Geochemistry of meteoric calcite cements in some Pleistocene limestones

In this study, the stable isotope and trace element geochemistries of meteoric cements in Pleistocene limestones from Enewetak Atoll (western Pacific Ocean), Cat Island (Bahamas), and Yucatan were characterized to help interpret similar cements in ancient rocks. Meteoric calcite cements have a narrow range of δ¹⁸O values and a broad range of δ¹³C values in each geographical province. These Pleistocene cements were precipitated from water with stable oxygen isotopic compositions similar to modern rainwater in each location. Enewetak calcite cements have a mean δ¹⁸O composition of ?6.5%₀ (PDB) and δ¹³C values ranging from ?9.6 to +0.4%0 (PDB). Sparry calcite cements from Cat Island have a mean δ¹⁸O composition of ?4.1%₀ and δ¹³C values ranging from ?6.3 to + 1.1%₀. Sparry cements from Yucatan have a mean δ¹⁸O composition of ?5.7%₀ and δ¹³C values of ?8.0 to ?2.7%₀. The mean δ¹⁸O values of these Pleistocene meteoric calcite cements vary by 2.4%₀ due to climatic variations not related directly to latitude. The δ¹³C compositions of meteoric cements are distinctly lower than those of the depositional sediments. Variations in δ¹³C are not simply a function of distance below an exposure surface. Meteoric phreatic cements often have δ¹³C compositions of less than —4.0%₀, which suggests that soil-derived CO₂ and organic material were washed into the water table penecontemporaneous with precipitation of phreatic cements. Concentrations of strontium and magnesium are quite variable within and between the three geographical provinces. Mean strontium concentrations for sparry calcite cements are, for Enewetak Atoll, 620 ppm (σ= 510 ppm); for Cat Island, 1200 ppm (σ= 980 ppm); and for Yucatan, 700 ppm (σ= 390 ppm). Equant cements, intraskeletal cements, and Bahamian cements have higher mean strontium concentrations than other cements. Equant and intraskeletal cements probably precipitated in more closed or stagnant aqueous environments. Bahamian depositional sediments had higher strontium concentrations which probably caused high strontium concentrations in their cements. Magnesium concentrations in Pleistocene meteoric cements are similar in samples from Enewetak Atoll (mean =1.00 mol% MgCO₃; σ= 0.60 mol% MgCO₃) and Cat Island (mean = 0.84 mol% MgCO₃; σ= 0.52mol% MgCO₃) but Yucatan samples have higher magnesium concentrations (mean = 2.20 mol% MgCO₃: σ= 0.84mol% MgCO₃). Higher magnesium concentrations in some Yucatan cements probably reflect precipitation in environments where sea water mixed with fresh water.     

Ocean floor metamorphism in the Betts Cove ophiolite,Newfoundland

The mineralogical and geochemical features of the lower Ordovician Betts Cove ophiolite of northeastern Newfoundland indicate that hydrothermal circulation of seawater near a mid-ocean ridge has been involved in the metamorphism of the complex. The degree of greenschist facies metamorphism increases with stratigraphie depth in the ophioli te. Calcite, hematite and epidote distributions show that the metamorphosing fluid penetrated downward and was reduced with depth. The mobilities of major and trace elements support the hypothesis of the interaction of seawater and basalt: Fe₂O₃, MgO, Na₂O and H₂O increase whereas CaO and Cu decrease in the rock after alteration; SiO₂, total iron, K₂O, Ba and Rb can either be depleted or enhanced in the altered material; TiO₂, P₂O₅, Zr, Y, Cr and Ni remain stable during the metamorphic episode. Finally, the occurrence of massive sulphides and incipient rodingitic gabbro is explicable in a circulatory seawater system.     

现代海底烟囱中流体包裹体的研究

大洋中脊的海底块状硫化物矿床是当前地球科学的一个热点。因为他不仅具有经济效益,而且可以直接观测到这些矿床的形成过程。这些矿床均有许多黑烟囱和白烟囱。在这些烟囱中成矿流体不断地流过,并同时沉淀出Cu,Pb,Zn硫化物和脉石矿物。本研究的样品是取自北纬21°N的太平洋洋脊中现代大洋海底的Zn(Cu)型硫化物烟囱。对这些烟囱的矿物共生组合进行研究发现其矿物组合相当简单,分硫化物和脉石矿物两种。硫化物中以其含量多少排列为闪锌矿,黄铁矿,黄铜矿和磁黄铁矿。脉石矿物以硬石膏为主,见少量重晶石。在烟囱中这些硫化物和脉石矿物的分布是有分带性的。从外到内为硬石膏带,黄铁矿带,闪锌矿带。闪锌矿带向里可见到少量黄铜矿和磁黄铜矿,及硬石膏,但它们尚未构成一个带。烟囱的中心常常是空的,因为是原来的热液通道。 发现两类流体包裹体:一类为水溶液相包裹体。另一类为CH_4的包裹体。其均一温度是从180～265℃。最外面的硬石膏带,均一温度从180～245℃(平均212℃)。黄铁矿带均一温度从185～260℃(平均218℃)。闪锌矿带均一温度从190～265℃(平均229℃)。从平均的均一温度看似乎从边上到中心从212—218—229℃向上升,说明一个趋势,中间的温度较高,边上的较低。成矿溶液的盐度与海水相差不大,但略大於海水     

Precipitation and lithification of magnesian calcite in the deep-sea sediments of the eastern Mediterranean Sea*

Magnesian calcite is an important sedimentary component in the deep-sea sediments of the eastern Mediterranean Sea, comprising an average of 20–50% of the carbonate fraction in most areas. The lack of any obvious biogenic source, plus similarities with magnesian-rich lutites from the Red Sea and deep-sea cements from other areas suggest that this magnesian calcite was precipitated inorganically. Although the exact mode of precipitation is not understood at present, it probably occurred at the water-sediment interface under elevated salinity and temperature conditions, such as those present in the modern eastern Mediterranean. Precipitation did not occur during periods of lower temperatures and/or salinities such as during the stagnant conditions caused by the influx of fresh waters from melting Pleistocene glaciers. The eastern Mediterranean magnesium-rich sediments appear to represent an intermediate stage between normal deep-sea sediments and those from the warm hpyersaline Red Sea. Normal deep-sea carbonates are composed almost entirely of biogenic calcite, whereas the Red Sea magnesian calcite alternates with layers of aragonite that were precipitated under elevated salinity and temperature conditions brought about by lowered stands of sea level.     

Geologic features and durability of limestones at the sphinx

Geologic features considered to influence durability of the limestone at the sphinx are depositional history, evolution of porosity, and development of joints. These strata have two orthogonal groups of vertical joints. Where these joints intersect, wedge-shaped blocks are separating, causing loss of material from the core. Major reduction of the sphinx, however, is occurring due to salt crystallization aided by the ink-bottle pore systems prevailing in these rocks.The weathering profile exhibits alternating layers, less and more highly weathered. The less weathered rock is a biomicritic grainstone with smaller quantities of halite and gypsum and a larger large-pore-to-throat ratio than the indented, predominantly micritic, layers with larger concentration of salts and a smaller large-pore-to-throat ratio. Based upon poresize distributions, pressures generated in the pores have been calculated using thermodynamic principles, and an equation has been derived that provides a quantitative measure of durability of these rocks.     

Undications of current action in late Jurassic limestones,radiolarian limestones,saccocoma limestones and associated rocks from the subbetic of SE Spain

In the Vélez Blanco region (province of Almeia), filament limestones occur associated with pellet limestones, crinoidal limestones, radiolarian limestones, Saccocoma limestones and tintinnid limestones. These predominantly Late Jurassic rocks are underlain by Middle Jurassic oolitic limestones and overlain by Cretaceous pelagic limestones and marls.A distinction can be made between long and short filaments. The former are interpreted as undamaged valves, the latter as shell fragments of the pelagic pelecypod Bositra buchi. Bositra valves and fragments have been sorted by weak current (and/or wave) action.In the Saccocoma limestones, evidence for similar sorting of Saccocoma debris has been found.The radiolarian limestones represent a low-energy basin environment, but are not comparable with recent deep-sea radiolarian oozes.Nodular limestone intercalations and hiatuses represent a current- (and/or wave-) swept environment.The occurrence of filament-rich and Radiolaria-bearing, but benthos-poor, intervals within the oolitic limestone indicates that the deposition of such rocks can take place at moderate sea depths.     

Nyerereite from calcite carbonatite at the Kerimasi Volcano,Northern Tanzania

The extinct Quaternary Kerimasi volcano located in the southern part of the Gregory Rift, northern Tanzania, contains both intrusive and extrusive calciocarbonatites. One carbonate mineral with a high content of Na and Ca has been found in a sample of volcanic carbonatite, which is probably a cumulate rock. On the basis of Raman spectroscopy and SEM/EDS, this mineral was identified as nyerereite, ideally Na₂Ca(CO₃)₂. It occurs as solid inclusions up to 300 × 200 μm in size in magnetite and contains (wt. %) 25.4–27.4 Na₂O, 26.0–26.8 CaO, 1.6–1.9 K₂O, 0.6–1.8 FeO, 0.3–0.6 SrO, <0.4 BaO, 1.4–2.3 SO₃, and 0.6–0.9 P₂O₅. The average mineral formula is (Na_1.84K_0.08)_Σ1.92(Ca_1.00Fe_0.03Sr_0.01)_Σ1.04[(CO₃)_1.91(SO₄)_0.05(PO₄)_0.02]_Σ1.98. A few inclusions in magnetite also contain calcite, which is considered here to be a late-stage, subsolidus mineral. The occurrence of nyerereite in carbonatite supports Hay’s (1983) idea that some of the extrusive carbonatites at the Kerimasi volcano were originally alkaline rich and contained both calcite and nyerereite as primary minerals.     

Magnetic anisotropy of calcite at room-temperature

The intrinsic room temperature magnetic properties of pure calcite were determined from a series of natural crystals, and they were found to be highly dependent on the chemical composition. In general, dia-, para-, and ferromagnetic components contribute to the magnetic susceptibility and the anisotropy of magnetic susceptibility (AMS). With a combination of magnetic measurements and chemical analysis these three contributions were determined and related to their mineralogical sources. The intrinsic diamagnetic susceptibility of pure calcite is − 4.46 ± 0.16 × 10^− 9 m³/kg (− 12.09 ± 0.5 × 10^− 6 SI) and the susceptibility difference is 4.06 ± 0.03 × 10^− 10 m³/kg (1.10 ± 0.01 × 10^− 6 SI). These diamagnetic properties are easily dominated by other components. The paramagnetic contribution is due to paramagnetic ions in the crystal lattice that substitute for calcium; these are mainly iron and manganese. The measured paramagnetic susceptibility agrees with the values calculated from the known concentration of paramagnetic ions in the crystals according to the Curie law of paramagnetic susceptibility. Substituted iron leads to an increase in the AMS. The paramagnetic susceptibility difference was found to correlate linearly with the iron content for concentrations between 500 and 10,000 ppm. An empirical relation was determined: (k₁ − k₃)^para (kg/m³) = Fe-content (ppm) × (1 ± 0.1) × 10^− 12 (kg/m³/ppm). The maximum susceptibility difference (Δk = k₁ − k₃) was found to be unaffected by iron contents below 100 ppm. Ferromagnetic contributions due to inclusions of ferromagnetic minerals can dominate the susceptibility. They were detected by acquisition of isothermal remanent magnetization (IRM) and their contribution to the AMS was separated by high-field measurements.     

Mesozoic (Lower Jurassic) red stromatactis limestones from the Southern Alps (Arzo, Switzerland): calcite mineral authigenesis and syneresis-type deformation

The Broccatello lithological unit (Lower Jurassic, Hettangian to lower parts of Upper Sinemurian) near the village of Arzo (southern Alps, southern Switzerland) is a mound-shaped carbonate deposit that contains patches of red stromatactis limestone. Within the largely bioclastic Broccatello unit, the stromatactis limestone is distinguished by its early-diagenetic cavity system, a relatively fine-grained texture, and an in-situ assemblage of calcified siliceous sponges (various demosponges and hexactinellids). A complex shallow subsurface diagenetic pathway can be reconstructed from sediment petrography in combination with comparative geochemical analysis (carbon and oxygen isotopes; trace and rare earth elements, REE + Y). This pathway includes organic matter transformation, aragonite and skeletal opal dissolution, patchy calcification and lithification, sediment shrinkage, sagging and collapse, partial REE remobilization, and multiple sediment infiltration. These processes occurred under normal-marine, essentially oxic conditions and were independent from local, recurring syn-sedimentary faulting. It is concluded that the stromatactis results from a combination of calcite mineral authigenesis and syneresis-type deformation. The natural stromatactis phenomenon may thus be best explained by maturation processes of particulate polymer gels expected to form in fine-grained carbonate sediments in the shallow subsurface. Conditions favorable for the evolution of stromatactis appear to be particularly frequent during drowning of tropical or subtropical carbonate platforms.

太平洋富稀土深海沉积物中稀土元素赋存载体研究

太平洋深海沉积物中富含稀土(含Y,简称REY),尤其是(含)沸石粘土,其主要由粘土组分、沸石、鱼牙骨、微结核及生物残渣等组成,目前对于该类稀土矿床中REY的赋存载体存在争议。本文在中、西太平洋选取两个富REY的沸石粘土样品利用地球化学和矿物学对稀土赋存状态进行定量研究。矿物微区成分表明,鱼牙骨主要成分为磷灰石,含有最高的REY含量,为2497×10~(- 6)~18623×10~(- 6),微结核和沸石颗粒含有较低的REY含量,分别为246×10~(- 6)~333×10~(- 6)和29.36×10~(- 6)~256×10~(- 6)。通过三种矿物相在沉积物63~250μm粒级组分中各自所占质量比例,计算得出磷灰石对REY的贡献率可达90%以上,说明此粒级中磷灰石为主要REY赋存载体,然而相对全岩总的REY含量,该粒级中磷灰石的贡献仍较小。通过对全岩和粉砂级组分(小于63μm)主微量地球化学分析和XRD矿物相分析表明,2个样品中REY主要存在于粉砂级组分中,其中的磷灰石对全岩REY的贡献最高均可达70%左右。另外通过对粘土组分(2μm)研究发现2个样品粘土组分的REY含量相似,分别为530×10~(- 6)和631×10~(- 6),粘土组分对全岩沉积物的REY贡献意义不大,对整个沉积物REY而言其贡献率仅为2%~5%左右。因此认为磷灰石为整个沸石粘土中REY主要赋存载体。     

Microspar development during early marine burial diagenesis: a comparison of Pliocene carbonates from the Bahamas with Silurian limestones from Gotland (Sweden)

Comparison of ultrastructures in Pliocene periplatform carbonates from the Bahamas with Silurian limestones from Gotland (Sweden) reveals that despite the differences in primary sediment composition and age, they reflect a similar mechanism of lithification. In both sequences calcite microspar was formed as a primary cement at an early stage of marine burial diagenesis. Neither significant compression nor meteoric influence are necessary for the formation of calcite microspar. A model is proposed for the process of microsparitic cementation of fine-grained aragonite needle muds comprising four stages: (1) unconsolidated, aragonite-dominated carbonate mud; (2) precipitation of microspar that engulfs aragonite needles; (3) dissolution of aragonite, resulting in pitted surfaces of the microspar crystals; and (4) slight recrystallization. Our results contradict the widespread opinion that microspar necessarily is a product of secondary recrystallization of a previously lithified micrite.     

Electromagnetometry at the sea floor

Electromagnetometry at the sea floor has been developed over the last two decades taking advantage of the progress of positioning and acoustic technology in marine region. In spite of its risks and costs, electromagnetometry at the sea floor has significantly contributed to the study of conductivity anomalies through direct observations of electromagnetic variations at the sea floor. Some of the fruitful results of the ocean bottom observations around Japan as well as data processing of sea floor electromagnetic measurements are reviewed. Future problems in electromagnetometry at the sea floor are also discussed. In conclusion, the importance of establishing semipermanent electromagnetic observatories at the sea floor is emphasized.     

Ocean floor and subduction record in the Zermatt‐Saas rodingites,Valtournanche, Western Alps

Multiscale structural analysis and petrological modelling were used to establish the pressure‐peak mineral assemblages and pressure–temperature (P–T) conditions recorded in the rodingites of the upper Valtournanche portion of the oceanic Zermatt‐Saas Zone (ZSZ; Western Alps, northwestern Italy) during Alpine subduction. Rodingites occur in the form of deformed dykes and boudins within the hosting serpentinites. A field structural analysis showed that rodingites and serpentinites record four ductile deformation stages (D1–D4) during the Alpine cycle, with the first three stages associated with new foliations. The most pervasive fabric is S2 that is marked by mineral assemblages in serpentinite indicating pressure‐peak conditions, involving mostly serpentine, clinopyroxene, olivine, Ti‐clinohumite and chlorite. Three rodingite types can be defined: epidote‐bearing, garnet–chlorite–clinopyroxene‐bearing and vesuvianite‐bearing rodingite. In these, the pressure‐peak assemblages coeval with S2 development involve: (i) epidote_II + clinopyroxene_II + Mg‐chlorite_II + garnet_II ± rutile ± tremolite_I in the epidote‐bearing rodingite; (ii) Mg‐chlorite_II + garnet_II clinopyroxene_II ± vesuvianite_II ± ilmenite in the garnet–chlorite–clinopyroxene‐bearing rodingite; (iii) vesuvianite_II + Mg‐chlorite_II + clinopyroxene_II + garnet_II ± rutile ± epidote in vesuvianite‐bearing rodingite. Despite the pervasive structural reworking of the rodingites during Alpine subduction, the mineral relicts of the pre‐Alpine ocean floor history have been preserved and consist of clinopyroxene porphyroclasts (probable igneous relicts from gabbro dykes) and Cr‐rich garnet and vesuvianite (relicts of ocean floor metasomatism). Petrological modelling using thermocalc in the NCFMASHTO system was used to constrain the P–T conditions of the S2 mineral assemblages. The inferred values of 2.3–2.8 GPa and 580–660 °C are consistent with those obtained for syn‐S2 assemblages in the surrounding serpentinites. Multiscale structural analysis indicates that some ocean floor minerals remained stable under eclogite facies conditions suggesting that minerals such as vesuvianite, which is generally regarded as a low‐P phase, could also be stable in favourable chemical systems under high‐P/ultra‐high‐pressure (HP/UHP) conditions. Finally, the reconstructed P–T–d–t path indicates that the P/T ratio characterizing the D2 stage is consistent with cold subduction as estimated in this part of the Alps. The estimated pressure‐peak values are higher than those previously reported in this part of ZSZ, suggesting that the UHP units are larger and/or more abundant than those previously suggested.     

Diatoms and silicoflagellates in suspension and floor sediments of the Pacific Ocean

In the eight climatic zones of the Pacific, a direct spatial-geographical correspondence is proved between density of diatom populations (together with the quantitatively unimportant associated silicoflagellates) and the relative abundance of their siliceous relics in sediments on the oceanic floor. This correspondence is almost ideal in the Subantarctic zone, demonstrable in the Subarctic zone and the equatorial belt, but is complicated (beyond recognition, in places) by terrigenic and other diluent materials and/or by the high solubility of the shells of certain species which never reach the ocean floor. There is no evidence of any significant drift of diatom relics during their sedimentation; the practical absence of diatoms, as in the Southern Subtropical zone, has its clear expression in the absence of their relics in the zonal sediments. — IGR Staff.     

Geochemical and mineralogical control of different genetic types of deep-sea nodules from the Pacific Ocean

Deep-sea nodules from the Northeast Pacific nodule belt and the Southeast Pacific (Sonne Basin), being formed in areas bordering the equatorial zone of high biological productivity, accumulate by two basically different growth processes: (A) early diagenetic growth by supply from pore water and (B) hydrogenetic growth by supply from near-bottom sea-water. These growth processes lead to different genetic types of nodules: early diagenetic type A, hydrogenetic type B, and mixed-type AB; a further type A_C, very rich in Mn, is being formed by increasing influence of early diagenesis. These types can clearly be distinguished by their shapes, surface textures, mineral constituents of oxide fraction, internal microstructures, and geochemistry. A genetical classification is being proposed on the basis of statistically computed interelement relationships. Todorokite, very poor in Fe, is the main Mn phase in the early diagenetic substance; -MnO₂ intimately intergrown with FeOOH · xH₂O is the main phase in the hydrogenetic substance. Consequently an important difference can be pointed out: the metal supply for the growth of the early diagenetic nodules is based on an ionic solution of Me²⁺ (e. g. Mn²⁺, Ni²⁺, Cu²⁺, Zn²⁺), whereas the supply for the hydrogenetic nodules is caused by transport of colloidal particles. Mobilization of Mn²⁺ and fractionation from Fe is controlled by the amount of decomposing organic matter in the "peneliquid" layer of the sediments. The main factor controlling the intensity of early diagenesis is the biological productivity in surface waters. The crucial "point of reversal" at a Mn/Fe ratio of about 5, obtained by hyperbolical regression of the analyses of nodules from the Southeast Pacific, represents best concentrations in Ni and Cu. Mn/Fe quotients greater than 5 cause a decrease of Ni and Cu content. Nodules from the Northeast Pacific nodule belt generally contain higher concentrations in Cu than nodules from the Southeast Pacific. This can be explained by an additional supply of Cu transported below CCD by siliceous plankton.     

High-temperature enthalpy at the orientational order-disorder transition in calcite: implications for the calcite/aragonite phase equilibrium

The enthalpy of calcite has been measured directly between 973 K and 1325 K by transposed-temperature- drop calorimetry. The excess enthalpy has been analysed in terms of Landau theory for this tricritical phase transition. The zero-point enthalpy and entropy allow estimates of the parameters a and C in the Landau expansion for free energy which expresses excess free energy G as a function of the order parameter Q and temperature T: G 1/2a(T _2c–T)Q ²+1/6CQ ⁶ with a=24 J·K·mol^-1, C = 30 kJ·mol^– T _c = 1260 ±5 K. The entropy of disorder below the transition has been formulated as a function of temperature allowing the calculation of the calcite/aragonite phase boundary when taking this extra entropy into account. There is remarkable agreement between the calculated equilibrium curve and previous experimental observations. The Landau theory predicts behaviour which fully accounts for the change in slope of the calcite/aragonite phase boundary, which is thus wholly due to the R¯3c –R¯3m transition in calcite.     

Controls on the distribution of rare earth elements in deep-sea sediments in the North Atlantic Ocean

Deep-sea sediments can contain relatively high concentrations of rare earth elements and yttrium (REY), with a growing interest in their exploitation as an alternative to land-based REY resources. To understand the processes that lead to enrichment of the REY in deep-sea sediments, we have undertaken a detailed geochemical study of sediments recovered from the Atlantic Ocean, on a transect along ~ 24°N that includes the deep Nares Abyssal Plain and the Canary and North America Basins.Total REY concentrations (ΣREY) range from 7.99 to 513 ppm, and total concentrations of the heavy REY (Eu - Lu) range from 0.993 to 56.3 ppm. REY concentrations are highest in slowly accumulating pelagic red clays, especially in samples that contain ferromanganese micronodules. Factor analysis reveals that hydrogenous Fe- and Mn-(oxyhydr)oxides are the primary REY carrier phase in the red clays. In situ analysis of individual micronodules confirms that they have high ΣREY (up to 3620 ppm). REY concentrations are higher in micronodules that have a hydrogenous source, characterised by higher Fe/Mn, compared to micronodules that have a diagenetic source.The ΣREY content of North Atlantic deep-sea sediments is ~ 4 times lower than in Pacific deep-sea sediments. We calculate that the area of seafloor required to extract ~ 10% of the global annual REY demand is ~ 100 km², assuming removal of the upper 1 m of sediment.