Alteration of volcanic matter in deep sea sediments: evidence from the chemical composition of interstitial waters from deep sea drilling cores

Six Deep Sea Drilling Project (DSDP) Sites (252, 285, 315, 317, 336, 386) were examined for the chemical composition of the dissolved salts in interstitial waters, the oxygen isotopic composition of the interstitial waters, and the major ion composition of the bulk solid sediments. An examination of the concentration-depth profiles of dissolved calcium, magnesium, potassium, and H₂¹⁸O in conjunction with oxygen isotope mass balance calculations confirms the hypothesis that in DSDP pelagic drill sites concentration gradients in Ca. Mg. K, and H₂¹⁸O are largely due to alteration reactions occurring in the basalts of Layer 2 and to alteration reactions involving volcanic matter dispersed in the sediment column. Oxygen isotope mass balance calculations require substantial alteration of Layer 2 (up to 25% of the upper 1000 m). but only minor exchange of Ca, Mg, and K occurs with the overlying ocean. This implies that alteration reactions in Layer 2 are almost isochemical.     

Geology and Geochemistry of Highly Metamorphosed Footwall Alteration Zones in the Hongtoushan Volcanogenic Massive Sulfide Deposit,Liaoning Province,China

The Hongtoushan Archean Cu–Zn volcanogenic massive sulfide (VMS) deposit, which was metamorphosed (3.0–2.8 Ga) to upper amphibolite facies at temperatures between 600 and 650°C, occurs in the Hunbei granite–greenstone terrane, Liaoning Province of NE China. Stratiform cordierite–anthophyllite gneiss (CAG) that occurs hundreds of meters below the ore horizon in the Hongtoushan district corresponds to the metamorphosed semi‐conformable alteration zone of the VMS hydrothermal system, whereas the CAG that contains abundant deformed sulfide‐bearing quartz veins immediately below the main ore layer represents the metamorphosed discordant alteration zone. Whole‐rock geochemistry indicates that stratiform CAG was derived ultimately from five lithologies (basalt, basaltic andesite, andesite, dacite, and rhyolite), while discordant CAG derived from a single lithology (rhyolite). Amphibolite and biotite‐rich gneiss are identified as a metamorphosed least‐altered precursor for these CAGs. Mass change calculation indicates that, compared to the least‐altered rocks, stratiform CAG is enriched in Fe and Mg, and depleted in Na, K, Ca, Cu, Pb and Zn, while discordant CAG is enriched in Fe, Mg, Si, Na, Pb, Cu and Zn, and depleted in K. HREE and HFSE (Zr, Ti, Nb and Ta) behaved inertly during submarine alteration, whereas Rb, Sr, Ba and LREE (especially Eu) were leached off. Both stratiform and discordant CAGs are depleted in ¹⁸O, with values up to 7‰ lower than their corresponding least‐altered precursors. Addition of Fe, Mg, and depletion of Ca, K, Sr, and ¹⁸O, indicate that hydrothermal alteration for both types of CAGs was characterized by chloritization prior to metamorphism. Stratiform CAG could be used to evaluate the mineralization potential of VMS in metamorphic terranes, while discordant CAG containing sulfide‐bearing quartz veins could be a good indication for overlying stratiform massive sulfide ores as well as an exploration target itself.     

Petrology, isotope geochemistry and chemical budgets of oceanic gabbros-seawater interactions in the Equatorial Atlantic

 Petrological and chemical variations, as well as oxygen and strontium isotopic data are presented for metagabbros from the Romanche and Vema fracture zones. These rocks were affected by several types and degrees of alterations ranging from slight hydrothermal alteration to complete amphibolitization. Five major kinds of alteration processes ranging from late-magmatic deuteric alteration (stage I) to low temperature (<150 °C) alteration (stage V) were identified. Water-rock interactions between 300 and 650 °C are the most dominant interactions resulting in the most prevailing secondary mineralogical assemblages which characterize the amphibolite and/or greenschist facies (amphibole ± plagioclase ± epidote ± titanite ± chlorite ± prehnite). Hydrothermal alteration of these gabbroic rocks results in isotopic exchanges between rocks and seawater-derived fluids. These exchanges lead to decrease of gabbroic δ¹⁸O toward values as low as +3.9‰, and larger Sr isotopic variations than other oceanic gabbroic rocks (⁸⁷Sr/⁸⁶Sr ratios shift to 0.7029–0.7051). Calculation of a chemical budget indicates that metagabbros are hydrated and enriched in Fe and probably in Mg and Cl, while Si, Ca and Ti are released to the hydrothermal fluids. In addition to metamorphic recrystallization and geochemical transformation, hydrothermal alteration of oceanic gabbros contributes to the control of the global ocean geochemistry. Received: 8 March 1999 / Accepted: 12 July 1999     

High precision measurements of Mg/Ca and Sr/Ca ratios in carbonates by cold plasma inductively coupled plasma quadrupole mass spectrometry

We present a new high precision analytical method for the determination of Mg/Ca and Sr/Ca ratios in carbonates using an inductively coupled plasma quadrupole mass spectrometer (ICP-QMS) with a 650-W cold plasma technique and a desolvation introduction system. Signal intensities are detected in pulse-counting mode and Mg/Ca and Sr/Ca ratios are calculated directly from intensity ratios of ²⁴Mg/⁴³Ca and ⁸⁶Sr/⁴³Ca using external matrix-matched standards for every 4–5 samples to correct for instrumental mass discrimination and low-frequency ratio drift. Significant matrix effect of Ca content on Mg/Ca determination (− 0.018 Mg/Ca (mmol/mol)/[Ca] (ppm)), can be overcome by diluting [Ca] to 6–8 ppm in the sample solution or using an empirical correction. The Sr/Ca ratio affects the Mg/Ca determination, with a factor of − 0.32% Mg/Ca per mmol/mol. This is mainly caused by the influence of doubly charged ⁸⁶Sr, which biases the intensity measurement of the ⁴³Ca⁺ ion beam. This effect results in a trivial offset of less than 0.1% on Mg/Ca measurements for Quaternary foraminiferal and coral samples. The internal precision of our method ranges from 0.1 to 0.2%. Replicate measurements made on standards and samples show long-term external uncertainties (2σ) of Mg/Ca = 0.84% and Sr/Ca = 0.49%. The minimum sample size requirement is only 3.5 μg of carbonate. The application of this newly developed technique on the planktonic foraminifera Globigerinoides ruber from a core recovered in the southern South China Sea yields a glacial–interglacial difference in sea surface temperature (SST) of 3 °C. Three-year coral Sr/Ca data suggest that the seasonal SST ranged from 22.6–23.8 °C in winter to 26.9–27.9 °C in summer in Nanwan, south Taiwan, during 2000–2002. The coral-Sr/Ca inferred SSTs in 2002 match well with instrumental records, which demonstrates the validity of this ICP-QMS method.     

The formation of high temperature clay minerals from basalt alteration during hydrothermal discharge on the East Pacific Rise axis at 21°N

Aluminous, high-temperature clay minerals form from alteration of tholeiitic basaltic glass and calcic plagioclase during hydrothermal venting on the crest of the East Pacific Rise at 21°N. The clay alteration assemblages are layered crusts (up to 1 mm thick) completely replacing glass and calcic plagioclase adjacent to surfaces exposed to hydrothermal fluids. The interiors of the affected basalt samples have unaltered appearances and oxygen isotopic compositions just slightly heavier than that of MORB. The surficial alteration crusts are mixtures of beidellitic smectite (aluminous, dioctahedral), randomly interstratified mixed-layer Al-rich chlorite/smectite, minor chlorite, an x-ray amorphous aluminosilicate material, and possible minor serpentine (amesite). A δ¹⁸O value of +4.1 ± 0.2%. (SMOW) is determined for the beidellitic smectite. Assuming that this smectite equilibrated with hydrothermal fluid having an oxygen isotope value between that of seawater (0%.) and 350°C hydrothermal fluid from EPR, 21°N vents (+1.6%.), an equilibration temperature between 290°C and 360°C is calculated for the beidellitic smectite. This is substantially higher than any previously reported temperature for an oceanic smectite. The mixed-layer Al-rich chlorite/smectite has a δ¹⁸O value of +3.5%., which corresponds to equilibration at 295°–360°C. The aluminous composition of the alteration assemblage is uncommon for clay minerals produced by submarine hydrothermal basalt alteration. We suggest that this assemblage is largely the product of high-temperature interaction between basalt glass + plagioclase and Mg-poor, acidic hydrothermal fluids, with possibly some contribution of Mg from bottom seawater, and that the aluminous clays either incorporate Al³⁺ remobilized from basalt by lowpH hydrothermal fluids, or are residual phases remaining after intense alteration of basaltic glass + plagioclase.     

Petrogenesis and mantle source characteristics of the late Cenozoic Baekdusan (Changbaishan) basalts,North China Craton

Late Cenozoic intraplate basaltic rocks in northeastern China have been interpreted as being derived from a mantle source composed of DMM and EM1 components. To constrain the origin of the enriched mantle component, we have now determined the geochemical compositions of basaltic rocks from the active Baekdusan volcano on the border of China and North Korea. The samples show LREE-enriched patterns, with positive Eu and negative Ce anomalies. On a trace element distribution diagram, they show typical oceanic island basalt (OIB)-like LILE enrichments without significant Nb or Ta depletions. However, compared with OIB, they show enrichments in Ba, Rb, K, Pb, Sr, and P. The Nb/U ratios are generally within the range of OIB, but the Ce/Pb ratios are lower than those of OIB. Olivine phenocrysts are characterized by low Ca and high Ni contents. The radiogenic isotopic characteristics (⁸⁷Sr/⁸⁶Sr = 0.70449 to 0.70554; ε_Nd = −2.0 to +1.8; ε_Hf = −1.7 to +6.1; ²⁰⁶Pb/²⁰⁴Pb = 17.26 to 18.12) suggest derivation from an EM1-like source together with an Indian MORB-like depleted mantle. The Mg isotopic compositions (δ²⁶Mg = −0.39 ± 0.17‰) are generally lower than the average upper mantle, indicating carbonates in the source. The ⁸⁷Sr/⁸⁶Sr ratios decrease with decreasing δ²⁶Mg values whereas the ¹⁴³Nd/¹⁴⁴Nd and (Nb/La)_N ratios increase. These observations suggest the mantle source of the Baekdusan basalts contained at least two components that resided in the mantle transition zone (MTZ): (1) recycled subducted ancient (∼2.2–1.6 Ga) terrigenous silicate sediments, possessing EM1-like Sr–Nd–Pb–Hf isotopic signatures and relatively high values of δ²⁶Mg; and (2) carbonated eclogites with relatively MORB-like radiogenic isotopic compositions and low values of δ²⁶Mg. These components might have acted as metasomatizing agents in refertilizing the asthenosphere, eventually influencing the composition of the MTZ-derived plume that produced the Baekdusan volcanism.     

Evolution of a hydrothermal fluid-rock interaction system as recorded by Sr isotopes: A case study from the Schwarzwald, SW Germany

Metasomatic and Sr-isotopic changes, associated with formation of zoned alteration halos along hydrothermal veins, are documented for a gneiss from the Artenberg quarry near Steinach (Kinzigtal, Schwarzwald, SW Germany). Veins are postorogenic, SW-NE-oriented, and cut straight through metaquartzdioritic Variscan gneiss, where flow of low-temperature fluids (～100–200°C) caused adularia-quartz-sericite-type alteration. Fluid-rock interaction occurred nearly 50 Ma after Variscan metamorphism, as constrained by a Rb–Sr multimineral isochron for unaltered gneiss of 327.1?±?3.1 Ma, and by two independent ages of 279.2?±?3.1 Ma and 274?±?13 Ma, based on Rb–Sr systematics of late-stage quartz from the veins. In a profile from unaltered gneiss towards a vein, alteration-induced mineralogical changes correlate with metasomatic net addition of K, Rb, and Cl to the alteration zone, combined with net loss of Na, Ca, and Sr. Strontium isotopes give a more detailed insight into the fluid-rock interaction process. ⁸⁷Sr/⁸⁶Sr ratios in a profile across the alteration zone are incompatible with simple Sr leaching but reflect partial replacement of the rocks’ Sr by fluid-derived Sr, the isotopic composition of which varied with time. Early fluids, with high ⁸⁷Sr/⁸⁶Sr ratios compared to unaltered gneiss, evolved into fluids with somewhat lower ratios, and finally reached a second maximum in ⁸⁷Sr/⁸⁶Sr ratios. This Sr-isotopic fluid evolution is equally revealed by the mineral sequence of the vein mineralization. It appears that the compositional evolution of the fluids correlates with the sequence of mineral breakdown reactions in the gneissic host rock, and that the Sr-isotopic evolution of the fluids can be fully explained as the result of internal, progressive reaction of fluid with the local rocks. Results also show that the spatial distributions of Sr isotopes in metasomatic alteration zones may reflect the complex evolution of fluid-rock interaction systems, and ultimately constrain the factors controlling both fluid compositions and alteration patterns.     

Partition of Sr,Ba, Ca,Y, Eu2+, Eu3+, and other REE between plagioclase feldspar and magmatic liquid: an experimental study

Plagioclase feldspar/magmatic liquid partition coefficients for Sr, Ba, Ca, Y, Eu²⁺, Eu³⁺ and other REE have been determined experimentally at 1 atm total pressure in the temperature range 1150–1400°C. Natural and synthetic melts representative of basaltic and andesitic bulk compositions were used, crystallizing plagioclase feldspar in the composition range An₃₅–An₈₅. Partition coefficients for Sr are greater than unity at all geologically reasonable temperatures, and for Ba are less than unity above approximately 1060°C. Both are strongly dependent upon temperature. Partition coefficients for the trivalent REE are relatively insensitive to temperature. At fixed temperature they decrease monotonically from La to Lu. The partition of Eu is a strong function of oxygen fugacity. Under extreme reducing conditions D_Eu approaches the value of D_Sr.     

Ostracod Mg/Sr/Ca and 87Sr/86Sr geochemistry from Tibetan lake sediments: Implications for early to mid‐Pleistocene Indian monsoon and catchment weathering

Jin, Z. D., Bickle, M. J., Chapman, H. J., Yu, J., An, Z., Wang, S. & Greaves, M. J. 2010: Ostracod Mg/Sr/Ca and ⁸⁷Sr/⁸⁶Sr geochemistry from Tibetan lake sediments: Implications for early to mid‐Pleistocene Indian monsoon and catchment weathering. Boreas, 10.1111/j.1502‐3885.2010.00184.x. ISSN 0300‐9483 Lacustrine sediment serves as a valuable archive for tracing catchment weathering processes associated with past climatic and/or tectonic changes. High‐resolution records of fossil ostracod Mg/Ca, Sr/Ca and ⁸⁷Sr/⁸⁶Sr ratios from a lake sediment core from the central Tibetan Plateau reveal a temporal link between lake‐water chemistry and catchment weathering and distinct monsoonal oscillations over the early to mid‐Pleistocene. Between 2.01 and 0.95 Ma, lake‐water chemistry was dominated by a high proportion of carbonate weathering related to variations in the Indian monsoon, resulting in relatively low and constant ostracod ⁸⁷Sr/⁸⁶Sr but obvious fluctuations in Mg/Ca, Sr/Ca and δ¹⁸O. Across the mid‐Pleistocene transition (MPT), a significant increase in ⁸⁷Sr/⁸⁶Sr and frequently fluctuating ratios of ostracod Mg/Ca, Sr/Ca and δ¹⁸O are coincident with increases in both Chinese loess grain size and Arabian Sea lithogenic flux. This correlation indicates an increased glaciation and a strong monsoon seasonal contrast over the plateau. The increase in lake‐water ⁸⁷Sr/⁸⁶Sr across the MPT highlights a change in catchment weathering patterns, rather than one in climate‐enhanced weathering intensity, with an increased weathering of ⁸⁷Sr‐rich minerals potentially induced by marked extensive glaciation and strong seasonality in the central plateau.     

Major cation gradients in DSDP interstitial waters: the role of diffusive exchange between seawater and upper oceanic crust

Interstitial water analyses from DSDP Legs 1–53 were surveyed to identify sites at which the dominant process supporting gradients of major seawater cations is alteration of the underlying oceanic crust. Sites with thin sediment cover are generally without gradients: sites with appreciable sediment accumulation are generally with gradients. The transition is probably the result of cessation of convective circulation within the sediments. A model is developed for the diffusive flux through an accumulating, unreactive sedimentary layer supported by continued reaction within the crust. The model is consistent with the observations provided that convection within the crust extends to depths > 1 km and that convective flow within the sediments ends once 100–150 m of sediment accumulates. The model suggests a steady state gradient inversely proportional to the sedimentation rate: this dependence is apparent in the data, however, some variation in the reaction rate is also required. Fluxes of Mg and Na are systematically related to the flux of Ca which because of its mobility serves as a tracer of hydrolysis of the basalt. When the Ca flux is low, the Mg flux serves as the principal sink for alkalinity produced during basalt hydrolysis. When the Ca flux is high, the Mg flux becomes diffusion-limited and Nabearing alteration phases must form. The fluxes resulting from these alteration reactions exert little influence on either the chemistry of seawater or that of the upper crust.     

Role of Subsurface Brines in Salt Balance: The Case Study of the Caspian Sea and Kara Bogaz Bay

The water level of the Caspian Sea fluctuated significantly during recent history, without consensus for the cause. The varied chemistry of the Caspian, Kara Bogaz and sediment a interstitial waters provides a further insight. Element concentrations and ⁸⁷Sr/⁸⁶Sr ratios of the interstitial waters were compared to those of Caspian and Kara Bogaz open waters, and of acid-leached extractable components. The ⁸⁷Sr/⁸⁶Sr ratios of the interstitial waters are explained by addition of subterranean waters similar to nearby spring waters. These subterranean waters yield chemical characteristics such as a Cl/SO₄, ⁸⁷Sr/⁸⁶Sr, Ca/Sr and K/Rb ratios of respectively 80, 0.7086, 250 and 1,800. However, their addition does not explain the large difference in the K/Rb ratio of the Caspian and Kara Bogaz waters, respectively at 7,630 and 17,550, which implies also a leaching of salt deposits by the upward migrating subterranean waters. The sediments of the southern Caspian basin, with low Na, Cl and SO₄ in their interstitial waters, deposited apparently in an anoxic environment. The related chemical changes in the waters are also indicative of a recent change in the hydrologic regime, possibly induced by a changing morphology of the drainage basin.     

Mantle metasomatism and magma formation in continental lithosphere: Data on xenoliths in alkali basalts from the Makhtesh Ramon,Negev desert,Israel

Mantle xenoliths (lherzolites, clinopyroxene dunites, wehrlites, and clinopyroxenites) in the Early Cretaceous volcanic rocks of Makhtesh Ramon (alkali olivine basalts, basanites, and nephelinites) represent metasomatized mantle, which served as a source of basaltic melts. The xenoliths bear signs of partial melting and previous metasomatic transformations. The latter include the replacement of orthopyroxene by clinopyroxene in the lherzolites and, respectively, the wide development of wehrlites and olivine clinopyoroxenites. Metasomatic alteration of the peridotites is accompanied by a sharp decrease in Mg, Cr, and Ni, and increase of Ti, Al, Ca contents and ³⁺Fe/²⁺Fe ratio, as well as the growth of trace V, Sc, Zr, Nb, and Y contents. The compositional features of the rocks such as the growth of ³⁺Fe/²⁺Fe and the wide development of Ti-magnetite in combination with the complete absence of sulfides indicate the high oxygen fugacity during metasomatism and the low sulfur concentration, which is a distinctive signature of fluid mode during formation of the Makhtesh Ramon alkali basaltic magma. Partial melting of peridotites and clinopyroxenites is accompanied by the formation of basanite or alkali basaltic melt. Clino- and orthopyroxenes are subjected to melting. The crystallization products of melt preserved in the mantle rock are localized in the interstices and consist mainly of fine-grained clinopyroxene, which together with Ti-magnetite, ilmenite, amphibole, rhenite, feldspar, and nepheline, is cemented by glass corresponding to quartz–orthopyroxene, olivine–orthopyroxene, quartz–feldspar, or nepheline–feldspar mixtures of the corresponding normative minerals. The mineral assemblages of xenoliths correspond to high temperatures. The high-Al and high-Ti clinopyroxene, calcium olivine, feldspar, and feldspathoids, amphibole, Ti-magnetite, and ilmenite are formed at 900–1000°. The study of melt and fluid inclusions in minerals from xenoliths indicate liquidus temperatures of 1200–1250°C, solidus temperatures of 1000–1100°C, and pressure of 5.9–9.5 kbar. Based on the amphibole–plagioclase barometer, amphibole and coexisting plagioclase were crystallized in clinopyroxenites at 6.5–7.0 kbar.     

Sub-volcanic infiltration and syn-eruptive quenching of liquids in cumulate wall-rocks: the example of the gabbroic nodules of Stromboli (Aeolian Islands, Italy)

Summary ¶Fine- to coarse-grained plutonic nodules within the Petrazza pyroclastics (Paleo-Stromboli I period) consist of gabbroic rocks with variable amounts of interstitial material. They are characterised by cumulate textures and low pressure modal mineralogy formed by plagioclase (An_96–87)+clinopyroxene (Mg-v 82–94)+olivine (Fo_83–74)±amphibole±opaque minerals; the interstitial material consists of newly crystallised microlites (quenching) of plagioclase (An_73–55)+amphibole+clinopyroxene±olivine±biotite±opaques and highly variable amounts of residual glasses that range in composition from shoshonite and high-K basaltic andesite to high-K andesite and latite. The interstitial material has a relatively high but variable degree of vesicularity. The whole rock incompatible element abundances are lower than – but the patterns are typical of – in subduction related magmas and the incompatible trace-elements are well correlated with the amount of the interstitial material. The Sr, Pb and Nd isotopic ratios resemble those of the extrusive rocks of Stromboli older series and the mineral chemistry of the gabbros is similar to that of the HKCA Paleo-Stromboli lavas. Modal mineralogy, mineral chemistry and chemical-isotopic whole rock compositions suggest that the cumulus portions of the gabbroic nodules crystallised from basaltic magmas compositionally compatible with those erupted by Stromboli volcano. The interstitial material does not represent the residual liquid after in situ crystallisation of the gabbros; it is also distinct from the juvenile host andesite magma. Textural evidence, Fe–Mg mineral/liquid partioning and mass balance calculations indicate that the interstitial material (quench crystals and vesicular glass) derived from infiltrated hydrous basaltic liquid undercooling and vesiculation of which occurred during the eruption of the Petrazza pyroclastics.Received April 17, 2002; revised version accepted November 14, 2002 Published online June 2, 2003     

Geochemistry and provenance of bed sediments of the large rivers in the Tibetan Plateau and Himalayan region

We investigated the geochemical characteristics of major, trace and rare earth elements and Sr–Nd isotope patterns of bed sediments from the headwaters and upper reaches of the six large rivers draining the Tibetan Plateau (the Jinsha River—Yangtze, Lancang River—Mekong, Nujiang River—Salween, Huang He—Yellow, Indus, and Yarlung Tsangpo—Brahmaputra). By using Ca/Al versus Mg/Al, La/Sc versus Co/Th, and ⁸⁷Sr/⁸⁶Sr versus ε_Nd (0) binary differentiation diagrams of provenance, some typical contributors to the different catchment sediments can be identified. In the Three-River (the Jinsha, Lancang, and Nujiang Rivers) tectonomagmatic belt, acidic–intermediate-acidic volcanic rocks are very important provenance of sediments. Carbonate rocks and Permian Emeishan basalts are dominant in the Jinsha River. The Yellow River sediments have similar geochemical characteristics with loess in catchments. The Indus and Yarlung Tsangpo Rivers sediments are mainly from ultra-K volcanic rocks and Cenozoic granitoids widely distributed in the Indus–Yarlung suture. The intensity of chemical weathering in these river catchments is evaluated by calculating the chemical indices of alteration (CIA) of sediments and comparing them with bedrocks. The CIA values of the six river sediments are from 46.5 to 69.6, closing to those of bedrocks in the corresponding catchment, which indicates relatively weak chemical weathering intensity. Lithology, climate, and topography affect the chemical weathering intensity in these river catchments.     

Geochemical fingerprints of dolomitization in Bahamian carbonates: Evidence from sulphur,calcium, magnesium and clumped isotopes

In an effort to constrain the mechanism of dolomitization in Neogene dolomites in the Bahamas and improve understanding of the use of chemostratigraphic tracers in shallow‐water carbonate sediments the δ³⁴S, Δ₄₇, δ¹³C, δ¹⁸O, δ^44/40Ca and δ²⁶Mg values and Sr concentrations have been measured in dolomitized intervals from the Clino core, drilled on the margin of Great Bahama Bank and two other cores (Unda and San Salvador) in the Bahamas. The Unda and San Salvador cores have massively dolomitized intervals that have carbonate associated sulphate δ³⁴S values similar to those found in contemporaneous seawater and δ^44/40Ca, δ²⁶Mg values, Sr contents and Δ₄₇ temperatures (25 to 30°C) indicating relatively shallow dolomitization in a fluid‐buffered system. In contrast, dolomitized intervals in the Clino core have elevated values of carbonate associated sulphate δ³⁴S values indicating dolomitization in a more sediment‐buffered diagenetic system where bacterial sulphate reduction enriches the residual in ³⁴S, consistent with high sediment Sr concentrations and low δ^44/40Ca and high δ²⁶Mg values. Only dolomites associated with hardgrounds in the Clino core have carbonate associated δ³⁴S values similar to seawater, indicating continuous flushing of the upper layers of the sediment by seawater during sedimentary hiatuses. This interpretation is supported by changes to more positive δ^44/40Ca values at hardground surfaces. All dolomites, whether they formed in an open fluid‐buffered or closed sediment‐buffered diagenetic system have similar δ²⁶Mg values suggesting that the HMC transformed to dolomite. The clumped isotope derived temperatures in the dolomitized intervals in Clino yield temperatures that are higher than normal, possibly indicating a kinetic isotope effect on dolomite Δ₄₇ values associated with carbonate formation through bacterial sulphate reduction. The findings of this study highlight the utility of applying multiple geochemical proxies to disentangle the diagenetic history of shallow‐water carbonate sediments and caution against simple interpretations of stratigraphic variability in these geochemical proxies as indicating changes in the global geochemical cycling of these elements in seawater.     

豫西鸡冠洞洞穴水及现代沉积物Mg, Sr和Ba记录及其意义

采用电感耦合等离子体质谱仪（ICP-MS）和电感耦合等离子体光谱仪（ICP-OES）对2009年12月-2013年8月采自河南省栾川县鸡冠洞洞穴水（滴水、池水及地下河水）和现代碳酸盐沉积物的 Ca、Mg、Sr和 Ba 微量元素地球化学指标进行了分析。结果显示：（1）鸡冠洞洞穴水的 Mg/Ca对地表环境的干湿条件变化响应迅速,具体表现为池水和地下河水 Mg/Ca旱季高而雨季低,而 Sr/Ca 和Ba/Ca的变化与降水和气温的关系并不明显;（2）鸡冠洞现代沉积物的 Mg/Ca 变化与滴水有着良好的对应关系,但现代沉积物的 Sr/Ca和 Ba/Ca可能受大气粉尘活动和地表土壤的影响,变化趋势与 Mg/Ca 相反;（3）鸡冠洞碳酸盐岩与岩溶水间 Sr/Ca和 Mg/Ca的分配系数KSr值在0.02-0.18之间,KMg值在0.01-0.03之间,KMg值与洞穴温度的正相关关系不明显。     

Origin of atoll dolomites distinguished by geochemistry and crystal chemistry: Kita-daito-jima,northern Philippine Sea

Kita-daito-jima is a carbonate island located at the northwestern region of the Philippine Sea (25°55.6′–57.6′N, 131°16.9′–19.8′E). Dolomites extend from the island surface to a depth of 100 m below the ground surface (mbgs). Strontium isotope stratigraphy indicates that subsurface Units C1 (0–49.7 mbgs) and C2 (49.7–103.4 mbgs) were dolomitized at 5.5 Ma and 2.0 Ma, respectively, and that island-surface dolomites are products of dolomitization at 1.6–2.0 Ma. X-ray diffraction analysis indicates that the island-surface and borehole dolomites comprise variable mixtures of four and three dolomite crystal phases, respectively. Each of these phases is distinguished by a different Ca and Mg content. Three textural types can be recognized in the Kita-daito-jima dolomites, fabric-preserving crystalline nonmimetic (CNM), crystalline mimetic (CM), and fabric-preserving microsucrosic (MS). CNM dolomites contain more calcian phases, whereas MS dolomites commonly are richer in more stoichiometric phases. Backscattered electron images indicate that calcian dolomite phases were precipitated earlier than the more stoichiometric dolomite phases and that there is no significant hiatus between the phases, although they are diachronous. Both the island surface and borehole cores dolomites show linear relationships between whole-rock δ¹⁸O composition and Mg contents and between whole-rock trace element concentrations (Sr and Na) and Mg contents. These covariances result from phase mixing, not stoichiometric effects. Deconvolution of whole-rock isotopic and elemental compositions based on the relative abundance of phases reveals that each phase has a distinct chemical and isotopic composition. Oxygen isotopic compositions of the island surface and borehole dolomites suggest that all dolomite phases formed in seawater and that dolomitization primarily occurred during glacio-eustatic sea-level lowstands and cooler ocean temperatures.     

Unique Clinkers and Paralavas from a New Nyalga Combustion Metamorphic Complex in Central Mongolia: Mineralogy,Geochemistry, and Genesis

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.     

Acid-sulphate Type Alteration and Mineralization in the Desmos Caldera, Manus Back-arc Basin, Papua New Guinea

Abstract: The Onsen acid‐sulphate type of mineralization is located in the Desmos caldera, Manus back‐arc basin. Hydrothermal precipitates, fresh and altered basaltic andesite collected from the Desmos caldera were studied to determine mineralization and mobility of elements under seawater dominated condition of hydrothermal alteration. The mineralization is characterized by three stages of advanced argillic alteration. Alteration stage I is characterized by coarse subhedral pyrophyllite with disseminated anhedral pyrite and enargite which were formed in the temperature range of 260–340°C. Alteration stage II which overprinted alteration stage I was formed in the temperature range of 270–310°C and is characterized by euhedral pyrite, quartz, natroalunite, cristobalite and mixed layer minerals of smectite and mica with 14–15 Å XRD peak. Alteration stage III is characterized by amorphous silica, native sulphur, covellite, marcasite and euhedral pyrite, which has overprinted alteration stages I and II. Relative to the fresh basaltic andesite samples, the rims and cores of the partly altered basaltic andesite samples have very low major, minor and rare earth elements content except for SiO₂ which is much higher (58–78 wt%) than SiO₂ content of the fresh basaltic andesite (55 wt%). REE patterns of the partly altered basaltic andesite specimens are variably depleted in LREE and have pronounced negative Eu anomalies. Normalization of major, minor and REE content of the partly altered basaltic andesites to the fresh basaltic andesite indicates that all the elements except for SiO2 in the partly altered basaltic andesite are strongly lost (e.g. Al₂O₃ = ‐8.3 to ‐10.9 g/100cm³, Ba = ‐2.2 to ‐5.6 mg/100cm³, La = ‐130 to ‐200 μg/100cm³) during the alteration process. Abnormal depletion of MgO, total Fe as Fe₂O₃, LREE especially Eu and enrichment of SiO₂ in the altered basaltic andesites from the Desmos caldera seafloor is caused by interaction of hot acidic hydrothermal fluid, which originates from a mixing of magmatic fluid and seawater.     

Lithogeochemistry of wainaleka Cu-Zn volcanogenic deposit, Viti Levu, Fiji, and possible applications for exploration in tropical terrains

A small Kuroko-type Cu-Zn deposit exhibiting metal zoning and alteration assemblages comparable with documented proximal volcanogenic deposits, occurs at the top of a felsic fragmental pile, mantling a large sodic rhyolite domal complex. The domal complex occurs within predominantly mafic to intermediate lavas and volcaniclastic rocks with low-potash island-arc tholeiitic affinities, representing the basal section of the early Tertiary (Eocene to middle Miocene) Wainimala Group near the southern coast of Viti Levu, Fiji.Lithogeochemical trends identified in analyses of rock chip samples from traverses across the domal complex reflect alteration zoning. Sodium, Ca and Sr are strongly depleted within the quartz-sericite foot-wall alteration zone (Zone I) 200 m below mineralization. Potassium, Rb and weaker Mn, Zn and Co depletion and Cu, Pb and Mg enrichment define clay-sericite (Zone II) and clay carbonate (Zone III) footwall alteration 600 to 1200 m below mineralization. Hanging-wall albite-chlorite-calcite-zeolite alteration (Zone IV) is accompanied by enhanced Zn, Pb, Co, Mn, Sr and Na values.Significant mine-scale lithogeochemical trends obtained from systematic sampling of a mineralized borehole section include K and Rb enrichment in the zone of strongest quartz-sericite alteration associated with mineralization and broad depletion of Mn, Na, Ca and Sr within altered footwall fragmental rocks. Minor Cu, Pb, Zn and Ag enrichment has accompanied low-grade propylitic alteration of hanging-wall rocks up to 50 m above mineralization. Analysis of weathered bedrock samples from traverses above the mineralized borehole section indicates that primary geochemical trends occur in the weathered zone. Outcropping gossan has strongly anomalous Cu (535 ppm-21.5%), Zn (3300 ppm-6.15%), Pb (420–8200 ppm), As (200–7000 ppm) and Hg (33–670 ppm) values.Application of lithogeochemistry as a follow-up exploration method in a tropical area such as Wainaleka was investigated as a possible replacement for ridge, spur and base-of-slope soil sampling techniques. Ridge-top auger samples and creek outcrop samples were collected at approximately 100 m intervals and a density of 70/km². Elements (including Cu, Pb, Zn, Mn, Rb, Sr, Na, K, Ca and Mg) were selected for analysis because of specific associations with mineralization and alteration, and low analytical costs. Single- and multi-element dispersions effectively outline mineralization and attendant alteration.