Aragonite laminae in hot water travertine crusts, Rapolano Terme, Italy

Small (5–30 μm) aggregates of aragonite needles occur in calcite crystal crusts of present day hot water slope travertines at Rapolano Terme in Tuscany, Italy. The aggregates are mainly concentrated in irregular, wispy and dark laminae which cross-cut calcite crystal feathers to create a pervasive millimetre scale banded appearance in the deposit; they also occur less commonly scattered irregularly through the calcite layers. The aragonite needle aggregates are in the form of crosses, fascicles (sheaf shaped bundles, or dumbbell shaped), rosettes and spherulites. Locally, irregular masses of needles also occur. The fascicles, rosettes and spherulites have hollow centres which resemble microbial components (?fungal spores, bacterial colonies and pollen), suggesting that the aragonite crystals are biotically nucleated. The lamination is interpreted to reflect diurnal control. Stimulation of microbial activity during daylight concentrates cells in laminae and promotes aragonite calcification. Calcite feather crystals, although traversed by the aragonite aggregate laminae, have a clear appearance under the light microscope. They form more or less continuously through the diurnal cycle by abiotic precipitation. The constant association of aragonite with organic nuclei, irrespective of whether the latter are in laminae or scattered through the calcite layers, supports a biotic control on aragonite formation. Lamination in Pleistocene travertines is superficially similar to that in the present day deposits, but is diagenetically altered. In the Pleistocene deposits, the calcite feathers appear dark under the light microscope and the aragonite aggregates, where they are not altered to dark calcite, are dissolved, together with parts of the adjacent spar calcite, and therefore appear light coloured.     

Paleoceanographic Setting and Preservation of Buried Manganese Deposits in DSDP/ODP Cores

Abstract. The occurrence, lithology, and stratigraphic setting of buried manganese deposits and associated host sediments in cores obtained on Legs 123–210 of the Ocean Drilling Program (ODP) are examined in order to establish the formative environment and conditions of preservation. Fossil manganese nodule and crusts are found to have formed or deposited throughout the period from 100 Ma to the present, with an additional example of formation near 137 Ma, suggesting that the deep-sea environment has been oxic and suitable for the formation of manganese nodules and crusts since the Cretaceous. Many manganese nodules and crusts occur on horizons corresponding to hiatuses in sedimentation or periods of slow sedimentation, consistent with the environment in which modern nodules form (sedimentation rate less than 10 m/m.y.). Sediments overlying the fossil nodules and crusts are oozes or biogenic sediments with sedimentation rates of 1–18 m/m.y. Low total organic carbon (<0.1 wt%) in the overlying sediments and high sulfate content (>25 mM) in interstitial water around the manganese horizon suggest that no strong reduction occurred within the overlying sediments. Coverage by biogenic sediments containing only small amounts of organic matter is therefore considered important for the preservation of manganese nodules and crusts. Manganese carbonate occurs sporadically as nodules, concretions or thin layers in various host sediments, including clay, calcareous ooze and siliceous ooze with sedimentation rates of 6–125 m/m.y. Hiatuses are rare around the host sediments of manganese carbonate. Higher total organic carbon (0.2–1.8 wt%) in the host sediments and lower sulfate content (0–25 mM) in interstitial water around the manganese carbonate horizon suggest that reduction in association with decomposition of organic matter would have proceeded in the host sediments.     

Pleistocene sea‐floor fibrous crusts and spherulites in the Danakil Depression (Afar,Ethiopia)

Pleistocene fibrous aragonite fabrics, including crusts and spherules, occur in the Danakil Depression (Afar, Ethiopia) following the deposition of two distinctive Middle and Late Pleistocene coralgal reef units and pre‐dating the precipitation of evaporites. Crusts on top of the oldest reef unit (Marine Isotope Stage 7) cover and fill cavities within a red algal framework. The younger aragonite crusts directly cover coralgal bioherms (Marine Isotope Stage 5) and associated deposits. Their stratigraphic position between marine and evaporitic deposits, and their association to euryhaline molluscs, suggest that the crusts and spherules formed in restricted semi‐enclosed conditions. The availability of hard substrate controls crust formation with crusts more often found on steep palaeo‐slopes, from sea level up to at least 80 m depth, while spherules mainly occur associated with mobile substrate. Crusts reach up to 30 cm in thickness and can be microdigitate, columnar (branching and non‐branching) or non‐columnar, with laminated and non‐laminated fabrics. Two different lamination types are found within the crystalline fabrics: (i) isopachous lamination; and (ii) irregular lamination. These two types of lamination can be distinguished by the organization of the aragonite fibres, as well as the lateral continuity of the laminae. Scanning electron microscopy with energy dispersive X‐ray spectroscopy analyses on well‐preserved samples revealed the presence of Mg‐silicate laminae intercalated with fibrous aragonite, as well as Mg‐silicate aggregates closely associated with the fibrous aragonite crusts and spherules. The variety of observed fabrics results from a continuum of abiotic and microbial processes and, thus, reflects the tight interaction between microbially mediated and abiotic mineralization mechanisms. These are the youngest known isopachously laminated, digitate and columnar branching fibrous crusts associated with a transition from marine to evaporitic conditions. Understanding the context of formation of these deposits in Afar can help to better interpret the depositional environment of the widespread Precambrian sea‐floor precipitates.     

Brick-like texture and radial rays in Triassic pisolites of Lombardy,Italy: A clue to distinguish ancient aragonitic pisolites

Triassic pisolites from the Calcare Rosso, Lombardy, Italy, were formed in a hypersaline vadose environment and now show alternating dolomite and calcite laminae. The calcite consists either of microsparite laminae with a brick-like fabric, or of a mass of mosaic crystals with the external form of square-ended rays.These features suggest that the original laminae and rays were aragonitic, like those of the Holocene supratidal pisolites of the Persian Gulf, which consist of alternating laminae of unoriented nannomicrite with Mg-rich mucilaginous material, and aragonitic fibers with radial orientation separated by mucilaginous films. It is suggested that the transformation to brick-like and ray textures passed through the following diagenetic path: (1) original formation of fibrous aragonite laminae; (2) local aggrading recrystallization of aragonite fibers to large square-ended rays during hypersaline phases; (3) dolomitization of Mg-rich mucilaginous nannomicrite laminae during hyposaline phases; (4) inversion of the aragonite fibers and rays to calcite on a piece-by piece basis that preserved the original textural details, when the pH or Mg/Ca ratio dropped.The brick-like and ray fabrics have not been found in laminae of continental freshwater pisolites because these were deposited as equant and stable crystals of low-Mg calcite. These textures consequently make it possible to establish the chemistry of the depositional and early diagenetic milieu for some ancient pisolitic rocks.     

Manganese minerals and associated fine particulates in the streambed of Pinal Creek,Arizona, U.S.A.: a mining-related acid drainage problem

The Pinal creek drainage basin in Arizona is a good example of the principal non-coal source of mining-related acid drainage in the U.S.A., namely copper mining. Infiltration of drainage waters from mining and ore refining has created an acid groundwater plume that has reacted with calcite during passage through the alluvium, thereby becoming less acid. Where O₂ is present and the water is partially neutralized, iron oxides have precipitated and, farther downstream where the pH of the stream water is near neutral, high-Mn crusts have developed.Trace metal composition of several phases in the Pinal Creek drainage basin illustrates the changes caused by mining activities and the significant control Mn-crusts and iron oxide deposits exert on the distribution and concentration of trace metals. The phases and locales considered are the dissolved phase of Webster Lake, a former acid waste disposal pond; selected sections of cores drilled in the alluvium within the intermittent reach of Pinal Creek; and the dissolved phase, suspended sediments, and streambed deposits at specified locales along the perennial reach of Pinal creek.In the perennial reach of Pinal Creek, manganese oxides precipitate from the streamflow as non-cemented particulates and coatings of streambed material and as cemented black crusts. Chemical and X-ray diffraction analyses indicate that the non-cemented manganese oxides precipitate in the reaction sequence observed in previous laboratory experiments using simpler solution composition, Mn₃O₄ to MnOOH to an oxide of higher oxidation number usually <4.0, i.e. Na-birnessite, and that the black cemented crusts contain (Ca,Mn,Mg)CO₃ and a 7-Åphyllomanganate mixture of rancieite ((Ca,Mn)Mn₄O₉ · (3H₂O)) and takanelite ((Mn,Ca)Mn₄O₉ · (3H₂O)). In the laboratory, aerating and increasing the pH of Pinal Creek water to 9.00 precipitated (Ca,Mn,Mg)CO₃ from an anoxic groundwater that contained CO₂ HCO₃, and precipitated Mn₃O₄ and subsequently MnOOH from an oxic surface water from which most of the dissolved CO₂ had been removed.It is suggested that the black cemented crusts form by precipitation of Fe on the Mn-enriched carbonates, creating a site for the MnFe oxidation cycle and thus encouraging the conversion of the carbonates to 7-Åphysllomanganates. The non-magnetic <63-μm size-fractions of the black cemented crusts consisted mostly of the manganese-calcium oxides but also contained about 20% (Ca,Mn,Mg)CO₃, 5% Fe (calculated as FeOOH), 2–4% exchangeable cations, and trace amounts of several silicates.     

Aragonite stromatolitic buildups from Santorini (Aegean Sea,Greece): Geochemical and palaeontological constraints of the caldera palaeoenvironment prior to the Minoan eruption (ca 3600 yr bp)

The pyroclastic deposits of the Minoan eruption (ca 3600 yr bp ) in Santorini contain abundant xenoliths. Most of these deposits are calcareous blocks of laminated‐botryoidal, stromatolite‐like buildups that formed in the shallow waters of the flooded pre‐Minoan caldera; they consist of (i) light laminae, of fibrous aragonite arranged perpendicular to layering, and (ii) dark laminae, with calcified filaments of probable biological origin. These microstructures are absent in the light laminae, suggesting a predominant inorganic precipitation of aragonite on substrates probably colonized by microbes. Internal cavities contain loose skeletal grains (molluscs, ostracods, foraminifera and diatoms) that comprise taxa typical of shallow marine and/or lagoon environments. Most of these forms are typical of warm water environments, although no typical taxa from hydrothermal vents have been observed. Past gasohydrothermal venting is recorded by the occurrence of barite, pyrolusite and pyrite traces. The most striking features of the stable isotopic data set are: (i) an overall wide range in δ¹³C_PDB (0·16 to 12·97‰) with a narrower variation for δ¹⁸O_PDB (?0·23 to 4·33‰); and (ii) a relatively uniform isotopic composition for the fibrous aragonite (δ¹³C = 12·40 ± 0·43‰ and δ¹⁸O = 2·42 ± 0·77‰, n = 21). The δ¹³C and δ¹⁸O values from molluscs and ostracods display a covariant trend, which reflects a mixing between sea water and a fluid influenced by volcano‐hydrothermal activity. Accordingly, ⁸⁷Sr/⁸⁶Sr from the studied carbonates (0·708758 to 0·709011 in fibrous aragonite and 0·708920 to 0·708991 in molluscs) suggests that the aragonite buildups developed in sea water under the influence of a hydrothermal/volcanic source. Significant differences in trace elements have been detected between the fibrous aragonite and modern marine aragonite cements. The caldera water from which the fibrous aragonite crusts formed received an input from a volcano‐hydrothermal system, probably producing diffuse venting of volcanogenic CO₂ gas and of a fluid enriched in Ca, Mn and Ba, and depleted in Mg and probably in Sr.     

西太平洋海底海山富钴结壳惰性气体同位素组成及其来源

采用高真空气体质谱系统测定了西太平洋麦哲伦海山富钴结壳不同层圈及其基岩的惰性气体丰度和同位素组成,结果显示:(1)西太平洋富钴结壳主要是水成成因,其中惰性气体来源不同,He 绝大多数来自宇宙尘(IDPs),少量来自陆源风成微粒;Ar 主要来自海水溶解的大气,少量来自陆源风成微粒或沉积岩建造水;Ne 和 Xe 主要来自海水中溶解大气, 少量来自宇宙尘;(2)在具三层结构的结壳中,亮煤层(致密层)的惰性气体同位素相对外层和疏松层有较大的不同,显示大洋磷酸岩化对早期沉积的结壳惰性气体组成有较大的影响,如导致~4He 的升高和~3He/~4He 的显著降低;(3)太平洋富钴结壳玄武岩基岩的~3He/~4He 非常低,为0.0095～0.074Ra,与本区磷块岩基岩(0.087Ra)相似,而远低于正常海底玄武岩的~3He/~4He 比值,显示这些基岩曾与富含放射性成因~4He 和 P 的上升洋流或沉积物中建造水发生过水/岩反应,这个过程将释放出较多的成矿元素,有利于富钴结壳的形成,海底海山玄武岩中较低的 He 同位素组成可作为富钴结壳的找矿标志之一。     

洞穴碳酸盐微层研究及其发展方向

近几年,在分辨率气候－环境变化研究中,洞穴碳酸盐微层逐渐受到人们重视。洞穴碳酸盐微层的类型较多,主要为年层。微层是在沉积条件发生高频率的周期性改变时形成的,要受到供水条件和碳酸钙浓度等多因素的控制。洞穴碳酸盐微层的稳定同位素组成,生长速率,微层结构与物质组分,微层厚度与灰度和光学特征等可以反映降水,温度,土壤成分及植被变化等信息。     

Managanese and iron in the White Sea: Sedimentation and diagenesis

Iron and manganese in bottom sediments studied along the sublatitudinal transect from Kandalaksha to Arkhangelsk are characterized by various contents and forms depending on sedimentation environments, grain size of sediments, and diagenetic processes. The latter include redistribution of reactive forms leading to enrichment in Fe and Mn of the surface sediments, formation of films, incrustations, and ferromanganese nodules. Variations in the total Fe content (2–8%) are accompanied by changes in the concentration of its reactive forms (acid extraction) and the concentration of dissolved Fe in the interstitial water (1–14 μM). Variations in the Mn content in sediments (0.03–3.7%) and the interstitial water (up to 500 μM) correspond to a high diagenetic mobility of this element. Changes in the valence of chemical elements results in the redox stratification of sediment strata with maximum concentrations of Fe, Mn, and sulfides. Organic matter of sediments with a considerable terrestrial constituent is oxidized by bottom water oxygen mainly at the sediment surface or in anaerobic conditions within the sediment strata. The role of inorganic components in organic matter oxidation changes from surface sediments, where manganese oxyhydroxide dominates among oxidants, to deeper layers, where sulfate of interstitial water serves as the main oxidant. Differences in river runoff and hydrodynamics are responsible for geochemical asymmetry of the transect. The deep Kandalaksha Bay serves as a sediment trap for manganese (Mn content in sediments varies within 0.5–0.7%), whereas the sedimentary environment in the Dvina Bay promotes its removal from sediments (Mn 0.05%).     

Black crusts on travertine: factors controlling development and stability

The travertine buildings of Budapest show extensive black crust formation, which is related to high concentration of atmospheric pollution and a continental climate. Laminar black crusts, framboidal black crusts and leached white surfaces are compared. Physical properties (Schmidt hammer rebound, Duroscope rebound), mineralogical composition and elemental composition are measured. Framboidal black crusts contain more than 50% of acicular gypsum. The crust surface displays idiomorphic rosette-like gypsum crystals with particulates, calcite and gypsum crystal aggregates. The sulphur isotopic composition of the black crusts pinpoints the involvement of rain and dust in crust formation. Thick framboidal black crust has the lowest strength while thin laminar black crust and white dissolved surfaces show minor decrease in surface strength compared to unaltered travertine. The crusts adhere to the travertine surface and rarely show mechanical decay forms that are typical features of porous limestone ashlars in Budapest.     

Evidence of Microbial Activity in the Formation of Manganese Wads at the Asahidake Hot Spring in Hokkaido, Japan

Abstract. Mt. Asahidake is an active volcano, with more than 90 active wells, in the Daisetsu volcanic group located in central Hokkaido, Japan. Wells along the Yukomanbetsu-sawa River showed high manganese concentrations and associated manganese deposits. These deposits consist of manganese oxides, and the concentration of iron is very low except for one sample collected from the upper reach of the river. Most of the wet samples showed basal diffraction characteristic of todorokite (9.6 Å). Cultivation tests showed that microorganisms were responsible for the oxidation of dissolved Mn²⁺ in the Asahidake hot spring. The dissolved Mn²⁺ concentration in the sterilized hot spring water was unchanged after four days, whereas the Mn²⁺ concentration in the sterilized hot spring water with a small amount of fresh manganese wad was decreased to zero after three days, and manganese oxide formed. This result implies that the activity of microorganism oxidizes dissolved Mn²⁺ and forms manganese oxide at the Asahidake manganese deposits. In addition to Komanoyu hot spring and Yunotaki Falls, this is the third report of microbial activity forming considerable deposits of manganese oxides in hot spring waters.     

Dissolution experiment and transformation condition analysis of Paleogene aragonite in the Jiyang Depression,China

In general, aragonite exists as a metastable carbonate mineral under near-surface conditions, and is commonly transformed into calcite under the subsurface and during diagenesis. It is thus seldom found in sedimentary rocks, but aragonite is common in the Paleogene lacustrine shales in the Jiyang Depression in eastern China. Dissolution experiments were conducted on the Paleogene aragonite-enriched and calcite-enriched shales at different temperatures, pressures and acetic acid concentrations, and in different types of solution. The results show that aragonite is insoluble in the in situ formation water but dissolved more readily under acetic acid conditions than calcite with the degree of dissolution increasing with increasing temperature, pressure and acetic acid concentrations. During the shallow burial diagenesis of the Paleogene sediment sequence in the Jiyang Depression, aragonite was relatively stable and was not dissolved by the connate pore water in the shales. Increasing burial (temperature) and maturity of the organic matter produced large amounts of organic acids that accelerated the dissolution of aragonite. In the late stage, as the organic matter became over-matured, the pore water changed from acidic to alkaline, and calcite precipitated from the carbonate-rich solution. Therefore, the conditions provided by organic acids enabled the conversion of aragonite to calcite during sedimentary diagenesis in the Paleogene lacustrine shales in the Jiyang Depression. This transformation corresponded to the thermal evolution of the organic matter within the shale sequence.     

On the distribution of iron and manganese at the sediment/water interface: thermodynamic versus kinetic control

Iron and manganese solubility at the sediment/water interface has been studied at a water depth of 20 m in Kiel Bight, Western Baltic. By means of an in situ bell jar system enclosing 3.14 m² sediment surface and 2094 l water a complete redox turn-over in the bottom water was simulated in an experiment lasting 99 days. The concentration of dissolved Fe in the bell jar water never exceeded 0.041 μmol · dm^?3during the first 50 days of the experiment and then rose abruptly as the Eh fell from +600 to ?200 mV. The concentration of dissolved Fe under oxic and anoxic conditions seems to be limited by equilibria with solid Fe-phases (hydroxides and amorphous sulphide, respectively). In contrast to Fe, manganese was released continuously from the bottom during the first 50 days of the experiment leading to exponentially increasing manganese concentrations in the bell jar water. During this time dissolved O₂ had become ready depleted and pH had dropped from 8.3 to 7.5. Contrary to iron, manganese being solubilized in reduced sediment layers can penetrate oxic strata in metastable form due to slow oxidation kinetics; when the redoxcline moves upwards Mn²⁺ is enriched in bottom waters. The maximum concentration of dissolved Mn under anoxic conditions is controlled by a solid phase with solubility properties similar to MnCO₃ (rhodochrosite). Bottom water enrichment in dissolved Mn²⁺ could be traced to originate from excess solid manganese within the top 3 cm of the sediment.     

Morphology and mineralogy of weathering crusts on highly porous oolitic limestones, a case study from Budapest

Black crusts are very common on limestones in polluted urban environments, but white crusts are less frequently developed. On the soft, porous and inherently weak oolitic limestone of Budapest both crusts are frequent, and indeed white ones are more common on the stone walls of the studied fortress. In this paper, black and white crusts and the host rock have been described using morphological criteria, mineralogical analyses (XRD, DTA), elements analyses (microprobe) and micro-morphological (SEM) tests. The analyses have shown that on white crusts the surface dissolution is combined with the precipitation of gypsum and calcite in the pores and accumulation of gypsum on the underside of the crust. Thin white crusts are removed by a combination of salt crystallisation (gypsum) and frost action while very thick stone layers scale off due to freeze-thaw cycles. Black crusts are enriched in gypsum relative to white crusts. Gypsum accumulates on the crust surface and signs of dissolution have not been observed. Airborne particulates (flyash, silt-sized quartz, and organic debris) adhere to the crust surface of sheltered black crusts. These particles are later incorporated into the expanding gypsum crystals, that are visible on the underside of the crust. The host rock also contains gypsum, but it is washed off the surface when the crust is removed. Further exposure of the host rock may lead to the dissolution of calcite crystals as it is observed by SEM. The micro-environment influences the crust formation and adherence of the crusts. On frequently wet and dry surfaces crust removal is more common. The crust serves as a protective layer on the stone surface, but this protection is temporary since trigger mechanisms such as salt crystallisation or frost action can cause rapid surface loss.Special Issue: Stone decay hazards     

Noble Gas Isotopic Compositions of Cobalt-rich Ferromanganese Crusts from the Western Pacific Ocean and Their Geological Implications

1 Introduction Submarine metallic mineral resources consist mainly of polymetallic nodules and cobalt-rich ferromanganese crusts. Despite being discovered much later than the former, the latter are becoming one of the most important submarine polymetallic ore resources, because they containmany valuable metallic elements such as Co, platinum group elements (PGE), rare earth elements (REE), Ni and Cu, besides high contents of Fe and Mn (He et al., 2001). The Co-rich crusts are widely distr…     

A specific type of Fe-Mn mineralization on the Arctic seafloor

Three samples of Fe-Mn crusts overgrown on the surface of rocks are studied from the Mendeleev submarine rise located in the northern subpolar part of the Chukchi Sea. A massive crust up to 4–5 cm thick consists of an upper dense and lower denser layers similar in composition to the main one and contains 31–37% FeO and 11–13% MnO. Thin crusts and films are depleted in both components. Fe-vernadite is a major mineral of the crusts. The comparison of the major and trace element composition of the crusts with oceanic and marine nodules and hydrothermal crusts shows that they are mostly similar in composition to the nodules of the Bering Sea and are significantly distinct from the oceanic hydrothermal crusts. A small inclusion of the Pt-, Pd-, and Ru-rich (up to 1–2%) rock in one of the thin crusts points to the possible role of igneous rocks as a source of precious metals.     

麦哲伦海山群MK海山富钴结壳稀土元素的赋存相态

利用ICP-OES和ICP-MS,分析了麦哲伦海山群西北端MK海山2 170 m水深的MKD23B-3号富钴结壳样品,获得了其剖面上主元素、稀土元素（REE）和Y含量数据,并基于元素含量间的线性相关关系,研究了REE和Y的赋存相态。结果显示:该样品剖面从基岩到表面可划分为5层,第Ⅰ、Ⅱ层为磷酸盐化壳层,第Ⅲ、Ⅳ、Ⅴ层为未磷酸盐化壳层。在未磷酸盐化壳层中,REE和Y主要赋存在δ-MnO₂相中;而在磷酸盐化壳层中,REE和Y除了赋存在Fe、Mn氧化物相中外,主要赋存在独立于碳氟磷灰石（CFA）的矿物相态中,可能为稀土的磷酸盐。并提出利用磷酸盐中REE/Y 估算富钴结壳磷酸盐化壳层次生稀土的方法,据此估算了MK海山富钴结壳磷酸盐化壳层次生稀土的量。在该样品中,次生稀土占稀土总量的42%~88%,近一半以上的稀土是次生的,磷酸盐化作用对于REE和Y的次生富集具有显著的贡献;因此解读磷酸盐化富钴结壳的稀土元素（特别是Nd同位素）古海洋记录必须排除次生稀土元素的干扰。     

富钴结壳中的磷酸盐岩及其古环境指示意义

磷酸盐岩是富钴结壳老壳层的主要组分之一。本文对来自中太平洋海山的三块富钴结壳样品中的磷酸盐岩进行了研究,以期对富钻结壳形成环境的变化有所了解。通过扫描电镜发现结壳中磷酸盐岩的形态有六种,磷酸盐岩主要分布在老壳层,新壳层中偶见。结壳中的磷酸盐岩为碳氟磷灰石(CFA),经成分分析及电镜中反射色的差异可以区分出两种成因的CFA：一种为交代碳酸盐岩型的,相对富Si、Al、Fe;另一种为从结壳孔隙水中直接沉淀而成的,基本不含Si、Al、Fe。对CB12样品中磷酸盐岩脉进行生物地层学鉴定,得出其老壳层下部火焰状磷酸盐岩的形成年代为晚渐新世一早中新世(23.2-29．9Ma),而其上部充填脉状磷酸盐岩的形成年代为中中新世(10.8-16Ma)。老壳层中富集磷酸盐岩说明在结壳形成早期,结壳形成环境条件尚不够稳定,底部存在富磷深层储库,当底流突然增强时,可携带磷在海山上交代结壳中的碳酸盐岩或在结壳内部合适条件下直接沉淀形成磷酸盐岩充填脉。新壳层形成时底流已相对髂定,富磷深层储库已消失,不再有广泛磷酸盐化形成。     

Isotope geochemistry, petrology and depositional environments of the diatomite-dominated Tripoli Formation (Lower Messinian), Sicily

ABSTRACT The Tripoli Formation (Lower Messinian) in Sicily includes diatomites irregularly alternating with marl and carbonate beds and lies, stratigraphically, between the Tortonian pelagic marls and the evaporitic Calcare di base. The relationships between mineralogy, textural features and oxygen-carbon isotopic compositions of carbonate components point to a wide variability of depositional conditions and suggest that Tripoli sedimentation occurred in small basins characterized by periodic and marked restriction from the open sea.
The isotopic values of calcite and dolomite in the diatomites suggest an evolution from normal marine towards more restricted environments. Evaporating conditions are also indicated by the occurrence of anhydrite, length-slow chalcedonic quartz and moulds of gypsum. In a more advanced stage, the precipitation of heavy δ¹⁸0 dolomite in the interstitial pores of fossil-poor diatomites denotes an environment with highly evaporated water. Mixing of meteoric and marine waters, on the other hand, might have favoured the precipitation of a dolomite characterized by relatively low δ¹⁸0 and δ¹³C values.
The deposition of marl and carbonate beds alternating with or overlying the diatomites took place in an environment with highly evaporated marine waters on the basis of δl¹⁸O values of dolomite (up to + 9.10‰) and aragonite (up to + 5.83‰), occurrence of evaporitic minerals and lack of fossils. The presence at these levels of calcite with extremely negative δ¹³C values (down to - 38.40‰), filling gypsum moulds, suggests activity of sulphate-reducing bacteria. Some aragonitic marls, however, bear evidence of deposition in relatively normal marine conditions.     

Origin of high manganese concentrations in coal mine drainage, eastern Tennessee

The origin of high dissolved manganese concentrations in slightly acidic mine runoff from a surface mine operated by the Cumberland Coal Company in eastern Tennessee was investigated. Mineralogical and chemical analyses were performed on 31 samples of sandstone, shale, coal, and mudstone from the mine to identify the sources and stratigraphic distribution of high extractable manganese contents in the spoil materials. The samples were analyzed for their bulk mineral content by X-ray diffraction, net acid-base potential, and reaction to 2 or 4 chemical extraction procedures. A limited number of samples were analyzed for petrographic characteristics, clay mineral composition by X-ray diffraction, and mineral compositions by electron microprobe. Analysis of the data and consideration of the geochemical conditions at the mine were used to identify probable sources for the high extractable manganese contents.The results indicate 2 prominent, independent sources of extractable manganese. The first source is exchangeable manganese on clay minerals (mainly illite + muscovite and chlorite) and is concentrated in shale and mudstone rock types. The second and more significant source is manganese in siderite concretions and cement, mainly in shale and mudstone. Comparison to other coal-bearing strata indicates that manganese-rich siderite is common in fresh- to brackish-water subaqueous sediments that overlie coal. This is especially the case for coals formed in wet, tropical environments.Ratios of manganese to calcium and magnesium in mine runoff suggest that manganese from siderite is the major cause of the high dissolved manganese contents. A conceptual model is developed to explain the high manganese contents of the mine runoff. Oxidation of pyrite creates mildly acidic waters that are subsequently partially neutralized by reaction with impure siderite. Solubilized manganese remains dissolved in the slightly acidic runoff water, whereas dissolved iron precipitates as ferric hydroxide or goethite. Consideration of data from other coal mining regions suggests that similar reactions involving impure siderite may be responsible for high manganese concentrations in acidic to slightly acidic mine runoff. Geochemical reaction path modeling of pyrite and impure siderite with rainwater illustrate how resulting water compositions may vary depending on pyrite to siderite ratios in spoil materials. Spoil water compositions from the Cumberland mine are largely consistent with reaction of pyrite and impure siderite in proportions observed in the sediments; however, deviations may be explained by minor mixing with waters that reacted only with impure siderite or clay mineral exchange reactions.