Microbial remains in some earliest Earth rocks: Comparison with a potential modern analogue

Carbonaceous matter (CM) from ca. 3.5 Ga hydrothermal black cherts of the Pilbara Craton of Western Australia and the Barberton Greenstone Belt of South Africa yielded transmission electron microscopy (TEM) images that are suggestive of microbial remains and possible remnants of microbial cell walls. These are compared to a potential modern analogue, the hyperthermophilic Methanocaldococcus jannaschii, derived from an active seafloor hydrothermal environment and cultured under similar conditions. A striking resemblance to the early Archaean forms was evident in wall structure and thermal degradation mode. Cell disintegration of the cultures occurred at 100 °C marking the limits of life. Complete disintegration, deformation and shrinkage occurred at 132 °C. A multidisciplinary approach to the characterisation of the CM was undertaken using organic petrology, TEM coupled with electron dispersive spectral analysis (EDS), high resolution TEM (HRTEM) to determine molecular ordering, and elemental and carbon isotope geochemistry. Reflectance measurements of the CM to determine thermal stress yielded a range of values corresponding to several populations, and pointing to different sources and processes. The δ¹³C values of Dresser Formation CM (−36.5 to −32.1‰) are negatively correlated with TOC (0.13–0.75%) and positively correlated with C/N ratio (134–569), which is interpreted to reflect the relative abundance of high R_o/oxidised/recycled CM and preferential loss of ¹²C and N during thermal maturation. TEM observations, inferred carbon isotopic heterogeneity and isotope fractionations of −27 to −32‰ are consistent with the activity of chemosynthetic microbes in a seafloor hydrothermal system where rapid silicification at relatively low temperature preserved the CM.     

Vendian stage in formation of the Early Caledonian superterrane in Central Asia

Granitoids and metamorphic rocks of the Baidarik basement block of the Dzabkhan microcontinent are studied in terms of geology, geochronology (U-Pb dating of zircon microfractions and individual grains) and Nd isotopic-geochemical systematics. As is established, the formation history of metamorphic belt (disthene-sillimanite facies) in junction zone of the Baidarik block and Bayankhongor zone of the Late Riphean (～665 Ma) ophiolite association characterizes development of the Vendian (～560–570 Ma) active continental margin. The high-P metamorphic rocks of that time span evidence formation of structures with the Earth’s crust of considerable thickness. In Central Asia, events of the Vendian low-gradient metamorphism are established also in the Tuva-Mongolian massif, Kan block of the East Sayan Mountains, and South Chuya inlier of the Caledonides in the Altai Mountains. Based on these data, it is possible to distinguish the Late Baikalian stage in development of the Early Caledonian superterrane of Central Asia, which antedated the subsequent evolution of this structure during the Late Cambrian-Ordovician. The high-gradient metamorphism that affected most intensively the southeastern part of the Baidarik block can be correlated with the Early Paleozoic (525–540 Ma) evolution of active continental margin and associated development of the Vendian oceanic basins and island arcs of the Ozernaya zone.     

Identification of the origin of salinization in groundwater using multivariate statistical analysis and geochemical modeling: a case study of Kaohsiung,Southwest Taiwan

The study of brine aquifers in southern Taiwan is highly complicated by hybrid geochemical reactions, which obscure important geochemical information. Using multivariate analysis on major and minor ion compositions normalized by Cl⁻ content, chemical constituents were combined into two principal components representing brine mixing and mineral precipitation. Comparing to multivariate analysis on the original data, this procedure reveals more geochemical information. It demonstrates that the brine groundwater of the region is primarily composed of highly evaporated seawater. The evaporation ratio is >70%; a point at which calcite, dolomite and gypsum precipitate. Oxygen and hydrogen isotopic compositions confirm this inference; and further, geochemical modeling quantitatively determined the evaporation ratio to be about 85%. Natural boron contamination is a consequence of brine groundwater. Two evolutionary trends in the plotting of the Cl/B ratio versus Cl⁻ can be identified: (1) Cl/B ratio decreases with boron being released from clay minerals when brine aquifers are flushed with freshwater; and (2) Cl/B ratio increases when seawater of a high Cl/B ratio infiltrates coastal aquifers.     

Timing and cause of water level fluctuations in Kluane Lake, Yukon Territory, over the past 5000 years

We reconstructed late Holocene fluctuations of Kluane Lake in Yukon Territory from variations in bulk physical properties and carbon and nitrogen elemental and isotopic abundances in nine sediment cores. Fluctuations of Kluane Lake in the past were controlled by changes in climate and glaciers, which affected inflow of Slims and Duke rivers, the two largest sources of water flowing into the lake. Kluane Lake fluctuated within a narrow range, at levels about 25 m below the present datum, from about 5000 to 1300 cal yr BP. Low lake levels during this interval are probably due to southerly drainage of Kluane Lake to the Pacific Ocean, opposite the present northerly drainage to Bering Sea. Slims River, which today is the largest contributor of water to Kluane Lake, only rarely flowed into the lake during the period 5000 to 1300 cal yr BP. The lake rose 7-12 m between 1300 and 900 cal yr BP, reached its present level around AD 1650, and within a few decades had risen an additional 12 m. Shortly thereafter, the lake established a northern outlet and fell to near its present level.     

Origin and Evolution of Silicic Magmatism at Yellowstone Based on Ion Microprobe Analysis of Isotopically Zoned Zircons

The origin of large-volume Yellowstone ignimbrites and smaller-volumeintra-caldera lavas requires shallow remelting of enormous volumesof variably ¹⁸O-depleted volcanic and sub-volcanic rocks alteredby hydrothermal activity. Zircons provide probes of these processesas they preserve older ages and inherited ¹⁸O values. This studypresents a high-resolution, oxygen isotope examination of volcanismat Yellowstone using ion microprobe analysis with an averageprecision of ± 0·2 and a 10 µm spot size.We report 357 analyses of cores and rims of zircons, and isotopeprofiles of 142 single zircons in 11 units that represent majorYellowstone ignimbrites, and post-caldera lavas. Many zirconsfrom these samples were previously dated in the same spots bysensitive high-resolution ion microprobe (SHRIMP), and all zirconswere analyzed for oxygen isotope ratios in bulk as a functionof grain size by laser fluorination. We additionally reportoxygen isotope analyses of quartz crystals in three units. Theresults of this work provide the following new observations.(1) Most zircons from post-caldera low-¹⁸O lavas are zoned,with higher ¹⁸O values and highly variable U–Pb ages inthe cores that suggest inheritance from pre-caldera rocks exposedon the surface. (2) Many of the higher-¹⁸O zircon cores in theselavas have U–Pb zircon crystallization ages that postdatecaldera formation, but pre-date the eruption age by 10–20kyr, and represent inheritance of unexposed post-caldera sub-volcanicunits that have ¹⁸O similar to the Lava Creek Tuff. (3) Youngand voluminous 0·25–0·1 Ma intra-calderalavas, which represent the latest volcanic activity at Yellowstone,contain zircons with both high-¹⁸O and low-¹⁸O cores surroundedby an intermediate-¹⁸O rim. This implies inheritance of a varietyof rocks from high-¹⁸O pre-caldera and low-¹⁸O post-calderaunits, followed by residence in a common intermediate-¹⁸O meltprior to eruption. (4) Major ignimbrites of Huckleberry Ridge,and to a lesser extent the Lava Creek and Mesa Falls Tuffs,contain zoned zircons with lower-¹⁸O zircon cores, suggestingthat melting and zircon inheritance from the low-¹⁸O hydrothermallyaltered carapace was an important process during formation ofthese large magma bodies prior to caldera collapse. (5) The¹⁸O zoning in the majority of zircon core–rim interfacesis step-like rather than smoothly inflected, suggesting thatprocesses of solution–reprecipitation were more importantthan intra-crystalline oxygen diffusion. Concave-downward zirconcrystal size distributions support dissolution of the smallercrystals and growth of rims on larger crystals. This study suggeststhat silicic magmatism at Yellowstone proceeded via rapid, shallow-levelremelting of earlier erupted and hydrothermally altered Yellowstonesource rocks and that pulses of basaltic magma provided theheat for melting. Each post-caldera Yellowstone lava representsan independent homogenized magma batch that was generated rapidlyby remelting of source rocks of various ages and ¹⁸O values.The commonly held model of a single, large-volume, super-solidus,mushy-state magma chamber that is periodically reactivated andproduces rhyolitic offspring is not supported by our data. Rather,the source rocks for the Yellowstone volcanism were cooled belowthe solidus, hydrothermally altered by heated meteoric watersthat caused low ¹⁸O values, and then remelted in distinct pocketsby intrusion of basic magmas. Each packet of new melt inheritedzircons that retained older age and ¹⁸O values. This interpretationmay have significance for interpreting seismic data for crustallow-velocity zones in which magma mush and solidified areasexperiencing hydrothermal circulation occur side by side. Newbasalt intrusions into this solidifying batholith are requiredto form the youngest volcanic rocks that erupted as independentrhyolitic magmas. We also suggest that the Lava Creek Tuff magmawas already an uneruptable mush by the time of the first post-calderaeruption after 0·1 Myr of the climactic caldera-formingeruption. KEY WORDS: Yellowstone; oxygen isotopes; geochronology; isotope zoning; zircon; U–Pb dating; caldera; rhyolite; ion microprobe     

Magmatic Differentiation at an Island-arc Caldera: Okmok Volcano, Aleutian Islands, Alaska

Okmok volcano is situated on oceanic crust in the central Aleutianarc and experienced large (15 km³) caldera-forming eruptionsat 12 000 years BP and 2050 years BP. Each caldera-forming eruptionbegan with a small Plinian rhyodacite event followed by theemplacement of a dominantly andesitic ash-flow unit, whereaseffusive inter- and post-caldera lavas have been more basaltic.Phenocryst assemblages are composed of olivine + pyroxene +plagioclase ± Fe–Ti oxides and indicate crystallizationat 1000–1100°C at 0·1–0·2 GPain the presence of 0–4% H₂O. The erupted products followa tholeiitic evolutionary trend and calculated liquid compositionsrange from 52 to 68 wt % SiO₂ with 0·8–3·3wt % K₂O. Major and trace element models suggest that the moreevolved magmas were produced by 50–60% in situ fractionalcrystallization around the margins of the shallow magma chamber.Oxygen and strontium isotope data (¹⁸O 4·4–4·9,⁸⁷Sr/ ⁸⁶Sr 0·7032–0·7034) indicate interactionwith a hydrothermally altered crustal component, which led toelevated thorium isotope ratios in some caldera-forming magmas.This compromises the use of uranium–thorium disequilibria[(²³⁰Th/ ²³⁸U) = 0·849–0·964] to constrainthe time scales of magma differentiation but instead suggeststhat the age of the hydrothermal system is 100 ka. Modellingof the diffusion of strontium in plagioclase indicates thatmany evolved crystal rims formed less than 200 years prior toeruption. This addition of rim material probably reflects theremobilization of crystals from the chamber margins followingreplenishment. Basaltic recharge led to the expansion of themagma chamber, which was responsible for the most recent caldera-formingevent. KEY WORDS: Okmok; caldera; U-series isotopes; Sr-diffusion; time scales; Aleutian arc     

Magma sources and gold mineralisation in the Mount Leyshon and Tuckers Igneous Complexes, Queensland, Australia: U-Pb and Hf isotope evidence

In situ LAM-ICPMS U-Pb, Hf-isotope and trace-element analyses of zircon have been used to evaluate the relative contributions of juvenile mantle and crustal sources to the intrusive rocks of the mafic to intermediate, gold-poor Tuckers Igneous Complex (TIC), and the spatially and temporally related, felsic Mount Leyshon Igneous Complex (MLIC), which hosts a gold-rich porphyry system.

The TIC intrusions range in age from 304.2 ± 9.1 Ma to 288.5 ± 6.4 Ma, and the MLIC intrusions from 291.0 ± 4.8 Ma to 288 ± 6 Ma. Cross-cutting relationships define the intrusion sequence from oldest to youngest; Diorite, Monzodiorite, Mafic Granodiorite and Biotite Microgranite within the TIC; Early Dyke, Southern Porphyry and Late Dyke within the MLIC.

Zircons from the earliest rock type within each complex have a wide range in _Hf (5.2 to 14.8 for the TIC Diorite, 2.0 to 12.4 for the MLIC Early Dykes) suggesting the mixing of juvenile and crustal magmas. This interpretation is supported by trace-element data that show the presence of two distinct zircon populations in the MLIC Early Dyke. The later intrusive rocks have narrower ranges in _Hf (typically < 4 _Hf units) and trace-element patterns of zircon. This homogeneity suggests derivation from magmas produced by further mixing and fractional crystallisation of the TIC Diorite and the MLIC Early Dyke magmas respectively. A greater crustal contribution to the gold-rich MLIC is inferred from the range of median _Hf (3.2 to 4.5 for the MLIC, 5.4 to 8.7 for the TIC). We suggest that the MLIC was derived by melting of more felsic crustal rocks, and with less input from juvenile mantle, then the TIC; it was not derived by fractional crystallisation of an intermediate to mafic TIC-like magma. Modelling of Hf isotope data yields a mean model age of 1040 ± 10 Ma (at ¹⁷⁶Lu/¹⁷⁷Hf = 0.015) for the crustal component in both complexes.

Gold was precipitated in the MLIC Breccia during the emplacement of the Late Dykes. The isotopically homogenous nature of the Late Dykes suggests that no additional juvenile-mantle input was involved at the mineralisation stage. This supports a model in which gold and other metals were indigenous to the Late Dykes magma and were concentrated by magma differentiation and fluid-evolution processes.     

Geology,fluid inclusion and sulphur isotope characteristics of the El Cobre VHMS deposit,Southern Cuba

The El Cobre deposit is located in eastern Cuba within the volcanosedimentary sequence of the Sierra Maestra Paleogene arc. The deposit is hosted by tholeiitic basalts, andesites and tuffs and comprises thick stratiform barite and anhydrite bodies, three stratabound disseminated up to massive sulphide bodies produced by silicification and sulphidation of limestones or sulphates, an anhydrite stockwork and a siliceous stockwork, grading downwards to quartz veins. Sulphides are mainly pyrite, chalcopyrite and sphalerite; gold occurs in the stratabound ores. Fluid inclusions measured in sphalerite, quartz, anhydrite and calcite show salinities between 2.3 and 5.7 wt% NaCl eq. and homogenisation temperatures between 177 and 300°C. Sulphides from the stratabound mineralisation display δ ³⁴S values of 0‰ to +6.0‰, whilst those from the feeder zone lie between −1.4‰ and +7.3‰. Sulphides show an intra-grain sulphur isotope zonation of about 2‰; usually, δ ³⁴S values increase towards the rims. Sulphate sulphur has δ ³⁴S in the range of +17‰ to +21‰, except two samples with values of +5.9‰ and +7.7‰. Sulphur isotope data indicate that the thermochemical reduction of sulphate from a hydrothermal fluid of seawater origin was the main source of sulphide sulphur and that most of the sulphates precipitated by heating of seawater. The structure of the deposit, mineralogy, fluid inclusion and isotope data suggest that the deposit formed from seawater-derived fluids with probably minor supply of magmatic fluids.     

Hydrothermal gold mineralization at the Hira Buddini gold mine,India: constraints on fluid evolution and fluid sources from boron isotopic compositions of tourmaline

We determined the boron isotope and chemical compositions of tourmaline from the Hira Buddini gold deposit within the Archean Hutti-Maski greenstone belt in southern India to investigate the evolution of the hydrothermal system and to constrain its fluid sources. Tourmaline is a minor but widespread constituent in the inner and distal alteration zones of metabasaltic and metadacite host rocks associated with the hydrothermal gold mineralization. The Hira Buddini tourmaline belongs to the dravite–schorl series with variations in Al, Fe/(Fe+Mg), Ca, Ti, and Cr contents that can be related to their host lithology. The total range of δ¹¹B values determined is extreme, from −13.3‰ to +9.0‰, but 95% of the values are between −4 and +9‰. The boron isotope compositions of metabasalt-hosted tourmaline show a bimodal distribution with peak δ¹¹B values at about −2‰ and +6‰. The wide range and bimodal distribution of boron isotope ratios in tourmaline require an origin from at least two isotopically distinct fluid sources, which entered the hydrothermal system separately and were subsequently mixed. The estimated δ¹¹B values of the hydrothermal fluids, based on the peak tourmaline compositions and a mineralization temperature of 550°C, are around +1 and +10‰. The isotopically lighter of the two fluids is consistent with boron released by metamorphic devolatilization reactions from the greenstone lithologies, whereas the ¹¹B-rich fluid is attributed to degassing of I-type granitic magmas that intruded the greenstone sequence, providing heat and fluids to the hydrothermal system. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Metamorphic fluid origins in the Osborne Fe oxide–Cu–Au deposit,Australia: evidence from noble gases and halogens

The Osborne iron oxide–copper–gold (IOCG) deposit is hosted by amphibolite facies metasedimentary rocks and associated with pegmatite sheets formed by anatexis during peak metamorphism. Eleven samples of ore-related hydrothermal quartz and two pegmatitic quartz–feldspar samples contain similarly complex fluid inclusion assemblages that include variably saline (<12–65 wt% salts) aqueous and liquid carbon dioxide varieties that are typical of IOCG mineralisation. The diverse fluid inclusion types present in each of these different samples have been investigated by neutron-activated noble gas analysis using a combination of semi-selective thermal and mechanical decrepitation techniques. Ore-related quartz contains aqueous and carbonic fluid inclusions that have similar ⁴⁰Ar/³⁶Ar values of between 300 and 2,200. The highest-salinity fluid inclusions (47–65 wt% salts) have calculated ³⁶Ar concentrations of approximately 1–5 ppb, which are more variable than air-saturated water (ASW = 1.3–2.7 ppb). These fluid inclusions have extremely variable Br/Cl values of between 3.8 × 10⁻³ and 0.3 × 10⁻³, and I/Cl values of between 27 × 10⁻⁶ and 2.4 × 10⁻⁶ (all ratios are molar). Fluid inclusions in the two pegmatite samples have similar ⁴⁰Ar/³⁶Ar values of ≤1,700 and an overlapping range of Br/Cl and I/Cl values. High-salinity fluid inclusions in the pegmatite samples have 2.5–21 ppb ³⁶Ar, that overlap the range determined for ore-related samples in only one case. The fluid inclusions in both sample groups have ⁸⁴Kr/³⁶Ar and ¹²⁹Xe/³⁶Ar ratios that are mainly in the range of air and air-saturated water and are similar to mid-crustal rocks and fluids from other settings. The uniformly low ⁴⁰Ar/³⁶Ar values (<2,200) and extremely variable Br/Cl and I/Cl values do not favour a singular or dominant fluid origin from basement- or mantle-derived magmatic fluids related to A-type magmatism. Instead, the data are compatible with the involvement of metamorphic fluids that have interacted with anatectic melts to variable extents. The ‘metamorphic’ fluids probably represent a mixture of (1) inherited sedimentary pore fluids and (2) locally derived metamorphic volatilisation products. The lowest Br/Cl and I/Cl values and the ultra-high salinities are most easily explained by the dissolution of evaporites. The data demonstrate that externally derived magmatic fluids are not a ubiquitous component of IOCG ore-forming systems, but are compatible with models in which IOCG mineralisation is localised at sites of mixing between fluids of different origin. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorised users.