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1.
Organic-rich sediment samples collected from a transect within, and below, the Oman Margin oxygen minimum zone (OMZ) were analysed using a sequential leaching technique to characterise the diagenetic behaviour and speciation of Mn and Fe in operationally defined sediment host fractions. Trace metals showed distinct diagenetic behaviour in the two contrasting environments that were sampled. The absence of non-detrital Mn in the cores below the OMZ site is attributed to the lack of easily reducible oxides in surficial sediments and to the reduction and export of any moderately reducible aged oxides. The reactive form of solid phase Mn showed a classic feature of enrichment in the upper layer of the sediments at the abyssal site, reflecting the presence of an oxidising sedimentary layer which acts as a Mn trap during its recycling. The diagenetic Mn enrichment was inferred from typical downcore colour changes and an upward-increasing Mn content in the upper core sections. An easily reducible Fe oxide layer was observed in the abyssal sediments at an identical depth to the Mn enrichment suggesting that Fe associated with Mn oxides also has undergone sub-oxic diagenesis. However, the association of Fe with organic matter did not indicate diagenetic modification; i.e., the binding strength of the metal with organic materials appears to be sufficiently strong to preserve the trace metal. The speciation signature of non-detrital Fe differed from that of Mn. The association of Fe with organic matter suggests that this metal does not undergo diagenetic modification and is preserved in abyssal sediments. The contrasting behaviour of Mn and Fe observed between cores within the OMZ were particularly interesting. Another interesting observation was that, for cores below the OMZ, the iron oxides were associated with the Mn-oxide peak, rather than deeper in the sediments as observed by earlier studies in the Atlantic [Froelich et al. (1979). Geochim. et Cosmochim Acta 43, 1075–1090].This revised version was published online in May 2005 with corrections to the article title.  相似文献   

2.
Heavy metal contamination was the main environmental problem around the Jinchang Ni–Cu mine area of Gansu, Northwest China. The concentration of heavy metals (Cr, Cu, Ni, Pb, and Zn) in various environmental mediums around the Jinchang Ni–Cu mine area were analyzed using atomic absorption spectrometry (AAS). The different chemical speciation of heavy metals was extracted using BCR (European Community Bureau of Reference) sequential extraction procedure, and the concentration of chemical speciation of each heavy metal was measured by inductively coupled plasma-atomic emission spectrometry. The results showed that Cu and Ni were the most important heavy metal pollutants in various mediums including cultivated soils, dust on slagheap surfaces, tailings, and sediments in waste water drains. In the tailings and sediments, the concentrations of Ni were obviously higher than those of Cu, whereas, in the soil and dust, the concentrations of Cu were higher than those of Ni. Analysis of chemical speciation indicated that Cr and Zn were mainly in residual fraction; Cu was mainly in oxidizable fraction; Ni was mainly in reducible fraction and acid soluble fraction; and Pb was mainly in reducible fraction and residual fraction. The extent of contamination of various environmental mediums was different because the heavy metals were derived from different sources. Furthermore, the mobility of various heavy metals was different because of the different distribution of chemical speciation.  相似文献   

3.
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.  相似文献   

4.
《Applied Geochemistry》1999,14(5):621-633
Forms of Pb, Zn and Cd in the different size fractions (<2 μm, 2–53 μm and >53 μm) of waste dumps, stream sediments and surrounding soils from a former Au mine in Korea, were investigated chemically by sequential extraction analysis and mineralogically by XRD and analytical SEM, so as to clarify the relationships between chemical and mineralogical forms. Total concentrations for the waste dumps and the stream sediments range from 655 to 2920 mg/kg for Pb, 565 to 1191 mg/kg for Zn, and 24.4 to 71.4 mg/kg for Cd, while those for the surrounding soils do not exceed the natural background levels. Direct observations on the heavy mineral fractions of the waste dumps and the stream sediments indicates that the primary sphalerite is still the main pool of the Zn and Cd, while a large part of the primary galena has been changed into a carbonate-bound form. This is in a good agreement with the partitioning of chemical forms in the coarse fractions, in which most of the Zn (75.3 to 79.4% for the waste dumps) and Cd (54.8 to 60.1% for the waste dumps) are associated with the oxidizable form, while most of the Pb (68.8 to 71.0% for the waste dumps) is in the acid (NaOAc)-extractable form. On the other hand, the partitioning of metal forms in the clay fraction is characterised by the highest proportion of the reducible form for all metals (56.6 to 73.8% for Pb, 60.2 to 68.4% for Zn, and 27.1 to 36.8% for Cd in the waste dumps), suggesting precipitation of easily to moderately reducible oxides and hydroxides from the other forms during weathering. With the increase of pH, the dramatic changes of the acid-extractable Pb, the oxidizable Zn and Cd in the coarse fractions, and the exchangeable form, especially for Cd in the clay fraction indicate that pH is the prime factor controlling the partitioning of heavy metals.  相似文献   

5.
Heavy metals distribution in core sediments, different size fractions of bed sediments (>212 urn, 90-212 jam, 63–90 urn, 53–63 urn, < 53 urn), and suspended sediments (>30 urn, 20–30 m, 10–20 urn, 2–10 urn, <2 m) have been discussed. Pb, Zn, and Cr have been accumulating in recent years in the sediments. Si, Al, Fe, Ca, and Mg dominate the bed and suspended sediment composition. Metals show increasing concentrations in finer sediments. Applying multivariate analysis to sediment composition, metals have been grouped into different factors depending upon their source of origin. Chemical fractionation studies on suspended and bed sediments show Fe, Zn, Cu, and Pb are associated with the residual fraction and Mn with the exchangeable fraction.  相似文献   

6.
青岛胶州湾沉积物痕量元素黄铁矿化程度及其剖面类型   总被引：4，自引：0，他引：4  
为了探索青岛近海不同沉积环境下不同痕量元素的黄铁矿化规律, 2003年5月潜水员潜入海底采集了4个不同沉积环境的未扰动柱样, 并利用Huerta-Diaz and Morse (1990)连续提取技术测试分析了沉积物痕量金属的不同存在形式(活性态和黄铁矿结合态) 在垂直剖面上的分布规律.结果表明: 除了在涨潮三角洲上部沉积和潮下带沉积物柱子的Cd和Cr外, 痕量元素的黄铁矿化度的增高取决于其相应剖面上的DOP的增高; 并且不同痕量元素向黄铁矿中转移的规模存在着较大的差别, 即元素As、Hg和Mo转移的规模最大, Cu、Zn、Cd、Cr、Co和Ni中等, Pb和Mn最小; 此外, 还进一步揭示了河流三角洲沉积物的下部各元素的黄铁矿化程度高, 而潮下带沉积物以及涨潮三角洲沉积物低.最后指出在河口水下三角洲进行的清淤工作应注意黄铁矿结合态痕量元素的活化而产生生物有效的毒性元素.   相似文献   

7.
The chemical partitioning of Pb and Zn was investigated in contaminated stream sediments from the River Ystwyth in mid-Wales, with changes in metal/substrate fixation being related to variations in channel morphology. Confinement of the channel by bedrock (chute zones) is sufficient to create very turbulent flow conditions facilitating the precipitation of Mn(IV) on surfaces of sand sized particles (2000-63 μm). Phase specific extraction of Pb (easily reducible fraction) from this particle size range indicates significant adsorption on precipitated forms of Mn. Conversely, under meandering conditions, association with the moderately reducible fraction (Fe-oxides) was more influential in the physico-chemical partitioning of Pb. Thus oxyhydroxide “precipitation zones” are created which affect heavy metal partitioning. These phenomena are, however, not observed on silt and clay sized particle coatings (<63 μm). The partitioning of Zn is not influenced by channel morphology due to a combined influence of the greater solubility of ionic species and subsequent transfer in solution and to the prevalence of total sediment Zn as sphalerite (ZnS).  相似文献   

8.
Axial surveys were performed in the two river tributaries of the Cochin estuary, SW India during November 1988. Surficial sediments were subjected to sequential chemical extractions to delineate five metal fractions, namely, exchangeable, carbonate bound, easily reducible, organic/sulfide bound, and residual. The results indicated selective accumulation of Mn and Ni in carbonate bound and organic/sulfide forms, along with marginal amounts of Co in the exchangeable fraction. Large portions of Fe and Cr occurred in the residual fraction, whereas composite fractionation of Zn species was noticed. The exchangeable fractions of Fe and Cr as well as of easily reducible cobalt were below detection limits. The levels of Cr and Zn indicate anthropogenic inputs in this estuary, whereas Co and Ni show regional contamination exceeding natural levels. The analytical speciation procedure helps to deduce the sedimental diagenetic processes in the estuarine environment.  相似文献   

9.
Sediments from a core retrieved during installation of a shallow drinking water well in Ambikanagar (West Bengal, India) were analyzed for various physical and chemical parameters. The geochemical analyses included: (1) a 4-step sequential extraction scheme to determine the distribution of As between different fractions, (2) As speciation (As3+ vs. As5+), and (3) C, N and S isotopes. The sediments have a low percentage of organic C and N (0.10-0.56% and 0.01-0.05%, respectively). Arsenic concentration is between 2 and 7 mg kg−1, and it is mainly associated with the residual fraction, less susceptible to chemical weathering. The proportion of As3+ in these sediments is high and ranges from 24% to 74%. Arsenic in the second fraction (reducible) correlates well with Mn, and in the residual fraction As correlates well with several transition elements. The stable isotope results indicate microbial oxidation of organic matter involving SO4 reduction. Oxidation of primary sulfide minerals and release of As from reduction of Fe-(oxy)hydroxides do not seem important mechanisms in As mobilization. Instead, the dominance of As3+ and presence of As5+ reducing microorganisms in this shallow aquifer imply As remobilization involving microbial processes that needs further investigations.  相似文献   

10.
H. Leenaers 《GeoJournal》1989,19(1):37-43
The floodplain soils in the Guel basin have unacceptably high levels of pollution,v brought about by metal mining and related industrial activities in the past. Spoil heaps still exist along the Geul river and these are susceptible to erosion and leaching processes. An additional source of metals is formed by erosion of older, locally highly contaminated streambank deposits. These older sediments are polluted as a result of solid waste disposal containing metalliferous ore and tailings in the sand fraction. At present, these sediments function as a major source of heavy metals during high flow stages when streambanks are undermined and suspended sediments are deposited on the floodplains. The flood deposits have a relatively coarse texture, i.e. 70% dry weight in the fraction > 63 um.In order to obtain an indication about the potential mobility of the heavy metals in these deposits, 16 samples (8 samples < 63 um and 8 samples > 63 um) out of a set of 122 were subjected to a sequential extraction scheme as proposed by Calmano & Förstner (1983). It was found that up to 80% of the metals may be present in the first three leaching stages (exchangeable cations, carbonate fraction and easily reducible fraction) and that hardly any difference exists between the chemical partitioning of metals in the size fractions < 63 um and > 63 um. Moreover, as the total metal concentrations exponentially decrease along the 40 km distance away from the source area, the percentage of metals in these 3 potentially mobile fractions steadily increases. It is concluded that despite the rapid decay of total metal concentrations, Large amounts of potentially mobile metals are probably stored in the floodplain sediments even at a large distance from the source area.  相似文献   

11.
Factors that govern heavy metal concentration in sediments were examined by a combined analytical, geochemical, and geological approach. The constrains encountered in the determination of the anthropogenic influence are exposed. The region examined was the Krka River estuary located in the typical karst region of the eastern Adriatic, Yugoslavia.Sedimentological research revealed that: the Krka River (main water supplier) is almost free of suspended terrigenous material; the main supplier of suspended terrigenous matter of flysch origin is a small torrent-type Gudua Creek, and that this fine grained terrigenous material is sedimented mostly in the central enlarged part of the estuary, the Prokljan Lake.Three different groups of heavy metals were identified in recent sediments. Increased concentrations of nickel and zinc were found in estuarine sediments due to strongnatural enrichment in source rocks. Manganese and chromium were found to benaturally enriched and depleted in surface layer respectively, due to the different postdepositional geochemical behavior. Lead and copper concentrations were found to be increased in surface sediments in the central part of the estuary, apparently from anthropogenic source.  相似文献   

12.
Tourmaline-rich rocks are common in the lowgrade, interior portions of the Barberton greenstone belt of South Africa, where shallow-marine sediments and underlying altered basaltic and komatiitic lavas contain up to 50% tourmaline. The presence of tourmaline-bearing rip-up clasts, intraformational tourmalinite pebbles, and tourmaline-coated grains indicates that boron mineralization was a low-temperature, surficial process. The association of these lithologies with stromatolites, evaporites, and shallow-water sedimentary structures and the virtual absence of tourmaline in correlative deep-water facies rocks in the greenstone bels strengthens this model.Five tourmaline-bearing lithologic groups (basalts, komatiites, evaporite-bearing sediments, stromatolitic sediments, and quartz veins) are distinguished based on field, petrographic, and geochemical criteria. Individual tourmaline crystals within these lithologies show internal chemical and textural variations that reflect continued growth through intervals of change in bulk-rock and fluid composition accompanying one or more metasomatic events. Large single-crystal variations exist in Fe/Mg, Al/Fe, and alkali-site vacancies. A wide range in tourmaline composition exists in rocks altered from similar protoliths, but tourmalines in sediments and lavas have similar compositional variations. Boron-isotope analysis of the tourmalines suggest that the boron enrichment in these rocks has a major marine evaporitic component. Sediments with gypsum pseudomorphs and lavas altered at low temperatures by shallow-level brines have the highest 11B values (+2.2 to-1.9); lower 11B values of late quartz veins (-3.7 to-5.7) reflect intermediate temperature, hydrothermal remobilization of evaporitic boron. The 11B values of tourmaline-rich stromatolitic sediments (-9.8 and-10.5) are consistent with two-stage boron enrichment, in which earlier marine evaporitic boron was hydrothermally remobilized and vented in shallow-marine or subaerial sites, mineralizing algal stromatolites. The stromatolite-forming algae preferentially may have lived near the sites of hydrothermal discharge in Archean times.  相似文献   

13.
Dissolved and particulate fractions extracted from a lake diatom ooze were examined for individual amino acids. The study focused on combined amino acids, the predominant form in the interstitial dissolved pool (> 90%). An abundance of glycine and -alanine was observed in porewater samples of sediments both squeezed manually and gathered with in-situ dialysis (peeper). Sedimentpress squeezing and leaching of the sediment by water gave higher total quantities and different compositions (with more aliphatic and aromatic protein amino acids, -alanine being predominant). These two methods modify the original composition, presumably due to the formation of Fe-oxides and dissolution of sediment organic fractions, the alteration being aggravated if squeezing is delayed.Filtration after acidification of porewaters enabled us to distinguish two compartments: a protein-like agglutinated fraction, and a filtrate with a high glycine and -alanine content. Further division of the filtrate by adsorption on XAD or cation-exchange resins did not reveal additional fractions with different individual amino acid compositions. A link is suggested between the agglutinated fraction and the special composition of the porewaters extracted with sediment-press.Dissolved organic carbon (DOC) and total dissolved hydrolysable amino acids (TDHAA) ( 10 mg/l and 13 M, respectively) did not increase with depth, as opposed to dissolved inorganic carbon and volatile carbon. Amino acid-C accounted for less than 4% of DOC in porewaters.Individual amino acid compositions in the sediments were similar in all grain size fractions. Chemically extracted fractions had specific compositions: (l) organic fractions (alkali extracts and HF-insoluble residues) have a similar protein amino acid composition; (2) acid extracts have more acidic amino acids (HCI) or more glycine and non protein amino acids (BF). The similarity of amino acid compositions in the sediment HF-soluble fraction and the dissolved pool is discussed with respect to interactions between iron-silicate authigenic phases and porewaters.  相似文献   

14.
The geochemical partitioning of ten elements in stratified Holocene sediments from Loch Dee, southwest Scotland, has been established by use of a five-stage sequential extraction procedure. Samples from below 15 cm sediment depth show minimal evidence of modification by anthropogenic contamination or active diagenesis and hold Fe, Mg, Cu, Cd, Co, Pb, and Ni primarily in detrital silicates or organic complexes, while Mn, Ca, and Zn reside largely in adsorbed and reducible oxide phases. In the uppermost ca 15 cm of sediment, enhanced total concentrations of Zn, Cu, and Pb reflect increased atmospheric deposition during the postindustrial period. Of these metals, only Pb displays any notable adjustment of partitioning in the enriched zone, showing disproportionate accumulation in labile oxides and organic-Pb phases. The lack of Pb and Zn carbonates in the contaminated horizon may reflect inherent thermodynamic instability under the acid surface and pore-water conditions of Loch Dee. Increments to total Mn and Co in the surficial ca 5 cm of sediment are attributable to the accumulation of secondary oxides and adsorbed species, consistent with precipitation from the interstitial pore-waters across a sedimentary redox front. The presence of metals such as Zn and Cd in soluble or acid-volatile phases in the interfacial sediment has implications for the future management of the Loch Dee basin, with leaching into the overlying waters likely, given the continuation of current trends of lake acidification.  相似文献   

15.
To evaluate the magnitude of variation in grain size distribution in the Krishna river, bed sediments and suspended sediments collected along the length of the river have been studied. There are both temporal and seasonal variation in the grain size distribution of suspended sediments. The statistical parameters show the change along the river in a non-linear fashion which may be due to human interference and due to different types of sediments contributed by tributaries to the Krishna river. The suspended sediments are mostly fine silt (4 to 16m), poorly sorted, showing coarse to fine skewed and are platyto leptokurtic. The bed sediments are mostly medium sand (350m) showing moderate to well sorted, coarse to fine skewed and are platy- to leptokurtic. The CM diagram of Krishna river bed sediments suggests that deposition takes place by (1) rolling (2) rolling and suspension and (3) graded suspension. The suspended sediments represent deposits of uniform suspension.  相似文献   

16.
Speciation of Cr in geochemical reference materials was characterised by sequential extraction and X‐ray absorption near‐edge structure (XANES) spectroscopy to identify Cr(III) resulting from the reduction of pollutant Cr(VI). Sequential extraction suggested that the amount of Cr associated with an acetic acid soluble fraction was low; Cr associated with a reducible phase and an oxidisable phase was extracted at 5–10% of the total Cr concentration, and the residual phase was found to be the dominant Cr‐containing fraction. Cr speciation in soil artificially doped with Cr(VI) and sediment samples collected from highly populated and industrialised areas was different from that in naturally occurring materials. Substantial Cr was extracted as a reducible phase (15–30%) and an oxidisable phase (30–60%) for these samples. Through subsequent XANES spectroscopy analysis, the reducible phase was explained by Cr bound to Fe hydroxide, while the oxidisable phase was a mixture of Cr bound to humic substances and Cr hydroxides. That is, Cr(VI) present as a contaminant in sediments and soils was reduced to Cr(III), which then bound to Fe hydroxide and humic substances, precipitating as a hydroxide. Thus, a combination of sequential extraction and XANES spectroscopy allows for effective identification and quantification of the chemical forms of Cr in sediments and soils.  相似文献   

17.
Sulphur isotope compositions and S/C ratios of organic matter were analysed in detail by combustion-isotope ratio monitoring mass spectrometry (C-irmMS) in eastern Mediterranean sediments containing three sapropels of different ages and with different organic carbon contents (sapropel S1 in core UM26, formed from 5–9 ka ago with a maximum organic carbon content of 2.3 wt%; sapropel 967 from ODP Site 160-967C, with an age of 1.8 Ma and a maximum organic carbon content of 7.4 wt%; and sapropel 969 from ODP Site 160-969E, with an age of 2.9 Ma and a maximum organic carbon content of 23.5 wt%). Sulphur isotopic compositions (34S) of the organic matter ranged from -29.5 to +15.8 and the atomic S/C ratio was 0.005 to 0.038. The organic sulphur in the sediments is a mixture of sulphur derived from (1) incorporation of 34S-depleted inorganic reduced sulphur produced by dissimilatory microbial sulphate reduction; and (2) biosynthetic sulphur with an isotopic signature close to seawater sulphate. The calculated biosynthetic fraction of organic sulphur in non-sapropelic sediments ranges from 68–87%. The biosynthetic fraction of the organic sulphur of the sapropels (60–22%) decreases with increasing organic carbon content of the sapropels. We propose that uptake of reduced sulphur into organic matter predominantly took place within sapropels where pyrite formation was iron-limited and thus an excess of dissolved sulphide was present for certain periods of time. Simultaneously, sulphide escaped into the bottom water and into sediments below the sapropels where pyrite formation occurred.  相似文献   

18.
《Applied Geochemistry》2003,18(2):269-282
Urban sediments are part of a complex system in which particulates accumulate potentially toxic pollutants, ultimately posing a threat to urban water-bodies and public health. It is therefore important to recognise sources, signatures and pathways of urban particulates. Urban sediment samples were analysed from both inner and outer city road surfaces of Manchester, UK. High metal concentrations, coupled with the largely ferrimagnetic multi-domain (MD) mineral magnetic composition of the particulates, indicate inputs of anthropogenic origin, primarily particulates derived from automobiles, as being the dominant source to the urban sediment system. Iron and Pb concentrations show a clear spatial trend, whereby concentrations are enhanced in the inner city samples. Lead concentrations for inner and outer city samples average 354 and 185 μg g−1, respectively. Iron concentrations for inner and outer city samples average 11302 and 6486 μg g−1, respectively. Sequential extraction analysis shows the metals Mn, Fe, Zn and Pb are largely associated with the reducible fraction, whereas Cu is largely associated with the oxidisable fraction. Zinc is the only metal showing significant association with the exchangeable fraction (up to 33%), suggesting that it may be the most susceptible metal to mobilisation during runoff. Metal fractions identified as showing larger associations with the reducible and oxidisable fractions will continue to be vulnerable to mobilisation as a result of changes in ambient pH and/or redox conditions. Mineral magnetic concentration parameters, such as the saturation isothermal remanent magnetisation (SIRM), together with hysteresis parameters such as the coercive force and interparametric ratios (such as (Bo)cr/Hc and IRM-100mT/SIRM) show that ferrimagnetic MD minerals dominate the Manchester urban sediments. Average results for frequency-dependent susceptibility as a percentage (2%) suggest that the composition of these Manchester sediments is not dominated by soil-derived material, and therefore magnetically coarser, anthropogenically-derived material is dominant. Unlike Pb and Fe concentrations, mineral magnetic characteristics of the Manchester urban sediment samples exhibit no significant spatial variation.  相似文献   

19.
金昌市铜镍矿区周围土壤中重金属的迁移特征   总被引：4，自引：1，他引：3  
对金昌矿区不同区域土壤5~20 cm层中重金属各化学形态及活性态的迁移行为进行了研究,结果表明：土壤中重金属不同化学形态迁移率不同,弱酸提取态、可还原态、可氧化态和残渣态平均迁移率分别为0.13、0.51、0.30和0.54。重金属总量和活性态（包括弱酸提取态、可还原态、可氧化态）迁移率也表现出很大差异,尾矿区土壤Cr总量迁移率较高为0.65,而其活性态迁移率较低为0.26,Ni与Cr迁移特征完全相反,总量迁移率为0.26,而活性态迁移率为0.67;农田土壤中Pb总量迁移率低而活性态迁移率高,Ni与Zn特征相似,总量迁移率高而活性态迁移率相对较低;大棚地土壤中重金属迁移率均较低,Cu和Ni活性态几乎未发生向下迁移。可见,重金属的迁移与其化学形态分布关系密切,与重金属总量的迁移率相比,活性态迁移率能够更有效地反映出土壤中重金属的迁移特征和潜在危害性。  相似文献   

20.
In order to understand the fractionation of Re and Os in marine environments, their removal from artificial seawater to Tokyo Bay sediments is studied using a multitracer technique. The chemical processes of the removal of Re and Os are also estimated based on their speciation analyses by X-ray absorption fine structure (XAFS) spectroscopy. The partitioning experiments, which use the multitracer technique, provide information on Re and Os regarding (i) their distributions between artificial seawater-sediment systems, (ii) their complexation with humic acid, and (iii) their carriers in sediments. In addition, XAFS spectroscopy provides direct information on the chemical states of Re and Os in the sediments.In an artificial seawater-sediment system containing a multitracer, Re is removed from the artificial seawater only under a reducing environment. The speciation of Re by X-ray absorption near-edge structure (XANES) suggests that the majority of Re remains as in the artificial seawater even under highly reducing conditions, during laboratory time scale (about 2 weeks). Moreover, XANES simulation shows that some Re exists at a lower oxidation state, such as ReO2, in the reducing sediment. These results can be explained by the slow kinetics of the reaction which is similar to those suggested by previous geochemical studies.In contrast, Os is readily removed from the artificial seawater into sediments under various redox conditions. Even under oxic conditions, a large fraction of Os is removed from the artificial seawater to sediments without organic matter. Based on the Os XANES study, it is confirmed that the oxidation states of Os incorporated in the reducing sediment and oxic sediment are trivalent and tetravalent, respectively. Sequential extraction suggests that the main carrier of Os in the organic-rich sediment is either ferromanganese oxides or organic matter, and that the Os in these two fractions may correspond to hydrolyzed insoluble Os species and Os species interacting with organic matter, at lower valence, respectively. The results of distribution study of Os in the absence and presence of humic acid (HA) also imply that Os assumes more than one chemical species, and a small fraction of Os may interact with HA in the experimental system. Meanwhile, extended X-ray absorption fine structure (EXAFS) confirms that the first neighboring atom of Os in the reducing sediment is oxygen. If Os(VIII) is the main dissolved species in seawater, as is expected thermodynamically, reductive removal may control the enrichment of Os in the sediment. Osmium, which is removed as Os(IV), is reduced further to Os(III) by a diagenetic process and may be complexed with organic matter in the reducing sediment.The results of the removal behaviors of Re and Os obtained in the current study show that Re can be removed from the artificial seawater only under highly reducing conditions within 2 weeks, but Os removal from the artificial seawater can be found under various redox conditions. Thus, a high 187Re/188Os ratio can occur only in reducing sediments, such as black shales. The high187Re/188Os ratio, in turn, makes black shales suitable for Re-Os dating. In contrast, authigenic sediments (and minerals) under oxic environments can enrich Os, but since Re is not distributed to the sediments under oxic conditions, this will cause a much lower 187Re/188Os ratio than that of seawater. The Os isotope system of these materials can be used as a paleo-marine environmental tracer since the 187Os/188Os ratio cannot grow significantly due to its extremely low 187Re/188Os ratio.  相似文献   

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