Sequential extractions on mine tailings samples after and before bioassays: implications on the speciation of metals during microbial re-colonization

Mine tailings may be remediated using metal tolerant microorganisms as they may solve the limiting conditions for healthy development of plants (i.e., low organic mater content and poor physical conditions). The aim of this study was to investigate the consequences of microbial colonization on the chemical speciation of trace metals. Surface samples from the Valenciana mine tailings (Guanajuato, Mexico) were used for long-term bioassays (BA), which consisted in the promotion of microorganisms, development on tailings material under stable laboratory conditions (humidity, temperature, and light exposure). A five-step sequential extraction method (exchangeable, carbonate/specifically adsorbed, Fe–Mn oxides, organic matter (OM)/sulfide, and residual fractions) was performed before and after BA. Extraction solutions and leachates were analyzed by inductively coupled plasma-mass spectrometry. OM content, cationic exchange capacity, and pH values were also assessed before and after BA. The results indicate that trace elements are generally present in nonresidual fractions, mainly in the Fe–Mn oxides fraction. The concentration of total Zn, As, Se, Pb, and exchangeable Cu and Pb is above the recommendable limits for soils. Despite the high bioavailability of the former elements, biofilms successfully colonized the tailing samples during the BA. Cyanobacteria and green algae, heterotrophic fungi, aerobic bacteria, and anaerobic bacteria composed the developed biofilms. Chemical controls of trace elements could be attributed to absorption onto inorganic complexes (carbonates, metal oxides), while biofilm occurrence seems to enhance complexation and immobilization of Cr, Ni, Cu, Zn, As, and Pb. The biofilm developed does not increase the bioavailable forms and the leaching of the trace elements, but significantly improves the OM contents (natural fertilization). The results suggest that biofilms are useful during the first steps of the mine tailings remediation.     

Soil and groundwater pollution of an urban catchment by trace metals: case study of the Addis Ababa region, central Ethiopia

Analysis of the total heavy metal (Cr, Cd, Pb, As, Cu, Ni, Zn, Co) concentration was performed on 33 soil samples taken from different profiles and soil types in a highly urbanized and industrial sector of Addis Ababa, central Ethiopia. They were analyzed using aqua regia extraction coupled with a four-stage sequential extraction (SE) procedure. The objectives of the analysis were to investigate the degree of soil heavy metal contamination, its binding forms, mobility and the implications for the groundwater resource. The results show a relatively high content of the analyzed trace metals in the soil attributed to anthropogenic and geogenic sources. Although most of the trace metals are found in the upper few centimeters of the residual soils, because of churning processes within the black cotton soils, vertical distribution of the trace metals is complex. According to the heavy metal SE analysis, the major heavy metal contribution is from the residual followed by the hydroxide phases. Groundwater heavy metal contamination is present with more than 90 and 50% of the analyzed groundwater samples exceeding WHO guidelines for Cr and Cd, respectively. Since the degree of soil heavy metal contamination has apparently not surpassed the soil’s buffering capacity, it appears that the transport path of these toxic metals to the groundwater is through fractures, joints, and related preferential flow paths.     

Selective chemical extraction of heavy metals in tailings and soils contaminated by mining activity: Environmental implications

Total concentrations of chemical elements in soils may not be enough to understand the mobility and bioavailability of the elements. It is important to characterise the degree of association of chemical elements in different physical and chemical phases of soil. Another geochemical characterisation methodology is to apply sequential selective chemical extraction techniques. A seven-step sequential extraction procedure was used to investigate the mobility and retention behaviour of Al, Fe, Mn, Cu, Zn, Pb, Cr, Co, Ni, Mo, Cd, Bi, Sn, W, Ag, As and U in specific physical–chemical and mineral phases in mine tailings and soils in the surroundings of the abandoned Ervedosa mine. The soil geochemical data show anomalies associated with mineralised veins or influenced by mining. Beyond the tailings, the highest recorded concentrations for most elements are in soils situated in mineralised areas or under the influence of tailings. The application of principal components analysis allowed recognition of (a) element associations according to their geochemical behaviour and (b) distinction between samples representing local geochemical background and samples representing contamination. Some metal cations (Mn, Cd, Cu, Zn, Co, Cr, Ni) showed important enrichment in the most mobilisable and bioavailable (i.e., water-soluble and exchangeable) fractions due likely to the acidic conditions in the area. In contrast, oxy-anions such as Mo and As showed lower mobility because of adsorption to Fe oxy-hydroxides. The residual fraction comprised largest proportions of Sn and Al and to a lesser extent Zn, Pb, Ni, Cr, Bi, W, and Ag, which are also present at low concentrations in the bioavailable fractions. The elements in secondary mineral phases (mainly Fe, Mn, Cu, Zn, Cd, Pb, W, Bi, Mo, Cr, Ni, Co, As and U) as well as in organic matter and sulphides are temporarily withheld, suggesting that they may be released to the environment by changes in physico-chemical conditions.     

Évaluation de la mobilité des métaux dans les sédiments fluviaux du bassin de la Vire (Normandie,France) par extractions simples ou séquentielles

This work compares the quantities of labile metals removed from the Vire River (Normandy) sediments by a sequential extraction procedure to those liberated by single leaches (Mg(NO₃)₂, HCl and EDTA). Compared to the other extractions, Mg(NO₃)₂ underestimated the mobility results. The sequential procedure was the most aggressive, except for Ca and Pb. The hypothetic correlation between quantities of an element removed by single leaches and its fractionation in the sediment according to the sequential procedure was not satisfying. Finally, it should be underlined that enrichments of Cd, Pb and Zn were noticed in the Vire sediments. To cite this article: L. Leleyter, F. Baraud, C. R. Geoscience 337 (2005).     

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.     

Changes in mobility and speciation of heavy metals in clay-amended incinerator fly ash

The generation of municipal solid waste incinerator fly ash (MSWIF) has been increasing significantly over the recent past, and its disposal is problematic and costly due to high concentration of leachable heavy metals present in the material. This study explored a potential stabilization of MSWIF by blending with a natural sorbent material with low permeability, clay, and assessed the potential release of heavy metals from the stabilized mixtures under various simulated subsurface environments. The leachability of heavy metals such as Pb, Cd, Cr, Zn and Cu in the MSWIF-clay mixtures cured for 1 to 360 days was investigated by performing leaching tests and sequential chemical extractions (SCE). Leaching tests were performed at acidic, neutral and alkaline pH values. The leaching test results suggested that the natural clay could turn the MSWIF into non-hazardous material. All the MSWIF-clay mixtures demonstrated leaching behavior different from that of the original MSWIF. SCE results revealed that the acidic and reducing conditions were the most unfavorable to the immobilization of the heavy metals in the stabilized MSWIF-clay matrix. Conversely, the oxidizing and alkaline conditions were not critical to the stabilized MSWIF-clay mixtures. Apparently, clay in the mixtures could function as an adsorptive micro-barrier to retain the heavy metals within the MSWIF-clay matrices.     

Mobilisation of traffic-derived trace metals from road corridors into coastal stream and estuarine sediments,Cairns, northern Australia

This investigation revealed the presence of traffic-derived metals within road, stream and estuarine sediments collected from a coastal catchment, northern Australia. Studied road sediments displayed variable total metal concentrations (median Cd, Cu, Pb, Pd, Pt, Ni and Zn values: 0.19, 42.6, 67.5, 0.064, 0.104, 36.7 and 698 mg/kg, respectively). The distinctly elevated Zn values are due to abundant tyre rubber shreds (as verified by SEM-EDS and correlation analysis). By comparison to the road sediments, background stream sediments taken upstream from roads have relatively low median Pb, Pd, Pt and Zn concentrations (7.3 mg/kg Pb, 0.01 mg/kg Pd, 0.012 mg/kg Pt, 62 mg/kg Zn). Stream and estuarine sediment samples collected below roads have median values of 21.8 mg/kg Pb, 0.014 mg/kg Pd, 0.021 mg/kg Pt and 71 mg/kg Zn, and exhibit ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb ratios that appear on a mixing line between the isotopically distinct background stream sediments and the road sediments. Thus, mobilisation of dusts and sediments from road surfaces has resulted in relatively elevated Pb, Pd, Pt and Zn concentrations and non-radiogenic Pb isotope ratios in local coastal stream and estuarine sediments. The investigation demonstrates that traffic-derived metals enter coastal stream and estuary sediments at the fringe of the Great Barrier Reef lagoon.     

Speciation and mobility of heavy metals in mud in coastal reclamation areas in Shenzhen,China

Coastal reclamation has been carried out along the coastal areas near Shenzhen, China in a large scale since 1980s by dumping fill materials over the marine mud at the sea bottom. Usually the area to be reclaimed is drained first and some of the mud is air-dried for a few weeks before it is buried by fill. After reclamation, the terrestrial groundwater, which is relatively acidic and with high dissolved oxygen, gradually displaces the seawater, which is alkaline with high salinity. The changes in the burial conditions of mud and the properties of the pore water in the mud may induce the release of some heavy metals into the mud. Field survey confirms that the pH and salinity of the groundwater in the reclamation site are much lower than the seawater. Chemical analyses of mud and groundwater samples collected from the reclamation sites reclaimed in different years indicate that most of the heavy metals in the mud decrease gradually with time, but the heavy metals in the groundwater are increased. The release of heavy metals into pore water due to reactivation of heavy metals in the mud is of environmental concern. To understand why some of the heavy metals can be released from the mud more easily than others, a sequential extraction method was used to study the operationally determined chemical forms of five heavy metals (Cu, Ni, Pb, Zn, and Cd) in the mud samples. Heavy metals can be presented in five chemical forms: exchangeable, carbonate, Fe–Mn oxide, organic, and residual. Ni and Pb were mainly associated with the Fe–Mn oxide fraction and carbonate fraction; Zn was mainly associated with organic fraction and Fe–Mn oxide fraction, while Cu and Cd were associated with organic fraction and carbonate fraction, respectively. If the residual fraction can be considered as an inert phase of the metal that cannot be mobilized, it is the other four forms of heavy metal that cause the noticeable changes in the concentration of heavy metals in the mud. On the basis of the speciation of heavy metals, the mobility of metals have the following order: Pb (36.63%) > Cu (31.11%) > Zn (20.49%) > Ni (18.37%) > Cd (13.46%). The measured metal mobility fits reasonably well with the degree of concentration reduction of the metals with time of burial observed in the reclamation site.     

Combination of single and sequential chemical extractions to study the mobility and host phases of potentially toxic elements in airborne particulate matter

Risk assessment of metals associated to airborne particulate matter (PM) has usually been based on the analysis of their total concentrations, which is a poor indicator of metal mobility. Chemical fractionation processes may provide an additional level of information, however, chemical complexity and small sample sizes do not allow to combine several extraction methods. Additionally, analysing the metal concentrations during the extractions exceptionally provides restricted information about metals’ speciation. To overcome these limitations we collected total suspended particulate matter (TSP) samples from the air filters placed in the air supply channel of methane-heated turbines of thermal power stations which allows collecting large amounts of TSP materials. Additionally, we combined single and sequential chemical extractions in which not only the concentrations of potentially toxic elements (PTE) (Cd, Cr, Cu, Ni, Pb, Zn) but also that of the major chemical components (Al, Ca, Fe, K, Mg, Mn, Na, P, S, Ti) were analysed. Our aims were to study these metals’ mobility and speciation through the study of their association to major chemical components.Accumulation of the studied PTEs in the TSP material suggests moderate contamination for Ni, Cd and Cr whereas a heavy one for Cu, Zn and Pb. Three groups of these PTEs could be distinguished based on their mobility. The highly mobile Zn and Cd (large ratios of water and weak acid soluble fractions) can be considered as especially harmful elements to environment. The moderately mobile Pb and Cu (large ratios of reducible and oxidizable fractions, respectively) may potentially have a negative effect on the environment, whereas the immobile Cr and Ni cannot be expected to pose a serious risk. Based on the statistical evaluation of extraction data, the potential phases for Zn and Cu are presented by metal-sulphates, -nitrates, -chlorides, -carbonates and -hydroxides, as well as sorbed forms. Lead primarily hosted by metal-carbonates and sorbed forms, as well as by -hydroxides, whereas Cu by organic matter. Finally, Cr and Ni are mostly incorporated into very resistant phases, most probably by magnetite or other resistant metal-oxides.Combination of single and sequential extractions, as well as that of the analysis of not only the target elements but also the major chemical components were found to be a very effective tool to study the host phases of PTEs in the TSP material. The necessity for relatively large sample amounts for such analyses could be fulfilled using special sampling methodology; however, obvious disadvantages of this kind of sampling must be taken into account when resulted data are evaluated.     

A GIS-based approach for detecting pollution sources and bioavailability of metals in coastal and marine sediments of Chabahar Bay,SE Iran

Chabahar Bay in SE of Iran is a shallow semi-enclosed environment affected by anthropogenic activities. In this paper, 19 sediment samples were collected and concentration of selected metals (Cu, Pb, Zn, Cd, Ni, Cr, Co, V and Fe) was determined using ICP-MS analytical method. Sediment samples from five stations were also selected for sequential extraction analysis and concentration of metals in each fraction was determined using ICP-OES. In order to investigate the environmental quality of Chabahar Bay, geographic information system (GIS) along with geochemical data, environmental indices and statistical analyses were used. Calculated contamination degree (C_d) revealed that most contaminated stations (Ch3, S1 and S3) are located SE of Chabahar Bay and contamination decreases in a NW direction. The S9 station, west of the bay, is also contaminated. High organic matter (OM) content in the sediments is most likely the result of fuel and sewage discharge from fishing vessels along with discharge of fishing leftovers. Significant correlation coefficient among OM, Fe, Cu, Pb, Zn and Cd seemingly reflects the importance of the role that OM and Fe oxy-hydroxides play in the metals mobility. The results of hierarchical cluster analysis (HCA), computed correlation coefficient and sequential extraction analysis suggest that Cu, Pb, Zn and Cd probably come from antifouling and sea vessel paints, while Ni, Cr, Co, V and Fe are most likely contributed by ophiolitic formations located north of the bay and/or deep sea sediments. Average individual contamination factors (ICFs) indicated that the highest health hazard from the bay is posed by Cu, Pb and Zn.     

Mineralogy and trace element relative solubility patterns of shallow marine sediments affected by submarine tailings disposal and artisanal gold mining,Buyat-Ratototok district,North Sulawesi,Indonesia

Shallow marine sediments of the Buyat-Ratototok district of North Sulawesi, Indonesia, are affected by submarine disposal of industrial gold mine tailings and small-scale gold mining using mercury amalgamation. Industrial mine tailings contained 590–660 ppm arsenic, 490–580 ppm antimony, and 0.8–5.8 ppm mercury. Electron microprobe survey found both colloidal iron–arsenic-phases without sulphur and arsenian pyrite in tailings and sites to which tailings had dispersed, but only arsenopyrite in sediments affected by artisanal mining. Antimony in tailings was present as antimony oxides, colloidal iron–antimony phases, colloidal iron–antimony phases, and stibnite in sediments affected by both types of mining. A sequential extraction found that 2% of arsenic held in tailings and tailings-contaminated sediments was exchangeable, 20–30% was labile, including weakly adsorbed, carbonate- and arsenate bound, 20–30% was metastable, probably incorporated into iron or manganese oxyhydroxides, or strongly adsorbed to silicate minerals, and 40–48% was relatively insoluble, probably incorporated into sulphides or silicates. Arsenic in sediments affected by artisanal gold mining was 75–95% relatively insoluble. Antimony in all sediments was >90% relatively insoluble. Relative solubility patterns of most other metals did not differ between industrial tailings-affected, artisanal-mining affected areas, and fluvial sediments. Results suggest that submarine tailings disposal is not suitable for refractory Carlin-like gold deposits because ore processing converts arsenic to forms unstable in anoxic marine sediments. Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.     

Comparison of three procedures (single,sequential and kinetic extractions) for mobility assessment of Cu,Pb and Zn in harbour sediments

The mobility of Cu, Pb and Zn in harbour sediments was investigated using single, sequential and kinetic extraction techniques. Each type of extraction provides different information on the mobility of these elements in the environment. The single HCl extraction assesses general mobility, the sequential extraction assesses geochemical partitioning and kinetic extraction allows quickly and slowly mobilized elements to be identified. Kinetic extraction also allows the influence of extraction duration to be assessed. The results presented in this paper highlight the complementary information provided by different types of mobility studies. The lack of correlation between element mobility and total metal concentration emphasises the inadequacy of using total metal concentrations in risk assessment.     

Temporal variability of trace metals in new jersey pinelands streams: relationships to discharge and pH

Dissolved and particulate trace metal (Al, Cd, Cu, Pb, and Zn) concentrations were determined over a 21 month time period at four streamwater sites in the Pinelands (New Jersey, USA), a coastal plain region characterized by low-pH waters and highly weathered soils. Al and Zn were also determined at two sites over a 5 day period following a major precipitation event. In the Batsto River (pH 4.4–6.3), a representative Pinelands stream draining a largely forested watershed moderately impacted by agriculture, discharge-weighted mean concentrations of dissolved metals were (in nM): Al = 4610; Cd = 0.39; Cu = 4.6; Pb = 1.0; and Zn = 149. Dissolved Cd, Cu, and Zn in the undeveloped Bass River (pH 4.1–4.8) are in a similar range, but Pb concentration is 2–3 times greater. Dissolved metals show highly significant positive correlations to discharge, and weaker inverse relationships to pH over both the long- and short-term time series. Overall, seasonal and short-term variability in dissolved metal concentrations is most consistent with control by hydrologic flow path changes during high discharge, when shallow groundwaters mobilize anthropogenic metals stored in near-surface soil horizons and bypass potential metal removal processes in bordering wetlands. The data also suggest that in-stream metal removal driven by summertime biological productivity may further reduce low-discharge metal concentrations, as a secondary effect. For these metals, the particulate fraction is generally minor, and variations in solution/particle partitioning are unimportant to spatial/temporal variations dissolved concentrations, except for Pb. Estimates of atmospheric input can account for riverine fluxes of these metals, and suggest that Zn retention is minimal in this system, while Pb, Cu and Cd are more strongly retained. The positive relationship between discharge and metals concentration, and the unusually high concentrations in Pinelands streams compared to other world rivers, suggest that riverine effects on metals distributions in the estuary and nearby coastal ocean will be measurable and strongly seasonal.     

Granulometric and chemical composition of the Sava River sediments upstream and downstream of the Krsko nuclear power plant

Total concentrations of 13 elements (K, Ca, Ti, Cr, Mn, Fe, Cu, Zn, Rb, Sr, Y, Zr, Pb) in the size-fractionated Sava River sediments upstream and downstream of the Krsko nuclear power plant together with metal speciation within bulk sediment have been investigated. Trace metals generally increase with decreasing particle size, however, because of entrapment of organic matter in the 0.63–1 mm fraction, concentrations in the coarser sediment fraction are higher than expected. Exchangeable Pb, Zn, Cu, Mn, Cr and Fe are generally found to represent a negligible fraction of the total metal concentration of the bulk sediment. Seasonal variations of the Pb, Zn and Cu concentrations in the <0.5 mm fraction reflect decreased values during the spring period. Heavy metal concentrations in the 2003 waste water discharges from the Krsko nuclear power plant released into the Sava River were much lower than their maximum allowed values. Combined rubidium and organic matter normalization of the Zn, Pb and Cu concentrations, which was applied on the minus 0.063 mm fraction, indicated three potential sources of contaminants.     

战术性与战略性的深穿透地球化学方法

金属活动态测量法是寻找隐伏矿的深穿透地球化学方法之一,目前有关金属活动态测量的应用研究较多,但对于活动态的提取和相态（包括水提取相）分析测定方法研究较少。传统的原子吸收光谱法只能测定单元素,而电感耦合等离子体质谱法（ICP-MS）最多同时测定水提取相中5个元素（Cr、Cu、Zn、Cd、Pb）,已不能满足当前化探任务中金属活动态测量的需要。本文建立了高分辨率电感耦合等离子体质谱（HR-ICP-MS）测定水提取相元素中59个元素的方法。通过试验,确定了59个元素的最佳提取条件为：提取时间24 h,提取温度35℃,液固比15:1,固液分离方法为离心分离。方法精密度（RSD,n=12）为3.11%~38.1%,其中RSD大于20%的数据只占全部试验结果的28.4%,表明该方法较为准确可靠,方法检出限满足元素活动态的分析要求。运用HR-ICP-MS测定水提取相元素的方法,不仅增加了测定元素的数量,也降低了检出限,提高了精密度,可以为勘查地球化学研究提供更为全面的信息。

     

Partitioning of trace metals between particulate,colloidal and truly dissolved fractions in a polluted river: the Upper Vistula River (Poland)

Metal partitioning depends on the physical–chemical conditions of a system and can be affected by anthropogenic inputs. In this study, the authors report the results of trace metal partitioning between particulate (>1.2 μm), colloidal (1.2 μm–1 kDa) and truly dissolved (<1 kDa) fractions in the polluted section of the Upper Vistula River compared with the non-polluted headwaters. It was found that the salt input in the Vistula River induced a decrease of colloid concentration and the increase of suspended particulate matter. Compared with upstream from the polluted section, the metal concentrations (Co, Cu, Cr, Mn and Zn) in the colloidal fraction were lower. It was mainly due to the rapid colloid coagulation at increased salinity, the competition with ligands and major ions (Ca and Mg) and the weak mobility of metals associated with particles at the pollution sources.     

Hafnium and neodymium isotopes in surface waters of the eastern Atlantic Ocean: Implications for sources and inputs of trace metals to the ocean

We present hafnium (Hf) and neodymium (Nd) isotopic compositions and concentrations in surface waters of the eastern Atlantic Ocean between the coast of Spain and South-Africa. These data are complemented by Hf and Nd isotopic and concentration data, as well as rare earth element (REE) concentrations, in Saharan dust.Hafnium concentrations range between a maximum of 0.52 pmol/kg in the area of the Canary Islands and a minimum value of 0.08 pmol/kg in the southern Angola Basin. Neodymium concentrations also show a local maximum in the area of the Canary Islands (26 pmol/kg) but are even higher between ∼20°N and ∼4°N reaching maximum concentrations of 35 pmol/kg. These elevated concentrations provide evidence of inputs from weathering of the Canary Islands and from the partial dissolution of dust from the Sahara/Sahel region. The inputs from ocean island weathering are also reflected in radiogenic Hf and Nd isotopes.The Hf isotopic compositions of dust samples themselves are highly variable, ranging between ε_Hf = −20 and −0.6. The combined Hf and Nd isotopic compositions of dust plot close to the “terrestrial array” during periods of appreciable dust load in the atmosphere. During low atmospheric dust loading combined Hf and Nd isotopic compositions similar to seawater are observed. Most of the variability can be explained in terms of variable degrees of zircon loss from the dust samples, which in turn is linked to sorting during atmospheric transport to the eastern Atlantic Ocean and possibly presorting by sedimentary redistribution on the continent. In addition, increasing relative proportions of radiogenic clay minerals with decreasing grain size may contribute to the radiogenic Hf isotopic compositions observed.While the Nd isotopic composition in the surface ocean reflects the Nd isotopic composition of the Saharan dust adjacent to the Sahara/Sahel region, the release of Hf from that dust appears to be incongruent and results in surface ocean Hf isotopic compositions which are ∼10 ε_Hf more radiogenic than the bulk dust. Radiogenic Hf appears to be released from clays and possibly from trace apatite. Rare earth element patterns of dust samples indicate the presence of apatite but provide no evidence for ferromanganese grain coatings, suggesting that such coatings are insignificant in the release of Hf and Nd from Saharan dust to the surface ocean.The Nd isotopic composition of the surface waters becomes less radiogenic south of the equator, most likely reflecting the release of Nd from Congo river sediments. The release of Hf from Saharan dust and the Congo river sediments, however, does not produce distinct Hf isotopic signatures in the surface ocean, implying that the mobile fraction of Hf integrated over large continental areas is isotopically uniform. The Hf isotopic uniformity in the surface ocean means that the limited variability in deep water isotopic compositions is consistent with a short deep water residence time and reflects homogenous continental inputs rather than efficient deep water homogenization.     

Geochemical fractionation of Ni,Cu and Pb in the deep sea sediments from the Central Indian Ocean Basin: An insight into the mechanism of metal enrichment in sediment

Metal speciation study in combination with major element chemistry of deep sea sediments provided possible metal enrichment pathways in sediments collected from environmentally different locations of Central Indian Ocean Basin (CIB). Metal speciation study suggests that Fe–Mn oxyhydroxide phase was the major binding phase for Ni, Cu and Pb in the sediments. The second highest concentrations of all these metals were present within the structure of the sediments. Easily reducible oxide phase (within the Fe–Mn oxyhydroxide binding phases) was the major host for all the three metals in the studied sediments. Major element chemistry of these sediments revealed that there was an increased tendency of Cu and Ni to get incorporated into the deep sea sediment via the non-terrigenous Mn-oxyhydroxide fraction, whereas, Pb gets incorporated mostly via amorphous Fe-hydroxides into the sediment from the CIB. This is the first attempt to provide an insight into the mechanism of metal enrichment in sediment that host vast manganese nodule.     

利用Mo-U等多指标判别黑色岩系中硅质岩形成氧化-还原环境的可行性分析及意义

硅质岩作为一种重要的沉积岩类型,是研究前新生代古海洋环境的重要手段,但其缺乏在氧化-还原环境方面的应用。同时硅质岩是黑色岩系的重要组成部分,拓展硅质岩在该方面的应用研究,有利于加深对黑色岩系形成机理的认识。本文综述了硅质岩的现有研究方法、黑色岩系中黑色页岩和硅质岩研究的局限性和互补性,并论述了将Mo-U等氧化-还原敏感金属多指标判别方法应用于硅质岩,用来判断氧化-还原环境和盆地局限性等方面的理论可行性。在分析扬子地块及其周缘黑色岩系及硅质岩研究现状的基础上,认为将在黑色页岩使用成熟的氧化-还原环境研究方法应用于互层的(热水沉积)硅质岩,理论上具有可行性,并在扬子地块西北缘若尔盖地区奥陶-志留纪黑色岩系中互层的黑色页岩和热水沉积硅质岩岩性组合中得到进一步验证。该方法的应用可深化对扬子地块西北缘黑色岩系沉积环境特殊性及其中U-Au-Ni-Mo-V多金属矿源层的认识。