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1.
ABSTRACT

Mesoproterozoic red beds near ancient coasts have not aroused extensive interest. A new geochemical study of the alternating red and grey dolostones from the Yangzhuang Formation provides a better understanding of the redox conditions of nearshore sedimentary environments. In this contribution, whole-rock samples are characterized by positive correlations of rare earth elements (REE) vs. Th and FeT vs. Th and flat-type REE distribution patterns, indicating massive terrigenous input, which is considered to be inherited from felsic rocks. Relatively high (Femag+Feox)/FeT and Fe3+/Fe2+ ratios in red beds indicate more oxidized conditions in supratidal environments compared with the lower oxygen contents in intertidal environments. Under these two distinct chemical sedimentary conditions, acetic acid-leached red and grey samples both have HREE-depleted distributions, suggesting significant freshwater invasion. Moreover, limited terrigenous redox-sensitive elements (RSEs) can reach the coast where the red beds are deposited, whereas relatively high RSE enrichment factors originating from shallow oceans are recorded in grey beds. In the Mesoproterozoic, limited oxidative weathering, shallow seawater desalination, and low organic production occurred near the coast. Meanwhile, a prolonged period of low Mo and U availability preserved in carbonate minerals confirmed that marine oxygen levels failed to satisfy the deposition of offshore red beds. During the regression, potentially exposed sediments connected to atmospheric oxygen guaranteed the oxidation of iron and the formation of red beds, and these events were coupled with negative δ13Ccarb shifts in the Yanliao rift zone.  相似文献   

2.
《Gondwana Research》2011,19(4):632-637
In South China, the Datangpo black shales (663 Ma–654.5 Ma) were deposited during the Cryognian interglacial time between the Sturtian and Marinoan glaciations. Multi-geochemical proxies, including different iron speciation and relevant ratios (FeHR/FeT, FeP/FeHR and FeT/Al ratios) and molybdenum concentrations, were used to reconstruct the paleo-depositional environment of this black shale horizon. The ratios of different iron species (FeHR/FeT > 0.38 and FeP/FeHR < 0.80) suggest an overall anoxic conditions (ferruginous) over the deposition of the black shales, although intermittent euxinic (FeHR/FeT > 0.38 and FeP/FeHR ≈ 0.80) and oxic (FeHR/FeT < 0.38) intervals could have occurred. Furthermore, FeT/Al ratios (FeT/Al ≤ 0.51) confirm that water column may not be persistent euxinia during the deposition of the Datangpo black shales. Meanwhile, molybdenum concentrations show a decreasing trend towards the top of the black shales, reconciling the gradual oxygenating trend during this period as stated above. Compared to δ34SPy values in the Mesoproterozoic deep ocean, more positive δ34SPy values of this study may result from a small size of sulfate reservoir. The small-size sulfate reservoir and concurrent enrichment of molybdenum indicate that the ocean chemistry in the Cryogenian Period is similar to that in the Archean Eon.  相似文献   

3.
In South China, the Datangpo black shales (663 Ma–654.5 Ma) were deposited during the Cryognian interglacial time between the Sturtian and Marinoan glaciations. Multi-geochemical proxies, including different iron speciation and relevant ratios (FeHR/FeT, FeP/FeHR and FeT/Al ratios) and molybdenum concentrations, were used to reconstruct the paleo-depositional environment of this black shale horizon. The ratios of different iron species (FeHR/FeT > 0.38 and FeP/FeHR < 0.80) suggest an overall anoxic conditions (ferruginous) over the deposition of the black shales, although intermittent euxinic (FeHR/FeT > 0.38 and FeP/FeHR ≈ 0.80) and oxic (FeHR/FeT < 0.38) intervals could have occurred. Furthermore, FeT/Al ratios (FeT/Al ≤ 0.51) confirm that water column may not be persistent euxinia during the deposition of the Datangpo black shales. Meanwhile, molybdenum concentrations show a decreasing trend towards the top of the black shales, reconciling the gradual oxygenating trend during this period as stated above. Compared to δ34SPy values in the Mesoproterozoic deep ocean, more positive δ34SPy values of this study may result from a small size of sulfate reservoir. The small-size sulfate reservoir and concurrent enrichment of molybdenum indicate that the ocean chemistry in the Cryogenian Period is similar to that in the Archean Eon.  相似文献   

4.
Isotopic compositions of organic (δ13C-Corg) and carbonate (δ13C-Ccarb) carbon were analyzed in the particulate matter (hereafter, particulates) and sediments from the North and Middle Caspian basins. Isotopic composition of Corg was used for assessing proportions of the allochthonous and autochthonous organic matter in the particulates. Difference between the δ13C-Corg values in surface sediments and particulates is explained by the aerobic and anaerobic diagenetic transformations. Isotopic composition of Corg in sediments may be used as a tool for reconstructing the Quaternary transgressive-regressive history of the Caspian Sea.  相似文献   

5.
Enrichments in reactive iron occur under euxinic marine conditions, that is, where dissolved sulfide is present in the water column. These enrichments result primarily from the export of remobilized iron from the oxic shelf, which is scavenged from the euxinic water column during syngenetic pyrite formation and deposited in the underlying sediments. Strongly elevated ratios of highly reactive iron to total iron (FeHR/FeT) and total iron to aluminum (FeT/Al) and high degrees of pyritization (DOP) are each products of this enrichment process. These paleoredox proxies are among the most faithful recorders of ancient euxinia.Contrary to previous arguments, iron enrichment is decoupled from biogenic sediment inputs, but it does appear to be a uniquely euxinic phenomenon. In other words, we can rule out a major contribution from preferential physical transport of FeHR-rich detrital sediment to the deep basin, which could also operate under oxic conditions. Furthermore, enrichment via the shuttling of iron remobilized from oxic shelves appears to be limited by inefficient transport and trapping processes in deep oxic basins. Elevated FeT/Al ratios in the euxinic sediments also cannot be a product of internal enhancement of the reactivity of the detrital iron pool without net FeHR addition. These conclusions are supported by observations in the modern Black Sea, Orca Basin, and Effingham Inlet.FeT/Al ratios are unambiguous recorders of paleoredox even in sediments that have experienced high degrees of metamorphic alteration. However, this study suggests that high siliciclastic accumulation rates can swamp the enrichment mechanism, resulting in only intermediate DOP values for euxinic sediments and FeT/Al ratios that mimic the oxic shelf. Such dilution effects are well expressed in Black Sea basinal turbidites and rapidly accumulating muds on euxinic basin margins. Under conditions of persistent euxinia, varying extents of FeHR enrichment can illuminate spatial and temporal gradients in siliciclastic sedimentation. The magnitude of enrichment is a function of the source (shelf) to sink (ocean basin) areal ratio, suggesting that iron proxies can also record ocean-scale paleoenvironmental properties through muted enrichments at times of very widespread euxinia. For the first time, manganese data are interpreted in light of the redox shuttle model. As for the iron data, the Black Sea, Orca Basin, and Effingham Inlet show enrichments in total manganese in the deep euxinic basin, suggesting export from the suboxic porewaters of the oxic shelf and scavenging and burial in the basin. The Black Sea data reveal iron and manganese enrichment across the broad, deep euxinic basin, suggesting efficient lateral transport and deep-water mixing tied to the physical properties of the water column.  相似文献   

6.
In order to better understand the paleoceanographic sedimentary environment of the Lower Cambrian black shales extensively distributed in South China, outcropped along the present southern margin of the Yangtze Platform with a width of ca. 200-400 km and a length of more than 1500 km, we present new paired δ13C data on carbonates (δ13Ccarb) and associated organic carbon (δ13Corg) and δ34Spy data on sedimentary pyrite in black shales from three sections (Ganziping, Shancha and Xiaohekou) located in NW Hunan, China. In these sections, a total of 82 Lower Cambrian black shale samples have δ13Ccarb values ranging from -4.0‰ to 1.7‰ with an average value of -2.1‰, and δ13Corg values between -34.9‰ and -28.8‰, averaging -31.9‰. The ?34Spy values of 16 separated sedi-mentary pyrite samples from the black shales vary between +10.2‰ and +28.7‰ with an average value of +19.5‰, presenting a small isotope fractionation between seawater sulfate and sedimentary sulfide. The model calculation based on credible data from the paired analyses for δ13Ccarb and δ13Corg of 11 black shale samples shows a high CO2 concentration in the Early Cambrian atmosphere, about 20 times higher than pre-industrial revolution values, consis-tent with previous global predictions. The small sulfur isotope fractionation between seawater sulfate and sedimen-tary sulfide in black shales, only 15.5‰ on average, implies a low sulfate level in the Early Cambrian seawater around 1 mmol. In combination with a high degree of pyritization (DOP) in the black shales, it is suggested that sul-fidic deep-ocean water could have lingered up to the earliest Cambrian in this area. The black shale deposition is envisaged in a stratified marine basin, with a surface euphotic and oxygenated water layer and sulfidic deeper water, controlled by a continental margin rift.  相似文献   

7.
We have investigated the effect of Fe on the stabilities of carbonate (carb) in lherzolite assemblages by determining the partitioning of Fe and Mg between silicate (olivine; ol) and carbonates (magnesite, dolomite, magnesian calcite) at high pressures and temperatures. Fe enters olivine preferentially relative to magnesite and ordered dolomite, but Fe and Mg partition almost equally between disordered calcic carbonate and olivine. Measurement of K d (X Fe carb X Mg ol /X Fe ol X Mg carb ) as a function of Fe/ Mg ratio indicates that Fe–Mg carbonates deviate only slightly from ideality. Using the regular solution parameter for olivine W FeMg ol of 3.7±0.8 kJ/mol (Wiser and Wood 1991) we obtain for (FeMg)CO3 a W FeMg carb of 3.05±1.50 kJ/mol. The effect of Ca–Mg–Fe disordering is to raise K d substantially enabling us to calculate W CaMg carb -W CaFe carb of 5.3±2.2 kJ/mol. The activity-composition relationships and partitioning data have been used to calculate the effect of Fe/Mg ratio on mantle decarbonation and exchange reactions. We find that carbonate (dolomite and magnesian calcite) is stable to slightly lower pressures (by 1 kbar) in mantle lherzolitic assemblages than in the CaO–MgO–SiO2(CMS)–CO2 system. The high pressure breakdown of dolomite + orthopyroxene to magnesite + clinopyroxene is displaced to higher pressures (by 2 kbar) in natural compositions relative to CMS. CO2. We also find a stability field of magnesian calcite in lherzolite at 15–25 kbar and 750–1000°C.  相似文献   

8.
Oxygenation of the Earth's atmosphere occurred in two major steps, near the beginning and near the end of the Proterozoic Eon (2500 to 542 Ma ago), but the details of this history are unclear. Chromium isotopes in iron-rich chemical sediments offer a potential to highlight fine-scale fluctuations in the oxygenation of the oceans and atmosphere and to add a further dimension in the use of redox-sensitive tracers to solve the question regarding fluctuations of atmospheric oxygen levels and their consequences for Earth's climate. We observe strong positive fractionations in Cr isotopes (δ53Cr up to + 5.0‰) in iron-rich cherts and banded iron formation horizons within the Arroyo del Soldado Group (Ediacaran; Uruguay) that can be explained by rapid, effective oxidation of Fe(II)-rich surface waters. These fluctuations are correlated with variations in ratios of highly reactive iron (FeHR) to total iron (Fetot) which indicate a predominance of anoxic water columns (FeHR/Fetot > 0.38) during the onset of oxidation pulses. We favor the scenario by which isotopically heavy Cr(VI) entered the basin after pulses of oxidative weathering on land and in which Fe(II) accumulated in the water column. Neodymium isotopes reveal that these oxygenation pulses were followed by increased influxes to the basin of continental crust-derived detrital components of Paleoproterozoic (Nd TDM model ages = 2.1–2.2 Ga) provenance typical of the Rio de la Plata Craton. The association of positive δ53Cr–ferruginous (FeHR/Fetot > 0.38) stratigraphic intervals with low-diversity acritarch assemblages dominated by Bavlinella faveolata strongly support models postulating a stratified, eutrophic Neoproterozoic ocean. Thus, even within a few million years of the Precambrian–Cambrian boundary, paleoceanographic conditions resembled more those of Paleoproterozoic oceans than Phanerozoic and present oceans. This highlights the sheer magnitude of ecological changes at the Precambrian–Cambrian transition, changes which ultimately led to the demise of the Precambrian world and the birth of the metazoan-dominated Phanerozoic.  相似文献   

9.
《Applied Geochemistry》2004,19(11):1837-1853
Iron monosulfide formation and oxidation processes were studied in the extensively drained acid sulfate soil environment of the Tweed River floodplain in eastern Australia. Porewater profiles of pH, Eh, SO42−, Fe2+, Fe3+, Cl−, HCO3−, and metals (Cd, Co, Cr, Cu, Ni, Pb and Zn) were obtained using in situ dialysis membrane samplers (`peepers'). Concentrations of acid volatile S (AVS), pyrite, total S, reactive Fe, total and organic C, simultaneously extracted metals (SEMs) and total elemental composition by X-ray fluorescence, were determined on sediment samples. The oxidation of pyrite in the surrounding landscape provides a source of acidity, Fe, Al, SO4 and metals, which are exported into the drainage system where they accumulate in the sediments and porewaters. Negative porewater concentration gradients of SO42− and Fe2+, and large AVS concentrations in the sediments, indicate Fe monosulfides form rapidly under reducing conditions and consume acidity and metals. Oxidation of the sediments during previous drought episodes has resulted in the conversion of monosulfides and pyrite to oxidised Fe minerals and the release of acidity, SO42−, Fe3+, and metals to the surface waters. These formation and oxidation cycles show that Fe monosulfides play an important role in controlling water quality in the drainage system.  相似文献   

10.
In order to understand spatial variations of stable isotope geochemistry in the Quruqtagh basin (northwestern China) in the aftermath of an Ediacaran glaciation, we analyzed carbonate carbon isotopes (δ13Ccarb), carbonate oxygen isotopes (δ18Ocarb), carbonate associated sulfate sulfur (δ34SCAS) and oxygen isotopes (δ18OCAS), and pyrite sulfur isotopes (δ34Spy) of a cap dolostone atop the Ediacaran Hankalchough glacial diamictite at four sections. The four studied sections (YKG, MK, H and ZBS) represent an onshore-offshore transect in the Quruqtagh basin. Our data show a strong paleobathymetry-dependent isotopic gradient. From the onshore to offshore sections, δ13Ccarb values decrease from −2‰ to −16‰ (VPDB), whereas δ18Ocarb values increase from −4‰ to −1‰ (VPDB). Both δ34SCAS and δ34Spy show stratigraphic variations in the two onshore sections (MK and YKG), but are more stable in the two offshore sections (H and ZBS). δ18OCAS values of onshore samples are consistent with terrestrial oxidative weathering of pyrite. We propose that following the Hankalchough glaciation seawater in the Quruqtagh basin was characterized by a strong isotopic gradient. The isotopic data may be interpreted using a three-component mixing model that involves three reservoirs: deep-basin water, surface water, and terrestrial weathering input. In this model, the negative δ13Ccarb values in the offshore sections are related to the upwelling of deep-basin water (where anaerobic oxidation of dissolved organic carbon resulted in 13C-depleted DIC), whereas sulfur isotope variations are strongly controlled by surface water sulfate and terrestrial weathering input derived from oxidative weathering of pyrite. The new data provide evidence for the oceanic oxidation following the Hankalchough glaciation.  相似文献   

11.
首次报道了扬子板块北缘镇巴地区中-晚三叠世界线黏土岩锂的超常富集,黏土岩产于关岭组(T2g)/须家河组(T3x)平行不整合界面,为古风化壳沉积物,Li2O品位0.08%～0.11%,最高达0.22%,超过了该类型矿产的边界品位(0.06%),界线黏土岩的岩石学特征、矿物组成及岩石成因亟待查明。本文通过XRD分析、TIMA分析以及详细的地球化学研究,查明了界线黏土岩的矿物组成,探讨了黏土岩形成的沉积环境及物质来源,提出了不整合面黏土岩类关键金属矿产的综合找矿方向。研究表明,镇巴地区T2/T3界线黏土岩主要由石英、伊利石、高岭石组成,并含有极少量绿泥石、蒙脱石和铝绿泥石。主量元素(SiO2、Al2O3、TFe2O3、TiO2)特征表明界线黏土岩属于铝土质泥岩,黏土岩CIA值(化学蚀变指数)为85～93,ICV值(成分变异指数)为0...  相似文献   

12.
Stream water from a stream network of 15 small boreal catchments (0.03-67 km2) in northern Sweden was analyzed for unfiltered (total) and filtered (<0.4 μm) concentrations of iron (Fetot and Fe<0.4) and manganese (Mntot and Mn<0.4). The purpose was to investigate the temporal and spatial dynamics of Fe, Mn and dissolved organic carbon (DOC) as influenced by snow melt driven spring floods and landscape properties, in particular the proportion of wetland area. During spring flood, concentrations of Fetot, Fe<0.4, Mntot, Mn<0.4 and DOC increased in streams with forested catchments (<2% wetland area). In catchments with high coverage of wetlands (>30% wetland area) the opposite behavior was observed. The hydrogeochemistry of Fe was highly dependent on wetlands as shown by the strong positive correlation of the Fetot/Altot ratio with wetland coverage (r2 = 0.89, p < 0.001). Furthermore, PCA analysis showed that at base flow Fetot and Fe<0.4 were positively associated with wetlands and DOC, whereas they were not associated during peak flow at spring flood. The temporal variation of Fe was likely related to varying hydrological pathways. At peak discharge Fetot was associated with variables like silt coverage, which highlights the importance of particulates during high discharge events. For Mn there was no significant correlation with wetlands, instead, PCA analysis showed that during spring flood Mn was apparently more dependent on the supply of minerogenic particulates from silt deposits on the stream banks of some of the streams. The influence of minerogenic particulates on the concentration of, in particular, Mn was greatest in the larger, lower gradient streams, characterized by silt deposits in the near-stream zone. In the small forested streams underlain by till, DOC was of greater importance for the observed concentrations, as indicated by the positive correlation of both Fetot and Fe<0.4 with DOC (r2 = 0.77 and r2 = 0.76, p < 0.001) at the smallest headwater forest site. In conclusion, wetland area and DOC were important for Fe concentrations in this boreal stream network, whereas silt deposits strongly influenced Mn concentrations. This study highlights the importance of studying stream water chemistry from a landscape perspective in order to address future environmental issues concerning mobility of Fe, Mn and associated trace metals.  相似文献   

13.
《Chemical Geology》2004,203(1-2):153-168
The importance of the magnetic iron sulfide minerals, greigite (Fe3S4) and pyrrhotite (Fe7S8), is often underappreciated in geochemical studies because they are metastable with respect to pyrite (FeS2). Based on magnetic properties and X-ray diffraction analysis, previous studies have reported widespread occurrences of these magnetic minerals along with magnetite (Fe3O4) in two thick Plio-Pleistocene marine sedimentary sequences from southwestern Taiwan. Different stratigraphic zones were classified according to the dominant magnetic mineral assemblages (greigite-, pyrrhotite-, and magnetite-dominated zones). Greigite and pyrrhotite are intimately associated with fine-grained sediments, whereas magnetite is more abundant in coarse-grained sediments. We measured total organic carbon (TOC), total sulfur (TS), total iron (FeT), 1N HCl extractable iron (FeA), and bulk sediment grain size for different stratigraphic zones in order to understand the factors governing the formation and preservation of the two magnetic iron sulfide minerals. The studied sediments have low TS/FeA weight ratios (0.03–0.2), far below that of pyrite (1.15), which indicates that an excess of reactive iron was available for pyritization. Observed low TS (0.05–0.27%) is attributed to the low organic carbon contents (TOC=0.25–0.55%), which resulted from dilution by rapid terrigenous sedimentation. The fine-grained sediments also have the highest FeT and FeA values. We suggest that under conditions of low organic carbon provision, the high iron activity in the fine-grained sediments may have removed reduced sulfur so effectively that pyritization was arrested or retarded, which, in turn, favored preservation of the intermediate magnetic iron sulfides. The relative abundances of reactive iron and labile organic carbon appear to have controlled the transformation pathway of amorphous FeS into greigite or into pyrrhotite. Compared to pyrrhotite-dominated sediments, greigite-dominated sediments are finer-grained and have higher FeA but lower TS. We suggest that diagenetic environments with higher supply of reactive iron, lower supply of labile organic matter, and, consequently, lower sulfide concentration result in relatively high Eh conditions, which favor formation of greigite relative to pyrrhotite.  相似文献   

14.
Analytical methods used for determining dissolved Fe(II) often yield inaccurate results in the presence of high Fe(III) concentrations. Accurate analysis of Fe(II) in solution when it is less than 1% of the total dissolved Fe concentration (FeT) is sometimes required in both geochemical and environmental studies. For example, such analysis is imperative for obtaining the ratio Fe(II)/Fe(III) in rocks, soils and sediments, for determining the kinetic constants of Fe(II) oxidation in chemical or biochemical systems operating at low pH, and is also important in environmental engineering projects, e.g. for proper control of the regeneration step (oxidation of Fe(II) into Fe(III)) applied in ferric-based gas desulphurization processes. In this work a method capable of yielding accurate Fe(II) concentrations at Fe(II) to FeT ratios as low as 0.05% is presented. The method is based on a pretreatment procedure designed to separate Fe(II) species from Fe(III) species in solution without changing the original Fe(II) concentration. Once separated, a modified phenanthroline method is used to determine the Fe(II) concentration, in the virtual absence of Fe(III) species. The pretreatment procedure consists of pH elevation to pH 4.2–4.65 using NaHCO3 under N2(g) environment, followed by filtration of the solid ferric oxides formed, and subsequent acidification of the Fe(II)-containing filtrate. Accuracy of Fe(II) analyses obtained for samples (Fe(II)/FeT ratios between 2% and 0.05%) to which the described pretreatment was applied was >95%. Elevating pH to above 4.65 during pretreatment was shown to result in a higher error in Fe(II) determination, likely resulting from adsorption of Fe(II) species and their removal from solution with the ferric oxide precipitate.  相似文献   

15.
Two Holocene sediment cores were retrieved respectively from the enclosed Lake Daihai in the monsoon/arid transition zone of North China and the Taihu Lake coast in the monsoonal area of the Yangtze delta, Eastern China. Distribution of major geochemical elements and their ratios were employed to reveal the characteristics of Holocene climate and associated environmental implications in the two regions. It is suggested that the temporal distribution of major elements serve as a useful indicator to denote the variations of monsoon effective precipitation for the enclosed lake area. High values of resistant elements such as Al2O3, SiO2, TiO2, (FeO + Fe2O3), MnO in the lake sediments correspond to the depressed chemical weathering and weakened mon-soon effective precipitation, while the highs of mobile and easy soluble elements such as MgO, CaO, Na2O reflect the enhanced chemical weathering and increased monsoon effective precipitation in the lake basin. In comparison, the behaviors of the major elements in sediments of the Taihu Lake coast were largely controlled by the changes both in sea transgression in the different Holocene time periods and the monsoon precipitation. The relatively highs of Al2O3, TiO2, (FeO + Fe2O3), in marine-influenced sediments suggest relatively strong coastal hydrodynamics and chemical weathering, and vice versa. Meanwhile, the lows of SiO2, Na2O and CaO in the non-marine-influenced sediments also denote relatively strong hydrodynamics and chemical weathering due to enhanced monsoon precipitation, and vice versa. Sedimentary environment should be taken into account when achieving a full understanding of their climate implications.  相似文献   

16.
The paper presents the results of study of ferromanganese carbonate rocks in the Sob area (Polar Urals), which is located between the Rai-Iz massif and the Seida–Labytnangi Railway branch. These rocks represent low-metamorphosed sedimentary rocks confined to the Devonian carbonaceous siliceous and clayey–siliceous shales. In terms of ratio of the major minerals, ferromanganese rocks can be divided into three varieties composed of the following minerals: (1) siderite, rhodochrosite, chamosite, quartz, ± kutnahorite, ± calcite, ± magnetite, ± pyrite, ± clinochlore, ± stilpnomelane; (2) spessartite, rhodochrosite, and quartz, ± hematite, ± chamosite; (3) rhodochrosite, spessartite, pyroxmanite, quartz ± tephroite, ± fridelite, ± clinochlore, ± pyrophanite, ± pyrite. In all varieties, the major concentrators of Mn and Fe are carbonates (rhodochrosite, siderite, kutnahorite, Mn-calcite) and chlorite group minerals (clinochlore, chamosite). The chemical composition of rocks is dominated by Si, Fe, Mn, carbon dioxide, and water (L.O.I.): total SiO2 + Fe2O 3 tot + MnO + L.O.I. = 85.6?98.4 wt %. The content of Fe and Mn varies from 9.3 to 55.6 wt % (Fe2O 3 tot + MnO). The Mn/Fe ratio varies from 0.2 to 55.3. In terms of the aluminum module AlM = Al/(Al + Mn + Fe), the major portion of studied samples corresponds to metalliferous sediments. The δ13Ccarb range (–30.4 to–11.9‰ PDB) corresponds to authigenic carbonates formed with carbon dioxide released during the microbial oxidation of organic matter in sediments at the dia- and/or catagenetic stage. Ferromanganese sediments were likely deposited in relatively closed seafloor zones (basin-traps) characterized by periodic stagnation. Fe and Mn could be delivered from various sources: input by diverse hydrothermal solutions, silt waters in the course of diagenesis, river discharges, and others. The diagenetic delivery of metals seems to be most plausible. Mn was concentrated during the stagnation of bottom water in basin-traps. Interruption of stagnation promoted the precipitation of Mn. The presence of organic matter fostered a reductive pattern of postsedimentary transformations of metalliferous sediments. Fe and Mn were accumulated initially in the oxide form. During the diagenesis, manganese and iron oxides reacted with organic matter to make up carbonates. Relative to manganese carbonates, iron carbonates were formed under more reductive settings and higher concentrations of carbon dioxide in the interstitial solution. Crystallization of manganese and iron silicates began already at early stages of lithogenesis and ended during the regional metamorphism of metalliferous sediments.  相似文献   

17.
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 Fe2O3T 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.  相似文献   

18.
Eclogites from the Kebuerte Valley, Chinese South Tianshan, consist of garnet, omphacite, phengite, paragonite, glaucophane, hornblendic amphibole, epidote, quartz and accessory rutile, titanite, apatite and carbonate minerals with occasional presence of coesite or quartz pseudomorphs after coesite. The eclogites are grouped into two: type I contains porphyroblastic garnet, epidote, paragonite and glaucophane in a matrix dominated by omphacite where the proportion of omphacite and garnet is >50 vol.%; and type II contains porphyroblastic epidote in a matrix consisting mainly of fine‐grained garnet, omphacite and glaucophane where the proportion of omphacite and garnet is <50 vol.%. Garnet in both types of eclogites mostly exhibits core–rim zoning with increasing grossular (Xgr) and pyrope (Xpy) contents, but a few porphyroblastic garnet grains in type I eclogite shows core–mantle zoning with increasing Xpy and a slight decrease in Xgr, and mantle–rim zoning with increases in both Xgr and Xpy. Garnet rims in type I eclogite have higher Xpy than in type II. Petrographic observations and phase equilibria modelling with pseudosections calculated using thermocalc in the NCKMnFMASHO system for three representative samples suggest that the eclogites have experienced four stages of metamorphism: stage I is the pre‐peak temperature prograde heating to the pressure peak (Pmax) which was recognized by the garnet core–mantle zoning with increasing Xpy and decreasing Xgr. The P–T conditions at Pmax constrained from garnet mantle or core compositions with minimum Xgr content are 29–30 kbar at 526–540 °C for type I and 28.2 kbar at 518 °C for type II, suggesting an apparent thermal gradient of ～5.5 °C km?1. Stage II is the post‐Pmax decompression and heating to the temperature peak (Tmax), which was modelled from the garnet zoning with increasing Xgr and Xpy contents. The P–T conditions at Tmax, defined using the garnet rim compositions with maximum Xpy content and the Si content in phengite, are 24–27 kbar at 590 °C for type I and 22 kbar at 540 °C for type II. Stage III is the post‐Tmax isothermal decompression characterized by the decomposition of lawsonite, which may have resulted in the release of a large amount of fluid bound in the rocks, leading to the formation of epidote, paragonite and glaucophane porphyroblasts. Stage IV is the late retrograde evolution characterized by the overprint of hornblendic amphibole in eclogite and the occurrence of epidote–amphibole facies mineral assemblages in the margins or in the strongly foliated domains of eclogite blocks due to fluid infiltration. The P–T estimates obtained from conventional garnet–clinopyroxene–phengite thermobarometry for the Tianshan eclogites are roughly consistent with the P–T conditions of stage II at Tmax, but with large uncertainties in temperature. On the basis of these metamorphic stages or P–T paths, we reinterpreted that the recently reported zircon U–Pb ages for eclogite may date the Tmax stage or the later decompression stage, and the widely distributed (rutile‐bearing) quartz veins in the eclogite terrane may have originated from the lawsonite decomposition during the decompression stage rather than from the transition from blueschist to eclogite as previously proposed.  相似文献   

19.
Relatively strongly magnetic fine components (< 30μm, XS-4J and DS-4J) which are most environmentally sensitive were separated from layer S5-1 in the Xifeng and Duanjiapo loess sections and analyzed by MPV-3 for their morphometric characteristics and reflectance, SEM-ESD for their element contents and XRD for their mineral phases, respectively. The results showed that minerals in both samples are dominated by detrial Fe-Ti oxides of aeolian origin. In sample XS-4J the reflectance and iron contents of magnetic minerals are usually high. In addition to magnetite (Fe3O4), maghemite (γFe2O3) and hematite (Fe2O3), some Fe-high oxide (72.25 wt%–86.67 wt%), ilmenite (FeTiO3), and magnetite-ulvöspinel [Fe(FeCr)O4, Fe (FeNi)O4] were also detected. In sample DS-4J obvious negative linear correlations were found between Ti and Fe, and the contents of Mn, Si, Al and Ca are usually high and the minerals are dominated by magnetite (maghemite), goethite (FeOOH) and limonite (containing Si and OH). In addition, the signs of corrosion of magnetic minerals and newly crystallized magnetite (maghemite) were recognized. Differences in the composition and assemblage characteristics of magnetite minerals between XS and DS reflect significant differences in source rocks and preserving conditions.  相似文献   

20.
The postperovskite phase transition of Fe and Al-bearing MgSiO3 bridgmanite, the most aboundant mineral in the Earth's lower mantle, is believed to be a key to understanding seismological observations in the D″ layer, e.g., the discontinuous changes in seismic wave velocities. Experimentally reported phase transition boundaries of Fe and Al-bearing bridgmanite are currently largely controversial and generally suggest wide two-phase coexistence domains. Theoretical simulations ignoring temperature effects cannot evaluate correctly two-phase coexistence domains under high-temperature. We show high-pressure and high-temperature phase transition boundaries for various compositions with geophysically relevant impurities of Fe2+SiO3, Fe3+Fe3+O3, Fe3+Al3+O3, and Al3+Al3+O3 derived from the ab initio finite-temperature free energies calculated combining the internally consistent LSDA + U method and a lattice dynamics approach. We found that at ～ 2500 K, incorporations accompanied by Fe3+ expand the two-phase coexistence domains distinctly, implying that D″ seismic discontinuities likely arise from the phase transition of Fe2+-bearing bridgmanite.  相似文献   

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