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1.
The Parnok deposit is made up of stratiform lodes of iron (magnetite) and manganese (oxide-carbonate, carbonate, and carbonate-silicate) ores localized among terrigenous-carbonate sediments (black shales) on the western slope of the Polar Urals. The lithological study showed that ore-bearing sediments were accumulated in a calm hydrodynamic setting within a relatively closed seafloor area (trap depressions). Periodic development of anaerobic conditions in the near-bottom seawater was favorable for the accumulation of dispersed organic matter in the terrigenous-carbonate sediments. Carbon required to form calcium carbonates in the ore-bearing sediments was derived from carbon dioxide dissolved in seawater. In the organic-rich sediments, carbonates were formed with the participation of carbon dioxide released by the destruction of organic matter. However, δ13C values (from 0.5 to ?4.4‰ PDB) suggest a relatively low fraction of the isotopically light biogenic carbon in the host calcite. The most probable sources of Fe and Mn were hydrothermal seepages at the seafloor. The Eh-pH conditions during stagnation were favorable for the precipitation of Fe and accumulation of Mn in a dissolved state. Transition from the stagnation regime to the concentration of oxygen in near-bottom waters was accompanied by oxidation of the dissolved Mn and its precipitation. Thus, fluctuations in Eh-pH parameters of water led to the differentiation of Fe and Mn. Initially, these elements were likely precipitated as oxides and hydroxides. During the subsequent lithification, Fe and Mn were reduced to form magnetite and rhodochrosite. The texture and structure of rhodochrosite aggregates indicate that manganese carbonates already began to form at the diagenetic stage and were recrystallized during the subsequent lithogenetic stages. Isotope data (δ13C from ?8.9 to ?17.1‰ PDB) definitely indicate that the oxidized organic matter of sediment served as the main source of carbon dioxide required to form manganese carbonates. Carbonates from host rocks and manganese ores have principally different carbon isotopic compositions. Unlike carbonates of host rocks, manganese carbonates were formed with an active participation of biogeochemical processes. Further processes of metagenesis (T ≈ 250–300°C, P ≈ 2 kbar) resulted in the transformation of textures, structures, and mineral composition of all rocks of the deposit. In particular, increase in temperature and pressure provided the formation of numerous silicates in manganese ores.  相似文献   

2.
The mineralogy of slightly metamorphosed manganese ore at the South Faizulino hydrothermalsedimentary deposit in the southern Urals has been studied; 32 minerals were identified. Quartz, hausmannite, rhodochrosite, tephroite, ribbeite, pyroxmangite, and caryopilite are major minerals; calcite, kutnahorite, alleghanyite, spessartine, rhodonite, clinochlore, and parsettensite are second in abundance. This mineralic composition was formed in the process of gradual burial of ore beneath the sequence of Middle Devonian-Lower Carboniferous rocks. The highest parameters of metamorphism are T ≈ 250°C and P ≈ 2.5 kbar. The relationships between minerals and their assemblages made it possible to reconstruct the succession of ore transformation with gradually increasing temperature and pressure. Manganese accumulated in the initial sediments as oxides and a gel-like Mn-Si phase. Rhodochrosite and neotocite were formed at the diagenetic stage. In the course of a further increase in temperature and pressure, neotocite was replaced with caryopilite; ribbeite, tephroite, pyroxmangite, and other silicates crystallized afterwards. In addition to the PT parameters, the formation of various metamorphic mineral assemblages was controlled by the Mn/(Mn + Si) ratio in ore and X CO2 in pore solution. The latter parameter was determined by the occurrence of organic matter in the ore-bearing rocks. Ore veinlets as products of local hydrothermal redistribution of Mn, Si, and CO2 were formed during tectonic deformations in the Middle Carboniferous and Permian.  相似文献   

3.
Idioblastic spessartine garnet pervasively developed in Mn-rich rocks and impure manganese carbonate ore at the Lower Proterozoic Nsuta manganese deposit, Western Ghana, contains abundant inclusions of micritic and microconcretionary carbonates and, to a lesser extent, quartz. Detailed mineralogical and microprobe studies indicate all the carbonate phases (i.e. carbonate inclusions in garnet, carbonates coexisting with garnet and carbonates not directly in contact with garnet, the latter hereafter referred to as matrix carbonates) lie within the rhodochrosite-kutnahorite solid solution series, i.e. ~Mn55-80(Ca + Mg)20-45CO3 to Ca42(Mn + Mg)58(CO3)2. Minor compositional differences occur in the various carbonate phases, but partition of major elements among coexisting phases indicate most carbonate minerals strongly fractionate Ca and Mg over coexisting spessartine. The nature, composition and textural relationship of coexisting minerals and inclusions in porphyroblastic spessartine indicate that the latter formed from metamorphic reactions in which rhodochrosite and/or kutnahorite and quartz were consumed, in part corroborating earlier observations on a rhodochrosite precursor for spessartine. Spessartine formation is thus envisaged to have taken place when the predominantly Mn carbonate-quartz assemblage became unstable in the presence of minor amounts of an unknown aluminous phase. Because all the carbonates appear to be low-temperature phases with no indications of significant recrystallisation or homogenisation, it could be argued that the spessartine + rhodochrosite - kutnahorite - quartz - pyrite assemblage stabilised during very low-grade greenschist facies metamorphism under relatively low but uniform fO2 conditions. These observations also suggest the stability field of spessartine could extend to relatively lower temperatures than currently envisaged.  相似文献   

4.
Intraclastic Mn carbonate rocks occur in the marginal areas of the manganese–carbonate orebody (manganesestone) of the Palaeoproterozoic Nsuta deposit in the Birimian of Ghana. Macroscopically the intraclastic rocks display graded bedding and are typified by a matrix-supported fabric with subangular to subrounded particles less than a millimetre to ∼1.5 × 0.5 cm. Both clasts and matrix consist mainly of varying proportions of microcrystalline and microconcretionary carbonates, quartz, muscovite and subordinate pyrite. Within individual intraclasts, carbonate minerals (including distinctly zoned microconcretions) are essentially Mg kutnahorite and Mg–Ca rhodochrosite, similar to the carbonate minerals in the manganesestone. Whole rock chemistry of the intraclastic carbonates shows significant variability in the amounts of SiO2, Al2O3, MnO, MgO, CaO, Na2O and, to a lesser extent, K2O. Major element contents of the manganesestone similarly vary widely, except that these have, in particular, comparably higher MnO but less SiO2 and Al2O3 than the intraclastic carbonates and host rock Mn phyllite. Rare earth element (REE) concentrations in the intraclastic carbonates are approximately an order of magnitude higher than in the manganesestone. Whereas both rocks exhibit positive Eu anomalies, only the manganesestone shows a discernibly negative Ce anomaly. Petrographic and geochemical features suggest that the intraclasts are fragments of reworked Mn carbonate sediments derived from intraformational erosion and subsequent (mass flow) deposition as carbonate “turbidite” mud. Processes such as submarine slumping, sliding and other sediment gravity flows may have likely interrupted Mn sedimentation and transported partially consolidated manganiferous sediments down slopes into the early Birimian ocean.  相似文献   

5.
Approximate mixing properties of the end-member components of the quarternary garnet solid solution, (Fe,Mg,Ca,Mn)3Al2Si3O12, have been derived through theoretical analysis of observational data, combined with certain experimental results and crystal chemical considerations. The results suggest that the mixing of pyrope with grossularite, spessartite, and almandine would involve significant positive excess free energies of mixing leading to the critical mixing temperatures of 694±55, 535±140, and 479±63 °C respectively. Spessartite would mix with almandine nearly ideally, and with grossularite with small positive deviation from ideality. The quarternary solution reduces essentially to a ternary mixture of pyrope, grossularite, and almandine + spessartite. The solid solubility relation, and tie line coordinates in this ternary system has been calculated as a function of temperature; the solid solution is found to be intrinsically stable for practically all ternary compositions at 600 °C.  相似文献   

6.
We studied calcite and rhodochrosite from exploratory drill cores (TH‐4 and TH‐6) near the Toyoha deposit, southwestern Hokkaido, Japan, from the aspect of stable isotope geochemistry, together with measuring the homogenization temperatures of fluid inclusions. The alteration observed in the drill cores is classified into four zones: ore mineralized zone, mixed‐layer minerals zone, kaolin minerals zone, and propylitic zone. Calcite is widespread in all the zones except for the kaolin minerals zone. The occurrence of rhodochrosite is restricted in the ore mineralized zone associated with Fe, Mn‐rich chlorite and sulfides, the mineral assemblage of which is basically equivalent to that in the Toyoha veins. The measured δ18OSMOW and δ13CPDB values of calcite scatter in the relatively narrow ranges from ?2 to 5‰ and from ?9 to ?5‰, respectively; those of rhodochrosite from 3 to 9‰ and from ?9 to ?5‰, excluding some data with large deviations. The variation of the isotopic compositions with temperature and depth could be explained by a mixing process between a heated surface meteoric water (100°C δ18O =?12‰, δ13C =?10‰) and a deep high temperature water (300°C, δ18O =?5‰, δ13C =?4‰). Boiling was less effective in isotopic fractionation than that of mixing. The plots of δ18O and δ13C indicate that the carbonates precipitated from H2CO3‐dominated fluids under the conditions of pH = 6–7 and T = 200–300°C. The sequential precipitation from calcite to rhodochrosite in a vein brought about the disequilibrium isotopic fractionation between the two minerals. The hydrothermal fluids circulated during the precipitation of carbonates in TH‐4 and TH‐6 are similar in origin to the ore‐forming fluids pertaining to the formation of veins in the Toyoha deposit.  相似文献   

7.
The paper presents mineralogical and geochemical data on clinkers and paralavas and on conditions under which they were formed at the Nyalga combustion metamorphic complex, which was recently discovered in Central Mongolia. Mineral and phase assemblages of the CM rocks do not have analogues in the world. The clinkers contain pyrogenically modified mudstone relics, acid silicate glass, partly molten quartz and feldspar grains, and newly formed indialite microlites (phenocrysts) with a ferroindialite marginal zone. In the paralava melts, spinel microlites with broadly varying Fe concentrations and anorthite–bytownite were the first to crystallize, and were followed by phenocrysts of Al-clinopyroxene ± melilite and Mg–Fe olivine. The next minerals to crystallize were Ca-fayalite, kirschsteinite, pyrrhotite, minerals of the rhönite–kuratite series, K–Ba feldspars (celsian, hyalophane, and Ba-orthoclase, Fe3+-hercynite ± (native iron, wüstite, Al-magnetite, and fresnoite), nepheline ± (kalsilite), and later calcite, siderite, barite, celestine, and gypsum. The paralavas contain rare minerals of the rhönite–kuratite series, a new end-member of the rhönite subgroup Ca4Fe 8 2+ Fe 4 3+ O4 [Si8Al4O36], a tobermorite-like mineral Ca5Si5(Al,Fe)(OH)O16 · 5H2O, and high- Ba F-rich mica (K,Ba)(Mg,Fe)3(Al,Si)4O10F2. The paralavas host quenched relics of microemulsions of immiscible residual silicate melts with broadly varying Si, Al, Fe, Ca, K, Ba, and Sr concentrations, sulfide and calcitic melts, and water-rich silicate–iron ± (Mn) fluid media. The clinkers were formed less than 2 Ma ago in various parts of the Choir–Nyalga basin by melting Early Cretaceous mudstones with bulk composition varies from dacitic to andesitic. The pyrogenic transformations of the mudstones were nearly isochemical, except only for volatile components. The CM melt rocks of basaltic andesitic composition were formed via melting carbonate–silicate sediments at temperatures above 1450°C. The Ca- and Fe-enriched and silicaundersaturated paralavas crystallized near the surface at temperatures higher than 900–1100°C and oxygen fugacity \(f_{O_2 }\) between the IW and QFM buffers. In local melting domains of the carbonate–silicate sedimentary rocks and in isolations of the residual melts among the paralava matrix the fluid pressure was higher than the atmospheric one. The bulk composition, mineral and phase assemblages of CM rocks of the Nyalga complex are very diverse (dacitic, andesitic, basaltic andesitic, basaltic, and silica-undersaturated mafic) because the melts crystallized under unequilibrated conditions and were derived by the complete or partial melting of clayey and carbonate–silicate sediments during natural coal fires.  相似文献   

8.
The legendary cruise of H.M.S. Challenger (1872-1876) around the globe must always occupy an eminent place in the annals of oceanography, as being the first systematic attempt made on a global scale to explore the ocean. This expedition made fundamental discoveries in biology and geology which have not been surpassed by any later scientific cruise. Sediment with high content of metals (later called “metalliferous”) was among the enigmatic findings taken onboard. Although the nature of metalliferous sediments is well known today, the very first sampled sediments of this type have not been studied to date. Motivated by the historical value of Challenger’s metalliferous sediment collection we undertook an investigation addressing two questions: (1) the composition of sediments from seafloor for which we have very limited data; (2) Sr-Nd-Pb-Fe-Zn-isotope signature of these sediments collected before the substantial human impact on the ocean during the 20th century.The SE Pacific metalliferous sediments sampled by the Challenger’s explorers are of 2 types: (1) metalliferous oozes blanketing ridge crests and flanks down to the calcite compensation depth (CCD); and (2) stripped of CaCO3 metalliferous sediments located beneath the CCD in the deeps near the mid-ocean ridges. The abiogenic part of these sediments is composed mainly of poorly-crystalline to X-ray amorphous Fe-Mn-oxyhydroxides, and an amorphous silicate phase. These sediments have geochemical features similar to those of all the other metalliferous sediments: very high Fe and Mn content (on abiogenic basis), very low Al/(Al + Fe + Mn), and high content (on abiogenic basis) of As, Ba, Be, Bi, Cd, Co, Cu, Mo, Ni, Pb, Sb, Th, Tl, U, V, W, Y, Zn and Zr. Their REE distribution patterns are similar to that of deep seawater and show weak signs of hydrothermal imprint (weak positive or no Eu anomaly).Seawater and/or terrigenous input from South America control the Sr-Nd-Pb-isotope signature of the Challenger metalliferous sediments and have almost completely obliterated any original MORB-derived hydrothermal signal. Zn isotopes are mainly contributed from seawater although other Zn sources (hydrothermal fluid and detrital aluminosilicates, barite and volcanic glass) are necessary to fully explain Zn-isotope ratios. Fe isotopes indicate relatively slow Fe2+ to Fe3+ oxidation in the non-buoyant plume, thus producing relatively lighter Fe-isotope signature of the FeOOH particles that formed the studied metalliferous sediments.  相似文献   

9.
《Precambrian Research》2002,113(1-2):43-63
Carbon, oxygen and strontium isotope compositions of carbonate rocks of the Proterozoic Vindhyan Supergroup, central India suggest that they can be correlated with the isotope evolution curves of marine carbonates during the latter Proterozoic. The carbonate rocks of the Lower Vindhyan Supergroup from eastern Son Valley and central Vindhyan sections show δ13C values of ∼0‰ (V-PDB) and those from Rajasthan section are enriched up to +2.8‰. In contrast, the carbonate rocks of the Upper Vindhyan succession record both positive and negative shifts in δ13C compositions. In the central Vindhyan section, the carbonates exhibit positive δ13C values up to +5.7‰ and those from Rajasthan show negative values down to –5.2‰. The δ18O values of most of the carbonate rocks from the Vindhyan Supergroup show a narrow range between –10 and –5‰ (V-PDB) and are similar to the ‘best preserved’ 18O compositions of the Proterozoic carbonate rocks. In the central Vindhyan and eastern Son Valley sections, carbonates from the Lower Vindhyan exhibit best-preserved 87Sr/86Sr compositions of 0.7059±6, which are lower compared to those from Rajasthan (0.7068±4). The carbonates with positive δ13C values from Upper Vindhyan are characterized by lower 87Sr/86Sr values (0.7068±2) than those with negative δ13C values (0.7082±6). A comparison of C and Sr isotope data of carbonate rocks of the Vindhyan Supergroup with isotope evolution curves of the latter Proterozoic along with available geochronological data suggest that the Lower Vindhyan sediments were deposited during the Mesoproterozoic Eon and those from the Upper Vindhyan represent a Neoproterozoic interval of deposition.  相似文献   

10.
Core sediments from two boreholes and groundwater from fifty four As-contaminated well waters were collected in the Chapai-Nawabganj area of northwestern Bangladesh for geochemical analysis. Groundwater arsenic concentrations in the uppermost aquifer (10 to 40 m of depth) range from 2.76?C315.15 mg/l (average 48.81 mg/l). Arsenic concentration in sediments ranges from 3.26?C10 mg/kg. Vertical distribution of arsenic in both groundwater and sediments shows that maximum As concentration (462 mg/l in groundwater and 10 mg/kg in sediments) occurs at a depth of 24 m. In January 2008, 2009 and 2010, maximum As concentration occurs at the same depth. Environmental scanning electron microscope (ESEM) with EDAX was used to investigate the presence of major and trace elements in the sediments. The dominant groundwater type is Ca-HCO3 with high concentrations of As and Fe, but with low levels of NO3 ? and SO3 ?2. Statistical analysis clearly shows that As is closely associated with Fe (R2 = 0.64) and Mn (R2 = 0.91) in sediments while As is not correlated with Fe and Mn in groundwater samples. Comparatively low Fe and Mn concentrations in some groundwater, suggest that probably siderite and/or rhodochrosite precipitated as secondary mineral on the surface of the sediment particles. The correlations along with results of sequential leaching experiments suggest that reductive dissolution of FeOOH and MnOOH mediated by anaerobic bacteria represents mechanism for releasing arsenic into the groundwater.  相似文献   

11.
The occurrence of early diagenetic Ca‐rhodochrosite [(Mn,Ca)CO3] is reported in association with ‘griotte’‐type nodular limestones from basinal settings in the geological record; however, without the comparison of analogous modern examples, the controls on precipitation remain speculative. Here the findings of four layers of primary Ca‐rich rhodochrosite recovered from a modern deep‐sea setting in the Eastern Equatorial Pacific, from bioturbated sediments 300 m below sea floor, are reported (Ocean Drilling Program, Leg 201, Site 1226). The mineralogy is similar to cements in burrows recovered during Deep Sea Drilling Project Leg 68 at Eastern Equatorial Pacific Site 503 and from Ca‐rhodochrosite laminae in sediments of the central Baltic Sea. Petrographic relationships and constant oxygen isotopic compositions in the Ca‐rhodochrosite around 5‰ at all depths indicate a shallow burial depth of formation. The onset of 1‰ heavier oxygen isotope composition of Ca‐rhodochrosite at Site 503, about 30 m below the Pliocene/Pleistocene boundary, further suggests that precipitation occurs in the range of 30 m below sea floor. The approximate depth of formation allowed an approximate empirical fractionation factor for marine Ca‐rhodochrosite to be constrained that strongly differs from previously published theoretical values. Based on the approximate precipitation depth, authigenic Ca‐rhodochrosite forms within the SO42?‐reduction zone. Moderately negative δ13C values (around ?3‰) and total organic carbon lower than 2 wt% indicate a relatively low contribution of CO32? from organic C mineralization within the expanded redox zonation in the Eastern Equatorial Pacific. It is suggested that the alkalinity is increased by a rise in pH at focused sites of Mn‐reduction coupled with S2? oxidation. High concentrations of Mn‐oxide can accumulate in layers or burrows because of Mn‐cycling in suboxic sediments as suggested for the Baltic Sea Ca‐rhodochrosites. This study demonstrates how early diagenetic precipitates document biogeochemical processes from past diagenetic systems.  相似文献   

12.
We document the development of a suite of carbonate mineral reference materials for calibrating SIMS determinations of δ18O in samples with compositions along the dolomite–ankerite solid solution series [CaMg(CO3)2–CaFe(CO3)2]. Under routine operating conditions for the analysis of carbonates for δ18O with a CAMECA IMS 1280 instrument (at WiscSIMS, University of Wisconsin‐Madison), the magnitude of instrumental bias along the dolomite–ankerite series decreased exponentially by ~ 10‰ with increasing Fe content in the dolomite structure, but appeared insensitive to minor Mn substitution [< 2.6 mol% Mn/(Ca+Mg+Fe+Mn)]. The compositional dependence of bias (i.e., the sample matrix effect) was calibrated using the Hill equation, which relates bias to the Fe# of dolomite–ankerite [i.e., molar Fe/(Mg+Fe)] for thirteen reference materials (Fe# = 0.004–0.789); for calibrations employing either 10 or 3 μm diameter spot size measurements, this yielded residual values ≤ 0.3–0.4‰ relative to CRM NBS 19 for most reference materials in the suite. Analytical precision was ± 0.3‰ (2s, standard deviations) for 10‐μm spots and ± 0.7‰ (2s) for 3‐μm spots, based on the spot‐to‐spot repeatability of a drift monitor material that ‘bracketed’ each set of ten sample‐spot analyses. Analytical uncertainty for individual sample analyses was approximated by a combination of precision and calibration residual values (propagated in quadrature), suggesting an uncertainty of ± 0.5‰ (2s) for 10‐μm spots and ± 1‰ (2s) for 3‐μm spots.  相似文献   

13.
The results of isotope-geochemical studies of carbonates of different mineral types from manganese and host rocks of the Famennian manganiferous formation of Pai-Khoi are reported. Kutnahorite ores are characterized by δ13C values from–6.6 to 1.3‰ and δ18O from 20.0 to 27.4‰. Rhodonite–rhodochrosite rocks of the Silovayakha ore occurrence have δ13C from–5.2 to–2.9 and δ18O from 25.4 to 24.3‰. Mineralogically similar rocks of the Nadeiyakha ore occurrence show the lighter carbon and oxygen isotopic compositions: δ13C from–16.4 to–13.1 and δ18O from 24.8 to 22.5‰. Similar isotopic compositions were also obtained for rhodochrosite–kutnahorite rocks of this ore occurrence: δ13C from–13.0 to–10.4‰ and δ18O from 24.6 to 21.7‰. Siderorodochrosite ores differ in the lighter oxygen and carbon isotopic compositions: δ18O from 18.7 to 17.6‰ and δ13C from–10.2 to–9.3‰, respectively. In terms of the carbon and oxygen isotopic compositions, host rocks in general correspond to marine sedimentary carbonates. Geological-mineralogical and isotope data indicate that the formation of the manganese carbonates was related to the hydrothermal ore-bearing fluids with the light isotopic composition of oxygen and carbon dissolved in CO2. The isotopic features indicate an authigenic formation of manganese carbonates under different isotopegeochemical conditions.  相似文献   

14.
The manganese deposit of Nsuta, in the Ashanti Belt of Southern Ghana, is sandwiched between Birimian metasedimentary rocks. The metasedimentary rocks contain interbedded carbonate-rich layers, which exhibit a characteristic banded appearance near the contact with the orebody. The orebody is a carbonate-type manganese-formation and in terms of origin is considered here as a Mn-analogue of the volcanogenic-exhalative Algoma type iron-formation. The protolith of the orebody (chemical sediment including Fe-bearing rhodochrosite and alabandite) is envisioned to have been formed in a marine basin with relatively high CO2 activity and Eh-pH conditions were extremely low (Eh 1 to −0.6 Volt and pH 8 to 11) during Birimian times (2170–2180 Ma). These conditions occurred immediately below the shelf break in a shallow-marine environment. Subsequent submarine weathering (halmyrolysis) followed later by metamorphism of Eburnian age (2100 Ma) led to the formation of Mg-Ca-Fe-bearing rhodochrosite, the dominant mineral in the orebody. Other minerals of the orebody are: sulfides (e.g. two generations of alabandite sphalerite, pyrite, millerite, niccolite, gersdorffite, and molybdenite), oxides and hydroxides (vanadium-bearing jacobsite, galaxite; brucite, Mn2+-todorokite), Mn-silicates and an unknown boron mineral. Pyrochroite, possibly preceded by manganosite, occurs as a retrograde mineral. This mineral assemblage forms the protore of the Nsuta deposit. Opaque Mn4+-todorokite replacing Mn2+-todorokite, manganite, manganomelane, pyrolusite and nsutite which formed at the expense of rhodochrosite, are of supergene origin and represent the economic part of the deposit. The orebody is interleaved between the associated pelitic-psammitic metasedimentary rocks suggesting that its protoliths was deposited over a time interval during the sedimentation of the latter. Both units underwent subsequent processes (submarine weathering and metamorphism) together. The compositional differences between the orebody with high Mn and CO2 and low Si and Al contents relative to the metasedimentary rocks are explained by a model involving the continuous sedimentation of continent-derived materials (protolith of the metasedimentary rocks). During this time a pulsatory phase of submarine volcanism and consequent precipitation of materials of essentially volcanogenic-exhalative origin occurred (protolith of the orebody). From the exhalations, the carbonate minerals in both the manganese-rich sediments and the metasedimentary host-rocks (in the latter in the form of layers and disseminations leading to relatively high concentrations of Mn, Ca and CO2) were precipitated. Received: 18 April 1997 / Accepted: 16 July 1998  相似文献   

15.
The dissolution behavior of natural, ordered kutnahorite (Mn1.14Ca0.82Mg0.04Fe0.012(CO3)2) and a disordered, calcian rhodochrosite (Mn1.16Ca0.78Mg0.06(CO3)2) precipitated in the laboratory was investigated in deionized distilled water and artificial seawater in both open and closed systems at 25 °C, one atmosphere total pressure, and various pCO2s. Both solids dissolved congruently in distilled water in an open system and yielded identical long-term equilibration or extrapolated ion activity products, IAPpkt = aCa 2+aMn 2+(aCO 3 2?)2 = 1.7 (±0.12)× 10?21 or pIAPpkt = 20.77 (±0.03). This value is believed to be the thermodynamic solubility product of pseudokutnahorite. In contrast, the steady state ion concentration products, ICPpkt = [Ca2+][Mn2+][CO3 2?]2, measured following the dissolution of both minerals in artificial seawater increase as the CO2 partial pressure decreases and the [Mn2+]:[Ca2+] ratio increases. These observations are interpreted as resulting from the formation of phases of different stoichiometry in response to large variations of the [Mn2+]:[Ca2+] ratio in solution. These data and results of calcite-seawater equilibration experiments in the presence of various dissolved Mn(II) concentrations define the fields of stability of manganoan calcites and calcian rhodochrosites in seawater within Lippmann phase diagrams for the CaCO3–MnCO3–H2O system. Results of this study reveal that the nature (i.e., mineralogy) and composition of manganese-rich carbonate phases that may form under suboxic/anoxic conditions in marine sediments are dictated by the porewater [Mn2+]:[Ca2+] ratio, the abundance of calcite surfaces and reaction kinetics.  相似文献   

16.
This study is Part II of a series that documents the development of a suite of calibration reference materials for in situ SIMS analysis of stable isotope ratios in Ca‐Mg‐Fe carbonates. Part I explored the effects of Fe2+ substitution on SIMS δ18O bias measured from the dolomite–ankerite solid solution series [CaMg(CO3)2–CaFe(CO3)2], whereas this complementary work explores the compositional dependence of SIMS δ13C bias (calibrated range: Fe# = 0.004–0.789, where Fe# = molar Fe/(Mg+Fe)). Under routine operating conditions for carbonate δ13C analysis at WiscSIMS (CAMECA IMS 1280), the magnitude of instrumental bias increased exponentially by 2.5–5.5‰ (session‐specific) with increasing Fe‐content in the dolomite structure, but appeared insensitive to minor Mn substitution [< 2.6 mole % Mn/(Ca+Mg+Fe+Mn)]. The compositional dependence of bias (i.e., the matrix effect) was expressed using the Hill equation, yielding calibration residual values ≤ 0.3‰ relative to CRM NBS‐19 for eleven carbonate reference materials (6‐μm‐diameter spot size measurements). Based on the spot‐to‐spot repeatability of a drift monitor material that ‘bracketed’ each set of ten sample‐spot analyses, the analytical precision was ± 0.6–1.2‰ (2s, standard deviations). The analytical uncertainty for individual sample analyses was approximated by combining the precision and calibration residual values (propagated in quadrature), suggesting an uncertainty of ± 1.0–1.5‰ (2s).  相似文献   

17.
Total trace metals (Cd, Co, Cu, Fe, Mn, Ni, Pb, Zn), Al, and pyrite- and reactive-associated metals were measured for the first time in a microbial mat and its underlying anoxic-sulfidic sediment collected in the saltern of Guerrero Negro (GN), Baja California Sur, Mexico. It is postulated that the formation of acid volatile sulfide (AVS) and pyrite in the area of GN could be limited by the availability of reactive Fe, as suggested by its limited abundance (mat and sediment combined average value of only 19 ± 10 ??mol g?1; n = 22) as well as the low pyrite (0.89?C7.9 ??mol g?1) and AVS (0.19?C21 ??mol g?1) concentrations (for anoxic-sulfidic sediments), intermediate degrees of pyritization (12?C50%), high degrees of sulfidization (14?C100%), generally low degrees of trace metal pyritization, and slight impoverishment in total Fe. This is a surprising result considering the large potential reservoir of available Fe in the surrounding desert. Our findings suggest that pyrite formation in the cycling of trace metals in the saltern of GN is not very important and that other sedimentary phases (e.g., organic matter, carbonates) may be more important reservoirs of trace elements. Enrichment factors [EFMe = (Me/Al)sample/(Me/Al)background] of Co, Pb, and Cd were high in the mat (EFMe = 2.2 ± 0.4, 2.8 ± 1.6 and 34.5 ± 9.8, respectively) and even higher in the underlying sediment (EFMe = 4.7 ± 1.5, 14.5 ± 6.2 and 89 ± 27, respectively), but Fe was slightly impoverished (average EFFe of 0.49 ± 0.13 and 0.50 ± 0.27 in both mat and sediment). Organic carbon to pyrite-sulfur (C/S) molar ratios measured in the mat (2.9 × 102?C27 × 102) and sediment (0.81 × 102?C6.6 × 102) were, on average, approximately 77 times higher than those typically found in marine sediments (7.5 ± 2.1). These results may indicate that ancient evaporation basins or hypersaline sedimentary environments could be identified on the basis of extremely high C/S ratios (e.g., >100) and low reactive Fe.  相似文献   

18.
In the Hunan-Guizhou-Guangxi area there have developed very thick bedded siliceous rocks of the late Sinian. The rocks have a fairly pure composition, with an average content of siliceous minerals exceeding 95%. They are relatively rich in Fe and Mn, and poor in Al, Ti and Mg. The Fe/Ti, (Fe+Mn)/Ti, Al/(Al+Fe+Mn) and U/Th ratios and the Al-Fe-Mn and Fe-Mn-(Ni+Co+Cu)×10 triangle diagrams all show that they are hydrothermal sedimentary siliceous rocks. In the rocks the total amount of REEs is low, the δCe shows an obvious negative anomaly and the 8Eu a weak anomaly, and LREE>HREE, all indicating that they are products of hydrothermal processes. The δ30Si and δ18O values, as well as the formation temperature of the rocks all clearly show that the silica forming the rocks comes from hot water. Besides, analyses of the depositional environment of the rocks using the MnO/TiO2 ratio and the δCe and δ30Si values yield the same conclusion that they are formed in environments from continental marginal slope  相似文献   

19.
Core sediments from three disturbed boreholes (JOR, GHAT, and RAJ) and two undisturbed boreholes (DW1 and DW2) were collected in the study area of the Chapai-Nawabganj district of northwestern Bangladesh for geochemical analyses. In the study area, groundwater samples from fourteen As-contained private wells and five nested piezometers at both the DW1 and DW2 boreholes were also collected and analyzed. The groundwater arsenic concentrations in the uppermost aquifer (10–40 m of depth) range from 3 to 315 μg/L (mean 47.73 ± 73.41 μg/L), while the arsenic content in sediments range from 2 to 14 mg/kg (mean 4.36 ± 3.34 mg/kg). An environmental scanning electron microscope (ESEM) with an energy dispersive X-ray spectrometer was used to investigate the presence of major and trace elements in the sediments. Groundwaters in the study area are generally the Ca–HCO3 type with high concentrations of As, but low levels of Fe, Mn, NO3 ? and SO 4 ?2 . The concentrations of As, Fe, Mn decrease with depth in the groundwater, showing vertical geochemical variations in the study area. Statistical analysis clearly shows that As is closely associated with Fe and Mn in the sediments of the JOR core (r = 0.87, p < 0.05 for Fe and r = 0.78, p < 0.05 for Mn) and GHAT core (r = 0.95, p < 0.05 for Fe and r = 0.93, p < 0.05 for Mn), while As is not correlated with Fe and Mn in groundwater. The comparatively low Fe and Mn concentrations in some groundwater and the ESEM image revealed that siderite precipitated as a secondary mineral on the surface of the sediment particles. The correlations along with results of sequential extraction experiments indicated that reductive dissolution of FeOOH and MnOOH represents a mechanism for releasing arsenic into the groundwater.  相似文献   

20.
Manganese at equilibrium in seawater occurs dominantly as Mn2+ and inorganic complexes at a concentration ratio of about 1:0.72; solubility decreases exponentially with increasing pH or Eh. However, the nodule oxides birnessite and todorokite are at least four orders of magnitude undersaturated relative to the Mn concentrations of seawater, and are metastable relative to hausmannite and manganite. This apparent lack of equilibrium is explicable by the mechanism of precipitation.Surfaces assist Mn precipitation by catalyzing equilibration between dissolved and reactive O2 and simultaneously also by adsorbing ionic Mn species. The effective Eh at the surface becomes 200–400 mV above that of seawater; the oxidation rate of Mn increases about 108 ×, and the activation energies for Mn oxidation decrease ~ 11.5 kcal/mole. Consequently, marine Mn nodules and crusts form by adsorption and catalytic oxidation of Mn2+ and ferrous ions at nucleating surfaces such as sea-floor silicates, oxyhydroxides, carbonates, phosphates and biogenic debris. The resulting ferromanganese surfaces autocatalyze further growth. In addition, Mn-fixing bacteria may also significantly accelerate accretion rates on these surfaces.Mn which accumulates in submarine sediments may be diagenetically recycled in response to steep solubility gradients causing upward migration from more acidic and reducing horizons toward the sea floor. In contrast, the concentrations of the predominant ferric complexes, Fe(OH)30 and Fe(OH)4?, are relatively less sensitive to the Eh's and pH's found in this environment; Fe is therefore not as readily recycled within buried sediments. Consequently, Fe is not so effectively enriched on the sea floor, although it precipitates more readily than Mn because seawater is saturated in amorphous Fe(OH)3.The metastable, perhaps kinetically-related, Mn oxides of nodules have a characteristic distribution: birnessite predominates in oxidizing environments of low sedimentation rate and todorokite where sedimentation rates and diagenetic Mn mobility are higher. Surface adsorption and cation substitution within the disordered birnessite-todorokite structure account for the high trace element content of Mn nodules.  相似文献   

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