P and heavy metal contamination, and was higher in the upper 45–90 cm than the lower depths of each core. The concentrations of P and heavy metals in the surface layers of sediments significantly increased, as compared with those in the sediments deeper than 45–90 cm. The PCA of water-soluble contaminants developed two factors. The second factor (Cu–P) was higher in the upper than the lower depths of the sediment, whereas the highest score of the first factor (Cd–Co–Cr–Ni–Pb–Zn–Mn) occurred below 100 cm. The water-soluble Cu and P concentrations were mainly dependent on their total concentrations in the sediments, whereas the water-soluble Cd, Co, Cr, Ni, Pb, Zn, and Mn concentrations were mainly controlled by pH.     

Organic matter-metal interactions in Recent sediments: the role of humic substances

Atomic emission spectrographic analysis of the trace inorganic constituents of marine humic substances gave the following range of concentrations: Si, 200 ppm to > 2%; Al, 400 ppm to ~ 1%; Fe, 600–3000 ppm; Ca, 600 ppm to > 2%; Mg, 20–6000 ppm; Na, 600 ppm to > 2%; Ag, < 6–600 ppm; B, < 60–1000 ppm; Cu, 600–4000 ppm; Mn, 8–100 ppm; Mo, <20–3000 ppm; Ni, 100–1000 ppm; Pb, < 40–600 ppm; Sn, 40–600 ppm; Ti, < 20–2500 ppm; V, 20–200 ppm; Zn, 350–4500 ppm; Zr, < 60–500 ppm.Humic substances contain a sizeable portion of the Cu, Mo and Zn found in sediments, but are less important for Ni, Co and Pb, and are insignificant for the Mn, V and Fe content. The metals are mostly introduced into the humates during their diagenetic formation in sediment by dissolution of metals from various mineralogical phases. A precursor of the sedimentary humates, the polymeric organic material dissolved in interstitial water, contains most of the Cu and Zn, about half of the Ni, Fe and Co, and very little of the Mn found in interstitial water. Comparison of the data on humates with that obtained by H₂O₂ treatment of sediments indicates that Cu, Zn and possibly most of the Mo are associated with organic matter, but that Ni and Co are associated with sulfides.     

Trace metal deposition and mobility in the sediments of two lakes near Sudbury,Ontario

The accumulation and mobility of Fe, Mn, Al, Cu, Ni and Pb in the sediments of two lakes (Clearwater, pH 4.5; and McFarlane, pH 7.5) near Sudbury, Ontario have been investigated. The Al, Cu and Ni concentrations are expectedly relatively high in the overlying waters of Clearwater Lake and much lower for Al and Cu in McFarlane Lake. The low trace metal concentrations found in the anoxic porewaters of Clearwater Lake could be explained by a sharp increase in porewater pH concomitant with SO₄² reduction and H₂S production within the first 1–2 cm of the sediments, which has conceivably led to the precipitation of mineral phases such as AL(OH)₃, NiS, and CuS. In both lakes, Fe concentrations in anoxic porewaters appear to be controlled by FeS and/or FeCO₃ formation. Solubility calculations also indicate MnCO₃ precipitation in McFarlane Lake. In Clearwater Lake, however, both porewater and total Mn were relatively low, a possible result of the continuous loss of Mn(II) through the acidic interface. It is suggested that upwardly decreasing total Mn profiles resulting from the removal of Mn from the top sediment layers under acidic conditions may constitute a reliable symptom of recent lake acidification.The downward diffusion of AI, Cu and Ni from the overlying water to the sediments has been estimated from their concentration gradients at the interface and compared to their total accumulation rates in the sediments. In both lakes the diffusion of Al is negligible compared to its accumulation rate. However, diffusion accounts for 24–52% of the accumulation of Cu in the sediments of Clearwater Lake, but appears negligible in McFarlane Lake. The downward diffusive flux of Ni is important and may explain 76–161% of the estimated Ni accumulation rate in Clearwater Lake, and 59% in McFarlane Lake. The porewater Cu and Ni profiles suggest that the subsurface sedimentary trace metal peaks observed in Clearwater Lake (as in other acid lakes) may not be caused by sediment leaching or by a recent reduction in sedimentation but may have a diagenetic origin instead. Diffusion to the sediments thus appears to be an important and previously overlooked trace metal deposition mechanism, particularly in acid lakes.     

Geochemistry of trace metals and Pb isotopes of sediments from the lowermost Xiangjiang River, Hunan Province (P. R. China): implications on sources of trace metals

This paper reports a geochemical study of trace metals and Pb isotopes of sediments from the lowermost Xiangjiang River, Hunan province (P. R. China). Trace metals Ba, Bi, Sc, V, Cr, Mn, Co, Ni, Cu, Zn, Mo, Cd, Sn, Sb, Pb, Tl, Th, U, Zr, Hf, Nb and Ta were analyzed using ICP-MS, and Pb isotopes of the bulk sediments were measured by MC-ICP-MS. The results show that trace metals Cd, Bi, Sn, Sc, Cr, Mn, Co, Ni, Cu, Zn, Sb, Pb and Tl are enriched in the sediments. Among these metals, Cd, Bi and Sn are extremely highly enriched (EF values >40), metals Zn, Sn, Sb and Pb significantly highly (5 < EF < 20), and metals Sc, Cr, Mn, Co, Ni, Cu and Tl moderately highly (2 < EF < 5) enriched in the river sediments. All these metals, however, are moderately enriched in the lake sediments. Geochemical results of trace metals Th, Sc, Co, Cr, Zr, Hf and La, and Pb isotopes suggest that metals in the river sediments are of multi-sources, including both natural and anthropogenic sources. Metals of the natural sources might be contributed mostly from weathering of the Indosinian granites (GR) and Palaeozoic sandstones (PL), and metals of anthropogenic sources were contributed from Pb–Zn ore deposits distributed in upper river areas. Metals in the lake sediments consist of the anthropogenic proportions, which were contributed from automobile exhausts and coal dusts. Thus, heavy-metal contamination for the river sediments is attributed to the exploitation and utilization (e.g., mining, smelting, and refining) of Pb–Zn ore mineral resources in the upper river areas, and this for the lake sediments was caused by automobile exhausts and coal combustion. Metals Bi, Cd, Pb, Sn and Sb have anthropogenic proportion of higher than 90%, with natural contribution less than 10%. Metals Mn and Zn consist of anthropogenic proportion of 60–85%, with natural proportion higher than 15%. Metals Sc, Cr, Co, Cu, Tl, Th, U and Ta have anthropogenic proportion of 30–70%, with natural contribution higher than 30%. Metals Ba, V and Mo might be contributed mostly from natural process.     

Geochemistry of surface sediments in the southwestern East/Japan Sea

We analyzed 77 surface sediment samples collected in the southwestern East/Japan Sea from the Korea Strait through the Ulleung Basin and the Korea Plateau for grain size, calcium carbonate, organic carbon, and major (Na, Mg, Al, Fe, K, Ca, and Ti) and trace elements (P, Mn, Sr, Li, Sc, V, Cr, Co, Ni, Zn, Cu, and Pb).The chemical composition of the surface sediments was found to be highly variable spatially. Cluster analysis of surface sediment chemical compositions indicated five major geochemical sedimentary environments: basin, lower slope, coast and upper slope, inner shelf, and outer shelf. Continental-shelf sediments were rich in shell fragments and had relict and coarse-grained characteristics. Recent fine-grained sediments were only distributed in coastal, slope, and basin areas. Concentrations of Al, K, Ca, Ti, Cr, and Sc were highest in the coastal and upper slope areas and decreased with water depth. Elemental ratios using major and trace elements indicated that coastal and upper slope detrital sediments were mixtures of sediments derived from the Changjiang (Yangtze) and Nakdong Rivers. Although the concentrations of organic carbon, P, Mn, V, Co, Ni, Cu, and Pb increased with water depth, their distribution patterns indicated authigenic (V, Cu, and Pb) and diagenetic (Fe, P, Mn, Co, and Ni) origins. The distribution pattern with water depth suggested that the chemical composition of surface sediment was determined by sedimentologic and geochemical processes, such as the supply of detrital and biogenic materials, and authigenic and post-depositional diagenetic processes in sediments.     

Environmental geochemistry of El Temsah Lake sediments, Suez Canal district, Egypt

The heavy metal contents of Mn, Ni, Cu, Zn, Cr, Co, Pb, Cd, Fe, and V in the surface sediments from five selected sites of El Temsah Lake was determined by graphite furnace atomic absorption spectrophotometer. Geochemical forms of elements were investigated using four-step sequential chemical extraction procedure in order to identify and evaluate the mobility and the availability of trace metals on lake sediments, in comparison with the total element content. The operationally defined host fractions were: (1) exchangeable/bound to carbonate, (2) bound to Fe/Mn oxide, (3) bound to organic matter/sulfides, and (4) acid-soluble residue. The speciation data reveals that metals Zn, Cd, Pb, Ni, Mn, Cu, Cr, Fe, and V are sink primarily in organic and Fe–Mn oxyhydroxides phases. Co is mainly concentrated in the active phase. This is alarming because the element is enriched in Al Sayadin Lagoon which is still the main site of open fishing in Ismailia. Average concentration of the elements is mostly above the geochemical background and pristine values of the present study. There is a difference on the elemental composition of the sediment collected at the western lagoon (Al Sayadin Lagoon), junction, the shoreline shipyard workshops, and eastern beach of the lake. Depending upon the nature of elements and local pollution source, high concentration of Zn, Pb, and Cu are emitted by industrial wastewater flow (shoreline workshops), while sanitary and agricultural wastewater (El Bahtini and El Mahsama Drains) emit Co and Cd in Al Sayadin Lagoon. On the other hand, there is a marked decrease in potentially toxic heavy metal concentrations in the sediments at the most eastern side of the lake, probably due to the successive sediment dredging and improvements in water purification systems for navigation objective. These result show that El Temsah receives concentrations in anthropogenic metals that risk provoking more or less important disruptions, which are harmful and irreversible on the fauna and flora of this lake and on the whole ecobiological equilibrium.     

Geochemical variations of major and trace elements in recent sediments,off the Gulf of Mannar,the southeast coast of India

The Gulf of Mannar along the Tuticorin coast is a coral base of the southeast coast of India. To obtain a preliminary view of its environmental conditions, geochemical distribution of major elements (Si, Al, Fe, Ca, Mg, Na, K, P), trace elements (Mn, Cr, Cu, Ni, Co, Pb, Zn, Cd) and acid leachable elements (Fe, Mn, Cr, Cu, Ni, Co, Pb, Zn, Cd) were analyzed in surface sediment samples from two seasons. Geochemical fractionation confirmed the lithogenic origin of metals, which were mainly associated with the detrital phase. The sediments in the gulf are sandy with abundant calcareous debris, which controls the distribution of total and acid leachable elements. Enrichment factors relative to crust vary by a magnitude of two to three and the presence of trace metals indicates the input of Cr, Pb, Cd, Cu and Zn in both forms through industrial activities. Factor analysis supports the above observation with higher loadings on acid leachable elements and its association with CaCO₃. The increase in concentration of trace metals (Cr, Pb, Cd, Cu, Co, Ni, Zn) along the Gulf of Mannar indicates that the area has been contaminated by the input from riverine sources and the industries nearby. The present study indicates that other sources should be evaluated in the long-term monitoring program.     

Speciation of some heavy metals in bottom sediments of the Ob and Yenisei estuarine zones

The speciation of Fe, Mn, Zn, Cu, Co, Ni, Cr, Pb, and Cd was studied in 52 samples of bottom sediments collected during Cruise 49 of the R/V Dmitrii Mendeleev in estuaries of the Ob and Yenisei rivers in the southwestern Kara Sea. Immediately after sampling, the samples were subjected to on-board consecutive extraction to separate metal species according to their modes of occurrence in the sediments: (1) adsorbed, (2) amorphous Fe-Mn hydroxides and related metals, (3) organic + sulfide, and (4) residual, or lithogenic. The atomic absorption spectroscopy of the extracts was carried out at a stationary laboratory. The distribution of Fe, Zn, Cu, Co, Ni, Cr, Pb, and Cd species is characterized by the predominance of lithogenic or geochemically inert modes (70–95% of the bulk content), in which the metals are bound in terrigenous and clastic mineral particles and organic detritus. About half of the total Mn amount and 15–30% Zn and Cu is contained in geochemically mobile modes. The spatiotemporal variations in the proportions of metal species in the surface layer of sediments along the nearly meridional sections and through the vertical sections of bottom sediments cores testify that Mn and, to a lesser extent, Cu are the most sensitive to changes in the sedimentation environment. The role of their geochemically mobile species notably increases under reducing conditions.     

Chemical fractionation of transition elements in Pacific pelagic sediments

Partitioning of transition elements in Pacific pelagic sediments (35 samples) was performed by sequential chemical leaching with barium chloride/triethanolamine (easily extractable fraction), acidic cation exchange resin (carbonate phases), and hydroxylamine hydrochloride and dilute hydrochloric acid solutions (hydrous oxides). Residual metal percentages are highest in red-brown clays and siliceous ooze, intermediate in calcareous materials and low in micronodules (2 samples, > 125 μm): residual metal contents seem to be controlled predominantly by the rate of admixture of volcanoclastic materials. At higher bulk metal concentrations, the non-residual fractions of Mn, Cu, Ni and Zn generally increase both in red-brown pelagic clays and in siliceous ooze. Mn, Ni, and Co concentrations are mainly associated with the easily reducible fraction (0.1 M NH₂OH·HCl), whereas Fe, Cu, and Zn exhibit higher percentages in the hydrochloric acid soluble fractions (0.3 M HCl); Zn and Cu are associated to some extent with the carbonate phase, copper with the easily extractable fraction.