2019 Vol. 10, No. 1
For our ancestors, oil seeps were both a fascination and a resource but as the planet's reserves of high quality low density oil becomes increasingly depleted, so there is now a renewed interest in heavier, biodegraded oils such as those encountered in terrestrial seeps. One such seep is Pitch Lake in the Caribbean island of Trinidad, which is the largest natural deposit of asphalt in the world. At the northern end of the Caribbean, oil emerges along a tectonic contact on the island on Cuba. The sources of the oils from these seeps are relatively recent and both are subject to intense weathering due to the tropical conditions. When analysed by gas chromatography (GC) both oils appear as unresolved complex mixtures (UCM) and show a very high degree of biodegradation thus presenting an analytical challenge. In this case study, these two Caribbean seep oils were analysed by comprehensive two dimensional GC with time of flight mass spectrometry (GC×GC-TOFMS) to expose many thousands of the individual compounds that comprise the UCM. The high chromatographic resolution of the GC×GC-TOFMS produced good quality mass spectra allowing many compounds including molecular fossil ‘biomarkers’ to be identified. Compound classes included diamondoid hydrocarbons, demethylated hopanes and seco-hopanes, mono- and tri-aromatic steroids. D-ring aromatised structures of the 8,14-seco-hopanes, including demethylated forms were present in both oils but further demethylation, probably at position C-25 during biodegradation, was only observed in the Pitch Lake oil. Many polycyclic aromatic hydrocarbons (PAHs) were absent although the fungal-derived pentacyclic PAH perylene was present in both oils. The presence of the angiosperm biomarker lupane in the Pitch Lake oil constrained the age to the Late Cretaceous. The higher degree of biodegradation observed in the Cuban oil was likely due to relatively slow anaerobic processes whereas oil within Pitch Lake was probably subject to additional more rapid aerobic metabolism within the lake.
In the Earth's upper crust, where aqueous fluids can circulate freely, most mineral transformations are controlled by the coupling between the dissolution of a mineral that releases chemical species into the fluid and precipitation of new minerals that contain some of the released species in their crystal structure, the coupled process being driven by a reduction of the total free-energy of the system. Such coupled dissolution-precipitation processes occur at the fluid-mineral interface where the chemical gradients are highest and heterogeneous nucleation can be promoted, therefore controlling the growth kinetics of the new minerals. Time-lapse nanoscale imaging using Atomic Force Microscopy (AFM) can monitor the whole coupled process under in situ conditions and allow identifying the time scales involved and the controlling parameters. We have performed a series of experiments on carbonate minerals (calcite, siderite, dolomite and magnesite) where dissolution of the carbonate and precipitation of a new mineral was imaged and followed through time. In the presence of various species in the reacting fluid (e. g. antimony, selenium, arsenic, phosphate), the calcium released during calcite dissolution binds with these species to form new minerals that sequester these hazardous species in the form of a stable solid phase. For siderite, the coupling involves the release of Fe2+ ions that subsequently become oxidized and then precipitate in the form of FeⅢ oxyhydroxides. For dolomite and magnesite, dissolution in the presence of pure water (undersaturated with any possible phase) results in the immediate precipitation of hydrated Mg-carbonate phases. In all these systems, dissolution and precipitation are coupled and occur directly in a boundary layer at the carbonate surface. Scaling arguments demonstrate that the thickness of this boundary layer is controlled by the rate of carbonate dissolution, the equilibrium concentration of the precipitates and the kinetics of diffusion of species in a boundary layer. From these parameters a characteristic time scale and a characteristic length scale of the boundary layer can be derived. This boundary layer grows with time and never reaches a steady state thickness as long as dissolution of the carbonate is faster than precipitation of the new mineral. At ambient temperature, the surface reactions of these dissolving carbonates occur on time-scales of the order of seconds to minutes, indicating the rapid surface rearrangement of carbonates in the presence of aqueous fluids. As a consequence, many carbonate-fluid reactions in low temperature environments are controlled by local thermodynamic equilibria rather than by the global equilibrium in the whole system.
The replacement of magnetite by hematite was studied through a series of experiments under mild hydrothermal conditions (140-220 ℃, vapour saturated pressures) to quantify the kinetics of the transformation and the relative effects of redox and non-redox processes on the transformation. The results indicate that oxygen is not an essential factor in the replacement reaction of magnetite by hematite, but the addition of excess oxidant does trigger the oxidation reaction, and increases the kinetics of the transformation. However, even under high O2(aq) environments, some of the replacement still occurred via Fe2+ leaching from magnetite. The kinetics of the replacement reaction depends upon temperature and solution parameters such as pH and the concentrations of ligands, all of which are factors that control the solubility of magnetite and affect the transport of Fe2+ (and the oxidant) to and from the reaction front. Reaction rates are fast at ∼200 ℃, and in nature transport properties of Fe and, in the case of the redox-controlled replacement, the oxidant will be the rate-limiting control on the reaction progress. Using an Avrami treatment of the kinetic data and the Arrhenius equation, the activation energy for the transformation under non-redox conditions was calculated to be 26 ±6 kJ mol-1. This value is in agreement with the reported activation energy for the dissolution of magnetite, which is the rate-limiting process for the transformation under non-redox conditions.
In an extensional shear zone in the Talea Ori, Crete, quartz veins occur in high-pressure low-temperature metamorphic sediments at sites of dilation along shear band boundaries, kink band boundaries and boudin necks. Bent elongate grains grown epitactically from the host rock with abundant fluid inclusion trails parallel to the vein wall indicate vein formation by crack-seal increments during dissolution-precipitation creep of the host rock. The presence of sutured high-angle grain boundaries and subgrains shows that temperatures were sufficiently high for recovery and strain-induced grain boundary migration, i.e. higher than 300-350 ℃, close to peak metamorphic conditions. The generally low amount of strain accumulated by dislocation creep in quartz of the host rock and most veins indicates low bulk stress conditions of a few tens of MPa on a long term. The time scale of stress-loading to cause cyclic cracking and sealing is assumed to be lower than the Maxwell relaxation time of the metasediments undergoing dissolution-precipitation creep at high strain rates (10-10 s-1 to 10-9 s-1), which is on the order of hundred years. In contrast, some veins discordant or concordant to the foliation show heterogeneous quartz microstructures with micro-shear zones, sub-basal deformation lamellae, short-wavelength undulatory extinction and recrystallized grains restricted to high strain zones. These microstructures indicate dislocation glide-controlled crystal-plastic deformation (low-temperature plasticity) at transient high stresses of a few hundred MPa with subsequent recovery and strain-induced grain boundary migration at relaxing stresses and temperatures of at least 300-350 ℃. High differential stresses in rocks at greenschist-facies conditions that relieve stress by creep on the long term, requires fast stress-loading rates, presumably by seismic activity in the overlying upper crust. The time scale for stress loading is controlled by the duration of the slip event along a fault, i.e. a few seconds to minutes. This study demonstrates that microstructures can distinguish between deformation at internal low stress-loading rates (to tens of MPa on a time scale of hundred years) and high (coseismic) stress-loading rates to a few hundred MPa on a time scale of minutes.
The Pb isotopic composition of rocks is widely used to constrain the sources and mobility of melts and hydrothermal fluids in the Earth's crust. In many cases, the Pb isotopic composition appears to represent mixing of multiple Pb reservoirs. However, the nature, scale and mechanisms responsible for isotopic mixing are not well known. Additionally, the trace element composition of sulphide minerals are routinely used in ore deposit research, mineral exploration and environmental studies, though little is known about element mobility in sulphides during metamorphism and deformation. To investigate the mechanisms of trace element mobility in a deformed Witwatersrand pyrite (FeS2), we have combined electron backscatter diffraction (EBSD) and atom probe microscopy (APM). The results indicate that the pyrite microstructural features record widely different Pb isotopic compositions, covering the entire range of previously published sulphide Pb compositions from the Witwatersrand basin. We show that entangled dislocations record enhanced Pb, Sb, Ni, Tl and Cu composition likely due to entrapment and short-circuit diffusion in dislocation cores. These dislocations preserve the Pb isotopic composition of the pyrite at the time of growth (∼3 Ga) and show that dislocation intersections, likely to be common in deforming minerals, limit trace element mobility. In contrast, Pb, As, Ni, Co, Sb and Bi decorate a high-angle grain boundary which formed soon after crystallisation by sub-grain rotation recrystallization. Pb isotopic composition within this boundary indicates the addition of externally-derived Pb and trace elements during greenschist metamorphism at ∼2 Ga. Our results show that discrete Pb reservoirs are nanometric in scale, and illustrate that grain boundaries may remain open systems for trace element mobility over 1 billion years after their formation.
Understanding the mechanisms of parent-daughter isotopic mobility at the nanoscale is key to rigorous interpretation of U-Th-Pb data and associated dating. Until now, all nanoscale geochronological studies on geological samples have relied on either Transmission Electron Microscope (TEM) or Atom Probe Microscopy (APM) characterizations alone, thus suffering from the respective weaknesses of each technique. Here we focus on monazite crystals from a ∼1 Ga, ultrahigh temperature granulite from Rogaland (Norway). This sample has recorded concordant U-Pb dates (measured by LA-ICP-MS) that range over 100 My, with the three domains yielding distinct isotopic U-Pb ages of 1034 ±6 Ma (D1; S-rich core), 1005 ±7 Ma (D2), and 935 ±7 Ma (D3), respectively. Combined APM and TEM characterization of these monazite crystals reveal phase separation that led to the isolation of two different radiogenic Pb (Pb*) reservoirs at the nanoscale. The S-rich core of these monazite crystals contains Ca-S-rich clusters, 5-10 nm in size, homogenously distributed within the monazite matrix with a mean inter-particle distance of 40-60 nm. The clusters acted as a sink for radiogenic Pb (Pb*) produced in the monazite matrix, which was reset at the nanoscale via Pb diffusion while the grain remained closed at the micro-scale. Compared to the concordant ages given by conventional micro-scale dating of the grain, the apparent nano-scale age of the monazite matrix in between clusters is about 100 Myr younger, which compares remarkably well to the duration of the metamorphic event. This study highlights the capabilities of combined APM-TEM nano-structural and nano-isotopic characterizations in dating and timing of geological events, allowing the detection of processes untraceable with conventional dating methods.
Ore forming processes involve the redistribution of heat, mass and momentum by a wide range of processes operating at different time and length scales. The fastest process at any given length scale tends to be the dominant control. Applying this principle to the array of physical processes that operate within magma flow pathways leads to some key insights into the origins of magmatic Ni-Cu-PGE sulfide ore deposits. A high proportion of mineralised systems, including those in the super-giant Noril'sk-Talnakh camp, are formed in small conduit intrusions where assimilation of country rock has played a major role. Evidence of this process is reflected in the common association of sulfides with vari-textured contaminated host rocks containing xenoliths in varying stages of assimilation. Direct incorporation of S-bearing country rock xenoliths is likely to be the dominant mechanism for generating sulfide liquids in this setting. However, the processes of melting or dissolving these xenoliths is relatively slow compared with magma flow rates and, depending on xenolith lithology and the composition of the carrier magma, slow compared with settling and accumulation rates. Chemical equilibration between sulfide droplets and silicate magma is slower still, as is the process of dissolving sulfide liquid into initially undersaturated silicate magmas. Much of the transport and deposition of sulfide in the carrier magmas may occur while sulfide is still incorporated in the xenoliths, accounting for the common association of magmatic sulfide-matrix ore breccias and contaminated “taxitic” host rocks. Effective upgrading of so-formed sulfide liquids would require repetitive recycling by processes such as re-entrainment, back flow or gravity flow operating over the lifetime of the magma transport system as a whole. In contrast to mafic-hosted systems, komatiite-hosted ores only rarely show an association with externally-derived xenoliths, an observation which is partially due to the predominant formation of ores in lava flows rather than deep-seated intrusions, but also to the much shorter timescales of key component systems in hotter, less viscous magmas. Nonetheless, multiple cycles of deposition and entrainment are necessary to account for the metal contents of komatiite-hosted sulfides. More generally, the time and length scale approach introduced here may be of value in understanding other igneous processes as well as non-magmatic mineral systems.
Proterozoic orogens commonly host a range of hydrothermal ores that form in diverse tectonic settings at different times. However, the link between mineralization and the regional-scale tectonothermal evolution of orogens is usually not well understood, especially in areas subject to multiple hydrothermal events. Regional-scale drivers for mineral systems vary between the different classes of hydrothermal ore, but all involve an energy source and a fluid pathway to focus mineralizing fluids into the upper crust. The Mount Olympus gold deposit in the Proterozoic Capricorn Orogen of Western Australia, was regarded as an orogenic gold deposit that formed at ca. 1738 Ma during the assembly of Proterozoic Australia. However, the trace element chemistry of the pyrite crystals closely resembles those of the Carlin deposits of Nevada, with rims that display solid solution gold accompanied by elevated As, Cu, Sb, Hg, and Tl, surrounding gold-poor cores. New SHRIMP U-Pb dating of xenotime intergrown with auriferous pyrite and ore-stage alteration minerals provided a weighted mean 207Pb*/206Pb* date of 1769 ±5 Ma, interpreted as the age of gold mineralization. This was followed by two discrete episodes of hydrothermal alteration at 1727 ±7 Ma and 1673 ±8 Ma. The three ages are linked to multiple reactivation of the crustal-scale Nanjilgardy Fault during repeated episodes of intracratonic reworking. The regional-scale drivers for Carlin-like gold mineralization at Mount Olympus are related to a change in tectonic regime during the final stages of the intracratonic 1820-1770 Ma Capricorn Orogeny. Our results suggest that substantial sized Carlin-like gold deposits can form in an intracratonic setting during regional-scale crustal reworking.
The West Qinling Orogen (WQO) in Central China Orogenic Belt contains numerous metasedimentary rock-hosted gold deposits (>2000 t Au), which mainly formed during two pulses: one previously recognized in the Late Triassic to Early Jurassic (T3-J1) and one only recently identified in the Late Jurassic to Early Cretaceous (J3-K1). Few studies have focused on the origin and geotectonic setting of the J3-K1 gold deposits.
Textural relationships, LA-ICP-MS trace element and sulfur isotope compositions of pyrites in hydrothermally altered T3 dykes within the J3-K1 Daqiao deposit were used to constrain relative timing relationships between mineralization and pyrite growth in the dykes, and to characterize the source of ore fluid. These results are integrated with an overview of the regional geodynamic setting, to advance understanding of the tectonic driver for J3-K1 hydrothermal gold systems. Pyrite in breccia- and dyke-hosted gold ores at Daqiao have similar chemical and isotopic compositions and are considered to be representative of J3-K1 gold deposits in WQO. Co/Ni and sulfur isotope ratios suggest that ore fluids were derived from underlying Paleozoic Ni- and Se-rich carbonaceous sedimentary rocks. The geochemical data do not support the involvement of magmatic fluids. However, in the EQO (East Qinling Orogen), J3-K1 deposits are genetically related to magmatism. Gold mineralization in WQO is contemporaneous with magmatic deposits in the EQO and both are mainly controlled by NE- and EW-trending structures produced by changes in plate motion of the Paleo-Pacific plate as it was subducted beneath the Eurasian continent. We therefore infer that the J3-K1 structural regime facilitated the ascent of magma in the EQO and metamorphic fluids in the WQO with consequent differences in the character of contemporaneous ore deposits. If this is correct, then the far-field effects of subduction along the eastern margin of NE Asia extended 1000's of km into the continental interior.
Formation of the Urals volcanic-hosted massive sulphide (VHMS) deposits is considered to be related with the intra-oceanic stage of island arc(s) development in the Upper Ordovician-Middle Devonian based on the biostratigraphic record of ore-hosting sedimentary rocks. However, the direct Re-Os dating of four known VHMS systems in the Urals gives significantly younger Re-Os isochron ages ranging from 355 ±15 Ma up to 366 ±2 Ma. To address this discrepancy, we performed SHRIMP U-Pb dating on zircons extracted from rhyodacites (Eifelian biostratigraphic age of 393-388 Ma) from the footwall of the Alexandrinka VHMS deposit which has a Re-Os isochron age of sulphides of 355 ±15 Ma.
New 206Pb/238U mean age of 374 ±3 Ma (MSWD = 1.4 and probability = 0.11) is considered to be the crystallisation age of the host volcanic rock. This age is ca. 15 Ma younger than the Eifelian (393-388 Ma) biostratigraphic age and overlaps the Frasnian-Famennian boundary (372 ±2 Ma), characterised by the final stages of Magnitogorsk Arc - East European continent collision. Such an inconsistency with geochronological age may be due to a reburial of conodonts during resedimentation as a result of erosion of older rocks in younger sedimentary sequences.
The thermal structure of subduction zones exerts a major influence on deep-seated mechanical and chemical processes controlling arc magmatism, seismicity, and global element cycles. Accretionary complexes exposed inland may comprise tectonic blocks with contrasting pressure-temperature (P-T) histories, making it possible to investigate the dynamics and thermal evolution of former subduction interfaces. With this aim, we present new Lu-Hf geochronological results for mafic rocks of the Halilbağı Complex (Anatolia) that evolved along different thermal gradients. Samples include a lawsonite-epidote blueschist, a lawsonite-epidote eclogite, and an epidote eclogite (all with counter-clockwise P-T paths), a prograde lawsonite blueschist with a “hairpin”-type P-T path, and a garnet amphibolite from the overlying sub-ophiolitic metamorphic sole. Equilibrium phase diagrams suggest that the garnet amphibolite formed at ∼0.6-0.7 GPa and 800-850 ℃, whereas the prograde lawsonite blueschist records burial from 2.1 GPa and 420 ℃ to 2.6 GPa and 520 ℃. Well-defined Lu-Hf isochrons were obtained for the epidote eclogite (92.38 ±0.22 Ma) and the lawsonite-epidote blueschist (90.19 ±0.54 Ma), suggesting rapid garnet growth. The lawsonite-epidote eclogite (87.30 ±0.39 Ma) and the prograde lawsonite blueschist (ca. 86 Ma) are younger, whereas the garnet amphibolite (104.5 ±3.5 Ma) is older. Our data reveal a consistent trend of progressively decreasing geothermal gradient from granulite-facies conditions at ∼104 Ma to the epidote-eclogite facies around 92 Ma, and the lawsonite blueschist-facies between 90 Ma and 86 Ma. Three Lu-Hf garnet dates (between 92 Ma and 87 Ma) weighted toward the growth of post-peak rims (as indicated by Lu distribution in garnet) suggest that the HP/LT rocks were exhumed continuously and not episodically. We infer that HP/LT metamorphic rocks within the Halilbağı Complex were subjected to continuous return flow, with “warm” rocks being exhumed during the tectonic burial of “cold” ones. Our results, combined with regional geological constraints, allow us to speculate that subduction started at a transform fault near a mid-oceanic spreading centre. Following its formation, this ancient subduction interface evolved thermally over more than 15 Myr, most likely as a result of heat dissipation rather than crustal underplating.
The post-Mesoproterozoic tectonometamorphic history of the Musgrave Province, central Australia, has previously been solely attributed to intracontinental compressional deformation during the 580-520 Ma Petermann Orogeny. However, our new structurally controlled multi-mineral geochronology results, from two north-trending transects, indicate protracted reactivation of the Australian continental interior over ca. 715 million years. The earliest events are identified in the hinterland of the orogen along the western transect. The first tectonothermal event, at ca. 715 Ma, is indicated by 40Ar/39Ar muscovite and U-Pb titanite ages. Another previously unrecognised tectonometamorphic event is dated at ca. 630 Ma by U-Pb analyses of metamorphic zircon rims. This event was followed by continuous cooling and exhumation of the hinterland and core of the orogen along numerous faults, including the Woodroffe Thrust, from ca. 625 Ma to 565 Ma as indicated by muscovite, biotite, and hornblende 40Ar/39Ar cooling ages. We therefore propose that the Petermann Orogeny commenced as early as ca. 630 Ma. Along the eastern transect, 40Ar/39Ar muscovite and zircon (U-Th)/He data indicate exhumation of the foreland fold and thrust system to shallow crustal levels between ca. 550 Ma and 520 Ma, while the core of the orogen was undergoing exhumation to mid-crustal levels and cooling below 600-660 ℃. Subsequent cooling to 150-220 ℃ of the core of the orogen occurred between ca. 480 Ma and 400 Ma (zircon [U-Th]/He data) during reactivation of the Woodroffe Thrust, coincident with the 450-300 Ma Alice Springs Orogeny. Exhumation of the footwall of the Woodroffe Thrust to shallow depths occurred at ca. 200 Ma. More recent tectonic activity is also evident as on the 21 May, 2016 (Sydney date), a magnitude 6.1 earthquake occurred, and the resolved focal mechanism indicates that compressive stress and exhumation along the Woodroffe Thrust is continuing to the present day. Overall, these results demonstrate repeated amagmatic reactivation of the continental interior of Australia for ca. 715 million years, including at least 600 million years of reactivation along the Woodroffe Thrust alone. Estimated cooling rates agree with previously reported rates and suggest slow cooling of 0.9-7.0 ℃/Ma in the core of the Petermann Orogen between ca. 570 Ma and 400 Ma. The long-lived, amagmatic, intracontinental reactivation of central Australia is a remarkable example of stress transmission, strain localization and cratonization-hindering processes that highlights the complexity of Continental Tectonics with regards to the rigid-plate paradigm of Plate Tectonics.
Models for when and how the continental crust was formed are constrained by estimates in the rates of crustal growth. The record of events preserved in the continental crust is heterogeneous in time with distinctive peaks and troughs of ages for igneous crystallisation, metamorphism, continental margins and mineralisation. For the most part these are global signatures, and the peaks of ages tend to be associated with periods of increased reworking of pre-existing crust, reflected in the Hf isotope ratios of zircons and their elevated oxygen isotope ratios. Increased crustal reworking is attributed to periods of crustal thickening associated with compressional tectonics and the development of supercontinents. Magma types similar to those from recent within-plate and subduction related settings appear to have been generated in different areas at broadly similar times before ∼3.0 Ga. It can be difficult to put the results of such detailed case studies into a more global context, but one approach is to consider when plate tectonics became the dominant mechanism involved in the generation of juvenile continental crust. The development of crustal growth models for the continental crust are discussed, and a number of models based on different data sets indicate that 65%-70% of the present volume of the continental crust was generated by 3 Ga. Such estimates may represent minimum values, but since ∼3 Ga there has been a reduction in the rates of growth of the continental crust. This reduction is linked to an increase in the rates at which continental crust is recycled back into the mantle, and not to a reduction in the rates at which continental crust was generated. Plate tectonics results in both the generation of new crust and its destruction along destructive plate margins. Thus, the reduction in the rate of continental crustal growth at ∼3 Ga is taken to reflect the period in which plate tectonics became the dominant mechanism by which new continental crust was generated.
U-Pb monazite and zircon geochronology and calculated metamorphic phase diagrams from drill holes in the northern Gawler Craton, southern Australia, reveal the presence of ca. 1.45 Ga magmatism and metamorphism. Magmatism and granulite facies metamorphism of this age has not previously been recognised in the Gawler Craton. The magmatic rocks have steep LREE-enriched patterns and high Ga/Al values, suggesting they are A-type granites. Calculated metamorphic forward models suggest that this event was associated with high apparent thermal gradients and reached pressures of 3.2-5.4 kbar and temperatures of 775-815 ℃. The high apparent thermal gradients may reflect pluton-enhanced metamorphism, consistent with the presence of A-type granites. The recognition of ca. 1.45 Ga tectonism in the northern Gawler Craton is added to a compilation of ca. 1.50-1.40 Ga magmatism, shear zone reactivation, rift basin development and isotope resetting throughout the South and North Australian Cratons that shows that this event was widespread in eastern Proterozoic Australia. This event is stylistically similar to ca. 1.45 Ga A-type magmatism and high thermal gradient metamorphism in Laurentia in this interval and provides further support for a connection between Australia and Laurentia during the Mesoproterozoic. The tectonic setting of the 1.50-1.40 Ga event is unclear but may record rifting within the Nuna (or Columbia) supercontinent, or a period of intracontinental extension within a long-lived convergent setting.
The Central Asian Orogenic Belt (CAOB) was built up through protracted accretion and collision of a variety of terranes/micro-continents during Neoproterozoic-Mesozoic time. To understand potential links among Paleozoic subduction and accretionary processes that were operative during the development of the southeastern CAOB, we conducted a combined U-Pb and Hf-isotope analysis of detrital zircons from previously defined Devonian, Carboniferous and Early Permian strata in the Bengbatu area, Inner Mongolia. Detrital zircons from (meta-) sandstones in these strata commonly yield major Paleozoic age populations at ca. 300-261 Ma, 351-300 Ma and 517-419 Ma, and also give several Precambrian ages that range from 2687 Ma to 544 Ma. The youngest ages redefine the deposition of all these strata to be in the Middle Permian (Wordian-Capitanian) or later, much younger than previously considered. These ages, coupled with regional magmatic records, support an interpretation of most surrounding areas as possible detritus sources, including the Mongolian arcs to the north, the Northern Accretionary Orogen to the south, and the intervening Erenhot-Hegenshan Ophiolite Belt. Zircons with magmatic ages of ca. 500-350 Ma and ca. 300-261 Ma display a large range of εHf(t) values (-13.97 to +15.31), whereas ca. 350-300 Ma zircons are dominated by positive εHf(t) values (+0.14 to +16.00). These results support the occurrence of two significant shifts of the zircon εHf(t) values, which has tectonic implications for the understanding of the Carboniferous-Permian evolution of the southeastern CAOB. A marked shift from mixed to positive zircon εHf(t) values at 350-330 Ma likely manifests the incipient opening of the Hegenshan Ocean, due to the slab rollback of the subducting Paleo-Asian Oceanic lithosphere. Another shift from positive to mixed zircon εHf(t) values at ca. 300 Ma likely corresponds to a tectonic switch from syn-orogenic subduction-related to post-orogenic extensional setting, genetically related to the tectonic collapse of a formerly overthickened crust.
The Helanshan tectonic belt is located to the west of the Ordos Basin, and separates the Alxa (or Yinshan) Massif to the west from the Ordos block to the east. Triassic sedimentation in the Helanshan tectonic belt records important information about tectono-sedimentary process between the Alxa Massif and the Ordos block. Detailed geological mapping and investigation on the lithological package, sedimentary facies and paleocurrent orientation have been conducted on the Middle to Upper Triassic clastic rocks in the Helanshan tectonic belt. The succession is characterized by upward-fining sequence and comprises coarse grained alluvial-fluvial facies in the lower part as well as deltaic-lacustrine facies in the upper part. Based on detailed study and comparisons on the sedimentary sequence along various sections, the Middle to Upper Triassic strata have been revealed that show clear southeastward-deepening sedimentary differentiation and transgression from southwest to northeast, which are consistent with the southeastward flowing paleocurrent. These features indicate a southeastward-dipping paleogeography in the Helanshan tectonic belt, which was original western part of southeastward orientated fluvial-lacustrine system in the northwestern proto-Ordos Basin. Further to the east, the Triassic succession in the Ordos Basin displays gradually thickening and alluvial-fluvial system flowed from southeast to northwest, showing a huge thick sedimentary wedge in the western basin margin. Together with the Late Permian-Early Triassic closure of the Paleo-Asian Ocean to the north, the Late Triassic extensional structures and diabase dykes in the Helanshan tectonic belt, all the above sedimentary features could be mostly interpreted as records of an extensional basin correlated to post-collisional collapse of the Central Asian Orogenic Belt.
The newly discovered large (350 m2) Yantan dinosaur tracksite, in the Lower Jurassic Ziliujing Formation of Guizhou Province, China, reveals at least 250 footprints of which ∼97 can be resolved into trackways of sauropodomorphs. All the trackways are sub parallel likely indicating gregarious behavior. One theropod track (cf. Grallator) was recorded. The sauropodomorph tracks predominantly represent quadrupedal progression (Morphotype A), and footprint morphology is similar to the ichnospecies Liujianpusshunan, characterized by outward pes rotation. Three trackways indicate bipedal progression, and two of these (Morphotype B) indicate inward pes rotation, accompanied by elongate pes digit scratch marks. For the latter phenomenon three possible scenarios are discussed: (1) significant rotation changes accompanying changes in gait, (2) swimming behavior, (3) formation of undertracks.
Sedimentological evidence indicates the tracks were made on a linguloid rippled, muddy, immature sandstone substrate characterized by significant differences in substrate consistency across the track-bearing surface. Microbially induced sedimentary structures (MISS) characterized by distinctive wrinkle marks indicate a stressed, probably semi-arid, paleoenvironment that was not conducive to habitation by invertebrate organisms. This is consistent with other evidence that Lower Jurassic sauropodomorph tracks are often associated with semi-arid paleoenvironments
The subduction factories in convergent plate margins exert crucial control on recycling terrestrial components and returning to the overlying crust. The Nd and Hf isotopic systems provide potential tracers to evaluate these processes. Here we present a case where these isotopic systems are decoupled in a suite of granites from the Chinese Altai, showing a wide range of εHf(t) values (from -4.7 to +10.8) in contrast to a limited range of εNd(t) values (from -5.8 to -1.9). The zircon xenocrysts occurring frequently in these rocks show markedly negative εHf(t) values (from -34.3 to -6.5) and positive δ7Li values (from +12.5 to +18.2). We propose a model to explain the observed relationship between residual zircon and Nd-Hf isotope decoupling. We suggest that the Altai granites originated from partial melting of subducted slab components under relatively low temperature conditions which aided the residual zircon from oceanic sediments to inherit and retain a significant amount of 177Hf in the source, thereby elevating the 176Hf/177Hf ratio of the melt, and decoupling from the 143Nd/144Nd ratio during the subsequent magmatic processes. Our study illustrates a case where sediment recycling in subduction zone contributes to decoupling of Nd and Hf isotopic systems, with former providing a more reliable estimate of the source characteristics of granitic magmas.
In this study, nineteen brine samples from the Qarhan Salt Lake (QSL) in western China were collected and analyzed for boron (B) and chlorine (Cl) concentrations, total dissolved solids (TDS), pH values and stable B isotopic compositions. The B concentrations and δ11B values of brines in the QSL range from 51.6 mg/L to 138.4 mg/L, and from +9.32‰ to +13.08‰, respectively. By comparison of B concentrations and TDS of brines in QSL with evaporation paths of brackish water, we found that B enrichment of brines primarily results from strong evaporation and concentration of Qarhan lake water. Combining with comparisons of B concentrations, TDS, pH values and δ11B values of brines, previously elemental ratios (K/Cl, Mg/Cl, Ca/Cl, B/Cl) and δ11B values of halite from a sediment core (ISL1A), we observe good correlations between B concentrations and TDS, TDS and pH values, pH and δ11B values of brines, which demonstrate that higher B concentrations and more positive δ11B values of halite indicate higher salinity of the Qarhan paleolake water as well as drier paleoclimatic conditions. Based on this interpretation of the δ11B values of halite in core ISL1A, higher salinity of the Qarhan paleolake occurred during two intervals, around 46-34 ka and 26-9 ka, which are almost coincident with the upper and lower halite-dominated salt layers in core ISL1A, drier climate phases documented from the δ18O record of carbonate in core ISL1A and the paleomoisture record in monsoonal central Asia, and a higher solar insolation at 30°N. These results demonstrate that the δ11B values of halite in the arid Qaidam Basin could be regarded as a new proxy for reconstructing the salinity record of paleolake water as well as paleoclimate conditions.
The assembly of Late Neoproterozoic-Cambrian supercontinent Gondwana involved prolonged subduction and accretion generating arc magmatic and accretionary complexes, culminating in collision and formation of high grade metamorphic orogens. Here we report evidence for mafic magmatism associated with post-collisional extension from a suite of gabbroic rocks in the Trivandrum Block of southern Indian Gondwana fragment. Our petrological and geochemical data on these gabbroic suite show that they are analogous to high Fe tholeiitic basalts with evolution of the parental melts dominantly controlled by fractional crystallization. They display enrichment of LILE and LREE and depletion of HFSE with negative anomalies at Zr-Hf and Ti corresponding to subduction zone magmatic regime. The tectonic affinity of the gabbros coupled with their geochemical features endorse a heterogeneous mantle source with collective melt contributions from sub-slab asthenospheric mantle upwelling through slab break-off and arc-related metasomatized mantle wedge, with magma emplacement in subduction to post-collisional intraplate settings. The high Nb contents and positive Nb-Ta anomalies of the rocks are attributed to inflow of asthenospheric melts containing ancient recycled subducted slab components and/or fusion of subducted slab materials owing to upwelling of hot asthenosphere. Zircon grains from the gabbros show magmatic crystallization texture with low U and Pb content. The LA-ICPMS analyses show 206Pb/238U mean ages in the range of 507-494 Ma suggesting Cambrian mafic magmatism. The post-collisional mafic magmatism identified in our study provides new insights into mantle dynamics during the waning stage of the birth of a supercontinent.
The Indus River flows through Ladakh, one of the driest and coldest places on earth, in a tectonically active domain. Fluvial, glaciofluvial, lacustrine and debris dominated sequences represent the Late Quaternary sedimentary record along the river course. Karakoram Fault, a major crustal scaled feature reported to be active during the Quaternary, is associated with the Indus River drainage. Linkages between a major, active fault and deposits formed during the activity period of the fault are explored using heavy mineral deduced provenance and Optically Stimulated Luminescence (OSL) chronology.
Five deposits in a ∼200 km long stretch of the Indus River have been examined for a ∼80 ka period to decipher the climate linked aggradation history. Damming of the Indus River at ∼79 ka and existence of the Spituk Lake for >30 ka is demonstrated. Using geology of the provenance in relation to the mineralogical attributes of the Quaternary deposits, the major drainage reorganization when the connection of the Tangtse Valley to the Indus was blocked, is inferred at ∼73 ka. It is supported by the geological-geomorphological evidence. The study demonstrates the application of provenance linked mineralogy in terrestrial aggradation in a tectonically active region.
The Marifil Volcanic Complex, exposed in the eastern North Patagonian Massif, Argentina, includes up to 550 m of red conglomerates, sandstones, black siltstones, limestones, and reworked tuff of the Puesto Piris Formation. The basal part of this unit, which was deposited in high-gradient topographic relief, is composed of conglomerates and sandstones with thin layers of reworked tuffs. The lithofacies associations of the basal part indicate that the depositional mechanisms were mantled and gravitational flows. The middle part of the unit consists of fine sandstones, limestones, and black siltstones that were deposited in low-energy fluvial and lacustrine environments. The outcrops are located along the NE-SW direction and the major thickest units represented by limestones and siltstones, occur near the southeastern border of this NE-SW depocenter. Since the rhyolitic and trachytic lava flows and tuffs of the Marifil Volcanic Complex are interbedded with the sedimentary sequences of the Puesto Piris Formation, both units are coeval. Zircon U-Pb age was obtained for a trachytic lava flow (193.4 ±3.1 Ma) suggesting that sedimentation and volcanism are Sinemurian. This extensional episode was recorded in the eastern, western, and southwestern sectors of the North Patagonian Massif, and is possibly associated with the Gondwana supercontinent breakup.
The Early Paleozoic evolution of the northern margin of Gondwana is characterized by several episodes of bimodal magmatism intruded or outpoured within thick sedimentary basins. These processes are well recorded in the Variscan blocks incorporated in the Ligurian Alps because they experienced low temperature Alpine metamorphism. During the Paleozoic, these blocks, together with the other Alpine basements, were placed between the Corsica-Sardinia and the Bohemian Massif along the northern margin of Gondwana. In this framework, they host several a variegated lithostratigraphy forming two main complexes (Complexs I and Ⅱ) that can be distinguished by both the protoliths and their cross-cutting relationships, which indicate that the acidic and mafic intrusives of Complex Ⅱ cut an already folded sequence made of sediments, basalts and granitoids of Complex I. Both complexes were involved in the Variscan orogenic phases as highlighted by the pervasive eclogite-amphibolite facies schistosity (foliation Ⅱ). However, rare relicts of a metamorphic foliation at amphibolite facies conditions (foliation I) is locally preserved only in the rocks of Complex I. It is debatable if this schistosity was produced during the early folding event - occurred between the emplacement of Complex I and Ⅱ - rather than during an early stage of the Variscan metamorphic cycle.
New SHRIMP and LA ICP-MS U-Pb zircon dating integrated with literature data, provide emplacement ages of the several volcanic or intrusive bodies of both complexes. The igneous activity of Complex I is dated between 507 ±15 Ma and 494 ±5 Ma, while Complex Ⅱ between 467 ±12 Ma and 445.5 ±12 Ma. The folding event recorded only by the Complex I should therefore have occurred between 494 ±5 Ma and 467 ±12 Ma. The Variscan eclogite-amphibolite facies metamorphism is instead constrained between ∼420 Ma and ∼300 Ma. These ages and the geochemical signature of these rocks allow constraining the Early Paleozoic tectono-magmatic evolution of the Ligurian blocks, from a middle-upper Cambrian rifting stage, through the formation of an Early Ordovician volcanic arc during the Rheic Ocean subduction, until a Late Ordovician extension related to the arc collapse and subsequent rifting of the PaleoThetys. Furthermore, the ∼420-350 Ma ages from zircon rims testify to thermal perturbations that may be associated with the Silurian rifting-related magmatism, followed by the subduction-collisional phases of the Variscan orogeny.
The Huoshenmiao deposit is Mo skarn deposit, located in the western part of the Luanchuan ore district. Mineralization process can be divided into a skarn and a quartz-sulfide episodes with six stages: prograde (I), retrograde (Ⅱ), quartz-K-feldspar (Ⅲ), quartz-molybdenite (IV), quartz-pyrite (V), and quartz-calcite (VI). A combined study of geochronology, fluid inclusion (FI), and stable isotopes was conducted to constrain the mineralization age, source of ore materials, as well as the origin and evolution of the ore-forming fluids. Molybdenite Re-Os dating indicates that the deposit was formed in the Late Jurassic (∼145 Ma). The δ34S values of sulfides range from 3.0‰ to 7.1‰, implying that the ore materials in the deposit are magmatic in origin. Three types and six subtypes of FIs are distinguished, namely, aqueous two-phase (W1- and W2-type), daughter mineral-bearing multiphase (S1- and S2-type), and CO2-bearing three-phase (C1- and C2-type). In stages I and Ⅱ, the W1-type FIs display homogenization temperatures (Th) from 496 ℃ to >600 ℃, with salinities of 14.9-18.3 wt.% NaCl eqv. The FIs in stages Ⅲ, IV and early stage V composed of coeval S-, C- and W-types, respectively homogenize at similar Th, suggesting the occurrence of boiling. The W1-type FIs in late stage V and stage VI, yield Th of 102-406 ℃ and salinities of 0-4.7 wt.% NaCl eqv. The δDH2O and δ18OH2O values of the ore-forming fluids in quartz-sulfide episode vary from -112‰ to -76‰, and 11.0‰ to 1.0‰, respectively. All these above observations reveal that the early ore-forming fluids are magmatic in origin, and characterized by high temperature and moderate to high salinity, and gradually evolve to low temperature, low salinity meteoric water. The Huoshenmiao Mo deposit is associated with the magmatism event induced by the protracted subduction of the Izanagi plate beneath the eastern China continent. The decrease in temperature, salinity and f(O2), as well as change of pH due to boiling and fluid-rock interaction, are the main factors controlling Mo deposition.
The surface sediments collected from the southern Mariana Trench at water depths between ca. 4900 m and 7068 m were studied using lipid biomarker analyses to reveal the origin and distribution of organic matters. For all samples, an unresolved complex mixture (UCM) was present in the hydrocarbon fractions, wherein resistant component tricyclic terpanes were detected but C27-C29 regular steranes and hopanes indicative of a higher molecular weight range of petroleum were almost absent. This biomarker distribution patterns suggested that the UCM and tricyclic terpanes may be introduced by contamination of diesel fuels or shipping activities and oil seepage elsewhere. The well-developed faults and strike-slip faults in the Mariana subduction zone may serve as passages for the petroleum hydrocarbons. In addition, the relative high contents of even n-alkanes and low Carbon Preference Indices indicated that the n-alkanes were mainly derived from bacteria or algae. For GDGTs, the predominance of GDGT-0 and crenarchaeol, together with low GDGT-0/Crenarchaeol ratios (ranging from 0.86 to 1.64), suggests that the GDGTs in samples from the southern Mariana Trench were mainly derived from planktic Thaumarchaeota. However, the high GDGT-0/crenarchaeol ratio (10.5) in sample BC07 suggests that the GDGTs probably were introduced by methanogens in a more anoxic environment. Furthermore, the n-alkanes C19-C22 and the n-fatty acids C20:0-C22:0 were depleted in 13C by 3‰ compared to n-alkanes C16-C18 and the n-fatty acids C14:0-C18:0, respectively, which was interpreted to result from the preferential reaction of fatty acid fragments with carbon “lighter” terminal carboxyl groups during carbon chain elongation from the precursors to products. The abundance of total alkanes, carboxylic acids, alcohols and total lipids were generally increased along the down-going seaward plate, suggesting the lateral organic matter inputs play an important role in organic matter accumulation in hadal trenches. The extremely high contents of biomarkers in sample BC11 were most likely related to trench topography and current dynamics, since the lower steepness caused by graben texture and proximity to the trench axis may result in higher sedimentation rate. This paper, for the first time, showed the biomarker patterns in surface sediments of the Mariana Trench and shed light on biogeochemistry of the hardly reached trench environment.