molybdenum isotope signatures in continental margin marine sediments abstract we present molybdenum isotope data for four sediment profiles from continental margin settings each profile has a distinctive average isotope composition ranging from 98 95 mo 0 5 to 1 3 relative to j and m laboratory standard this range lies between the modern ocean water value 2 3 and the values typical of mo adsorbed onto mn oxides 0 7 0 1 an important finding of this study is the apparent co variation between the mo isotope composition and the accumulation rate of authigenic mo under reducing conditions this relationship suggests that the chemical processes responsible for mo accumulation under reducing conditions produce an isotope signature in marine sediments in addition to the relationship between mo accumulation and the mo isotope signature there is also a relationship between these parameters and the rate of organic carbon oxidation and burial these relationships suggest that the mo isotope signature of reducing sediments may serve as a tracer for the cycling of organic carbon in continental margin sediments however additional data will be required to refine any such relationships

molybdenum behavior during early diagenesis insights from mo isotopes 1 we present molybdenum isotope and concentration data from 14 sites in the eastern pacific from the central california to the peru margin the environments studied have been chosen to represent a broad range in oxidation reduction redox potential which provide a framework for the behavior of this redox sensitive element manganese rich hemipelagic sediments from the eastern tropical pacific have a mean characteristic mo isotope signature 98 95mo 0 49 0 04 two times the standard deviation of the mean 2 sdom with n 14 that reflects fractionation between ocean water and authigenic mo associated with mn oxides authigenic fe mo s deposits from reducing continental margin settings also have a characteristic mo isotopic signature 98 95mo 1 64 0 04 2 sdom with n 136 both of these values are in contrast to highly sulfidic 11 m h2saq restricted basin environments which contain mo isotope values analytically indistinguishable from seawater in terms of the mo isotope composition the modern oceanic mo sink is dominated by continental margin type environments where 98 95mo 1 6 and mn rich sediments where 98 95mo approximately 0 5 with a minor contribution from euxinic settings where h2saq 11 m

tibetan tectonic evolution inferred from spatial and temporal variations in post collisional magmatism cenozoic magmatism on the tibetan plateau shows systematic variations in space and time that must be considered in models concerning tibetan tectonic evolution after the india asia collision which started in the early tertiary and terminated the gangdese arc magmatism in the lhasa terrane made of the southern tibetan plateau widespread potassium rich lavas and subordinate sodium rich basalts were generated from f50 to 30 ma in the qiangtang terrane of northern tibet subsequent post collisional magmatism migrated southwards producing ultrapotassic and adakitic lavas coevally between f26 and 10 ma in the lhasa terrane then potassic volcanism was renewed to the north and has become extensive and semicontinuous since f13 ma in the western qiangtang and songpan ganze terranes such spatial temporal variations enable us to elaborate a geodynamic evolution model which depicts when and how the indian continental lithospheric mantle started thrusting under asia by involving rollback and breakoff of the subducted neo tethyan slab followed by removal of the thickened lhasa lithospheric root we propose that only after the lithospheric removal which occurred at f26 ma could the indian mantle lithosphere have commenced its northward underthrusting and henceforth served as a pivotal control to the himalayan tibetan orogenesis consequently the tibetan plateau is suggested to have risen diachronously from south to north whereas the southern part of the plateau may have been created and maintained since the late oligocene the northern plateau would have not attained its present day elevation and size until the mid miocene when the lower part of the western qiangtang and songpan ganze lithospheres began to founder owing to the push of the underthrust indian mantle lithosphere d 2004 elsevier b v all rights reserved

contributions from mafic alkaline magmas to the bingham porphyry cu au mo deposit utah usa the bingham porphyry cu au mo deposit utah may only be world class because of substantial contributions of sulfur and metals from mafic alkaline magma to an otherwise unremarkable calc alkaline system volcanic mafic alkaline rocks in the district are enriched in cr ni and ba as well as cu au platinum group elements pge and s the bulk of the volcanic section that is co magmatic with ore related porphyries is dacitic to trachytic in composition but has inherited the geochemical signature of high cr ni and ba from magma mixing with the mafic alkaline rocks the volcanic section that most closely correlates in time with ore related porphyries is very heterogeneous containing clasts of scoriaceous latite latitic and minette and flows of melanephelinite shoshonite and olivine latite in addition to volumetrically dominant dacite trachyte bingham ore related porphyries show ample evidence of prior mixing with mafic alkaline magmas intrusive porphyries that have not been previously well studied have several chemical and mineralogical indications of magma mixing these mixed lithologies include the hybrid quartz monzonite porphyry biotite porphyry and minette dikes even some of the more silicic latite and monzonite porphyries retain high cr and ba contents indicative of mixing and contain trace amounts of sapphire 1 mm the heterogeneous block and ash flow deposits also contain sapphire and are permissively correlated with the intrusions based on chemical mineralogical and isotopic data magma mixing calculations suggest about 10 of the monzonitic latitic ore related magma may have been derived from mafic alkaline magma similar to the melanephelinite if the original s content of the mafic magma was about 2 000 4 000 ppm comparable with similar magmas then the mafic magma may have been responsible for contributing more than half of the s and a significant portion of the cu au and pge in the bingham deposit

tectonic trigger for the formation of late miocene cu rich breccia pipes in the andes of central chile during the late miocene the decreasing angle of subduction below the andes of central chile caused a reduction in the influx of new magma and heat into the base of magmatic systems that had been active throughout the miocene this led to their cooling and solidification triggering the release of large volumes of metal rich magmatic fluids from middle and upper crustal magma chambers and generating a group of economically significant cu rich breccia pipes the sr and nd isotopic compositions of the magmatic fluids that formed these brecccas determined from breccia matrix minerals were variable implying that these fluids were not exsolved from a specific cu porphyry magma as is often invoked to explain andean cu deposits instead the formation of the late miocene deposits in central chile was tectonically triggered by cooling of a variety of magma types during the last stages of existence of long lived andean magmatic systems as both subduction angle and as a result subarc magma supply decreased

the remarkable re os chronometer in molybdenite how and why it works the re os rhenium osmium chronometer applied to molybdenite mos2 is now demonstrated to be remarkably robust surviving intense deformation and high grade thermal metamorphism successful dating of molybdenite is dependent on proper preparation of the mineral separate and analysis of a critical quantity of molybdenite unique to each sample such that recognized spatial decoupling of 187re parent and 187os daughter within individual molybdenite crystals is overcome highly precise accurate and reproducible age results are derived through isotope dilution and negative thermal ion mass spectrometry id ntims spatial decoupling of parent daughter precludes use of the laser ablation icp ms microanalytical technique for re os dating of molybdenite the use of a reference or control sample is necessary to establish laboratory credibility and for interlaboratory comparisons the rb sr k ar and 40ar 39ar chronometers are susceptible to chemical and thermal disturbance particularly in terranes that have experienced subsequent episodes of hydrothermal magmatic activity and therefore should not be used as a basis for establishing accuracy in re os dating of molybdenite as has been done in the past re os ages for molybdenite are almost always in agreement with observed geological relationships and when available with zircon and titanite u pb ages for terranes experiencing multiple episodes of metamorphism and deformation molybdenite is not complicated by overgrowths as is common for some minerals used in u pb dating e g zircon monazite xenotime nor are re and os mobilized beyond the margins of individual crystals during solid state recrystallization moreover inheritance of older molybdenite cores incorporation of common os and radiogenic os loss are exceedingly rare whereas inheritance common pb and pb loss are common complications in u pb dating techniques therefore molybdenite ages may serve as point in time markers for age comparisons

natural mass dependent variations in the isotopic composition of molybdenum we present the first observations of natural mass dependent fractionation of the isotopic composition of molybdenum mo using multi collector inductively coupled plasma mass spectrometry variations in the isotopic composition of mo are reported as 97 95mo 97mo 95mo sample 97mo 95mo standard 1 1000 external analytical precision of 97 95mo is 1 between sediments deposited under anoxic conditions 97 95mo 1 02 to 1 52 relative to our in house standard and ferromanganese nodules 97 95mo 0 63 to 0 42 97 95mo of pacific ocean seawater 97 95mo 1 48 lies within the range of values for anoxic sediments closest to modern black sea anoxic sediments molybdenites from continental ore deposits have intermediate 97 95mo ranging from 0 26 to 0 09 variations in the abundances of 92mo 95mo 96mo 97mo and 98mo are consistent with mass dependent fractionation a sporadic unidentified interference occurs at mass 94 and 100mo is not measured we hypothesize that the 97 95mo offset between anoxic sediments and ferromanganese nodules results from mo isotope fractionation during inefficient scavenging of mo from seawater by mn oxides under oxic conditions the similarity in 97 95mo of anoxic sediments and seawater is consistent with the very efficient removal of mo from seawater under anoxic conditions in the presence of h2s the data can be interpreted in terms of a steady state mass balance between the mo flux into the oceans from the continents and the mo flux out of the oceans into oxic and anoxic sediments such an interpretation is quantitatively consistent with existing estimates of the removal fluxes of mo to anoxic and oxic sediments these findings suggest that 97 95mo in seawater may co vary with changes in the relative proportions of anoxic and oxic sedimentation in the oceans and that this variation may be recorded in 97 95mo of anoxic sediments hence the mo isotope system may be useful in paleoredox investigations

contribution of mantle components within juvenile lower crust to collisional zone porphyry cu systems in tibet most porphyry cu mo au deposits are found in magmatic arcs worldwide and are associated with hydrous high fo2 calc alkaline magmas derived from a mantle wedge that was metasomatized by the fluids from a subducted oceanic slab recently such deposits have been documented as occurring widely in collisional settings where they are associated with potassic magmas generated during the collisional process but the genesis of the fertile magmas and the mechanism of metallic enrichment remain controversial here we present new geochemical and sr nd hf isotopic data from the post collisional fertile and barren porphyries of the miocene gangdese porphyry belt in the tibetan orogen an orogen formed by the collision of india and asia in the early cenozoic both types of porphyry are characterized by high k2o contents and have geochemical affinities with adakite but the fertile magmas were most likely derived from the melting of a thickened juvenile mafic lower crust formed by the underplating of earlier asthenospheric melts at the base of crust whereas the derivation of the barren magmas involved variable amounts of old lower crust in tibet the melting of sulfide bearing phases in the juvenile mantle components of the tibetan lower crust probably provided cu au and s to the fertile magmas the breakdown of amphibole during melting at the source released the fluids necessary for the formation of the porphyry cu deposits in tibet the thickened crust up to 70 80 km due to collision is thought to be responsible for a decrease in the fo2 of the fertile magmas during their ascent to the upper crust thus preventing the generation of more porphyry cu au and epithermal au deposits in this collisional zone

u mo ratios and δ98 95mo as local and global redox proxies during mass extinction events abstract when used in conjunction with trace metal redox proxies the use of u mo ratios and 98 95 mo values can considerably enhance the interpretation of ocean oxygenation trends both locally and globally this is illustrated with studies from two biogenic chert dominated records of mass extinction the ordovician silurian boundary and the late permian in sections from the yangtze block in south china the latest ordovician mass extinction is well known to coincide with oxygenation episode in the hirnantian stage here revealed by trace metal proxies v v ni v cr ni co that show it sandwiched between anoxic euxinic black shales the predominantly anoxic euxinic ordovician silurian strata provide a record of seawater 98 95 mo values that are seen to gradually rise during the interval from 0 5 to 1 0 the exception to the 98 95 mo stability is the datum of the slight negatively 98 95 mo associated with decreasing of v cr and v v ni ratio suggesting the hirnantian oxygenation event the upper permian chert succession at shangsi reveals an overall better ventilated record in which the best oxygenated strata show the highest u mo values that is interpreted as relative enrichment of u in suboxic conditions at a few levels anoxic euxinic conditions show the 98 95 mo values to be 2 close to modern values implying that latest permian oceans were as well ventilated as those today the well known end permian oceanic anoxic event is therefore suggested to only develop at the end of this period

molybdenum isotope behaviour accompanying weathering and riverine transport in a basaltic terrain the application of the molybdenum mo isotope system as a proxy for determining changes in the redox state of the oceans is predicated on the assumption that the composition of continental input can be characterised from crustal rock types and remains constant however it has recently been shown that the 98 95mo composition of global rivers varies between 0 15 and 2 4 and is therefore systematically heavier than the average composition of the continental crust 0 in order to understand the processes that control mo isotope fractionation during weathering this study presents 98 95mo and mo abundance data for rivers and estuarine samples from iceland that drain predominantly basaltic terrains resolvable differences are observed in the isotopic composition of the riverine mo sources ice 98 95moice 1 8 basaltic bedrock 98 95mobedrock 0 0 and hydrothermal waters 98 95mohydrothermal 3 4 systematic changes in the dissolved mo isotope composition are also observed within river catchments with 98 95mo values increasing from 0 in glacial rivers close to the source to 1 downstream consistent with mo isotopes being fractionated during weathering analysis of other riverine phases bedload colloids and iron precipitates demonstrates that these phases preferentially incorporate light mo isotopes and remain coupled to the dissolved load during riverine transportation a 98 95mo profile through the borgarfjor eth ur estuary exhibits a predominantly conservative mixing behaviour but suggests that the release of isotopically light mo from the particulate and or colloidal phases may occur in the low salinity part of the estuarine mixing zone 2010 elsevier b v

zircon u pb and hf isotope constraints on the mesozoic tectonics and crustal evolution of southern tibet the first in situ hf and u pb isotope analyses of zircon separates from mesozoic granites in southern tibet identify a significant previously unknown stage of magmatism igneous zircons n 34 from a granite within the gangdese batholith show a weighted mean 206 pb 238 u age of 188 1 1 4 ma and e hf t the parts in 10 4 deviation of initial hf isotope ratios between the zircon sample and the chondritic reservoir values between 10 4 and 16 8 suggesting predominantly early jurassic intrusive activity with a juvenile mantle contribution of 40 inherited zircons from two cretaceous s type granites in the northern magmatic belt 23 delineate a slightly older 206 pb 238 u age cluster between 188 and 210 ma these zircons have e hf t values from 3 9 to 13 7 yielding crustal hf model ages from ca 1 4 to 2 1 ga suggesting a major episode of crustal growth in proterozoic time and remelting of this crust in early jurassic time combining these with literature data we interpret the jurassic gangdese magmatism as an early product of the neo tethyan subduction that played a long lasting role in the tectonic evolution of southern tibet prior to the india asia collision

geology of the post collisional porphyry copper molybdenum deposit at qulong tibet porphyry deposits are usually thought to form from subduction related calc alkaline magmas in magmatic arc settings although some porphyry deposits also occur in post collisional extensional settings the post collisional deposits remain poorly understood here we describe the igneous geology alteration mineralogy and mineralization history of qulong a newly discovered porphyry cu mo deposit in southern tibet that belongs to the post collisional class the deposit is associated with miocene monzogranite granodiorite intrusions and is hosted partly by jurassic andesitic dacitic volcanic rocks the deposit contains 7 1 mt cu and 0 5 mt mo metal the 19 5 ma granodioritic monzogranitic rongmucuola pluton with diorite enclaves is the earliest miocene intrusive unit it was intruded by a regularly shaped stock p porphyry and then thin dikes x porphyry of monzogranite at about 17 7 ma the main cu mo mineralization is associated with the p porphyry a barren diorite porphyry intruded the p and x porphyries around 15 7 ma petrologic trends of the intrusions suggest that the miocene intrusions have similar origins and probably formed by fractionation of a deeper magma chamber emplacement of miocene porphyries controlled by the qulong anticline is in direct response to the rapid uplift erosion of the gangdese arc batholiths in southern tibet miarolitic cavities and unidirectional solidification textures key evidence for volatile separation have been recognized in the p and x porphyries respectively early potassic alteration characterized by quartz k feldspar anhydrite pervades the p porphyry and rongmucuola pluton laterally this alteration grades into quartz biotite anhydrite k feldspar which affects all miocene intrusions except the latest dioritic porphyry wall rocks of rongmucuola pluton and jurassic andesitic dacitic volcanics within 1 1 5 km of the porphyries are dominated by pervasive potassic alteration an outer halo of propylitic alteration epidote chlorite calcite extends up to 2 km away from the deposit feldspar destructive alteration sericite chlorite clay minerals has overprinted most of the potassic and part of the propylitic alteration the alteration is strongly pervasive in the interior of the porphyry bodies and occurs as vein halos away from the porphyry bodies the earliest quartz k feldspar alteration and veins are barren whereas approximately 60 of the cu reserves is associated with slightly later quartz biotite anhydrite alteration barren assemblages are related to irregular quartz k feldspar anhydrite veins which are truncated by the x porphyry cu sulfide bearing assemblages are associated with discontinuous chalcopyrite biotite and continuous quartz anhydrite chalcopyrite molybdenite veins deposition of cu mo with abundant anhydrite occurred during or between emplacement of closely related porphyries from high temperature magmatically derived fluids and was probably caused by the disproportionation of so

the exhumation history of collision related mineralizing systems in tibet insights from thermal studies of the sharang and yaguila deposits central lhasa abstract the large newly discovered sharang porphyry mo deposit and nearby yaguila skarn pb zn ag mo deposit reside in the central lhasa terrane northern gangdese metallogenic belt tibet multiple mineral chronometers zircon u pb sericite 40 ar 39 ar and zircon and apatite u th he reveal that ore forming porphyritic intrusions experienced rapid cooling 100 c ma during a monotonic magmatic hydrothermal evolution the magmatic hydrothermal ore forming event at sharang lasted 6 0 myr 1 8 myr for cooling from 900 to 350 c and 4 0 myr for cooling from 350 to 200 c whereas cooling was more prolonged during ore formation at yaguila 1 8 myr from 900 to 500 c and a maximum of 16 myr from 900 to 350 c all porphyritic intrusions in the ore district experienced exhumation at a rate of 0 07 0 09 mm yr apatite he ages between 37 and 30 ma combined with previous studies this work implies that uplift of the eastern section of the lhasa terrane expanded from central lhasa 37 30 ma to southern lhasa 15 12 ma at an increasing exhumation rate all available geochronologic data reveal that magmatic hydrothermal exhumation activities in the sharang yaguila ore district occurred within four periods of magmatism with related mineralization significant porphyry type mo mineralization was associated with late cretaceous eocene felsic porphyritic intrusions in the central lhasa terrane resulting from neotethyan oceanic subduction and india asia continental collision

collision related genesis of the sharang porphyry molybdenum deposit tibet evidence from zircon u pb ages re os ages and lu hf isotopes article i nfo sharang is a low fluorine calc alkaline porphyry mo deposit hosted mainly in a granite porphyry of a multi stage plutonic complex in the northern gangdese metallogenic belt largely with stockwork and ribbon textured mineralization the observed age estimates suggest that the formation of the magmatic host complex 52 9 51 6 ma and the ore deposit itself 52 3 ma occurred during the main stage of the india asia collision the host rocks are characterized by lower zircon ehf t values than those of the pre ore and post ore rocks this suggests that the lhasa terrane basement might play an important role in the formation of sharang ore forming intrusions in view of the framework of magmatic metallogenic events we suggest that slab roll back may have induced melting of juvenile crust and ancient continental complexes during the india asia collision this proposal focuses exploration for additional molybdenum deposits on the collision zone

century long record of mo isotopic composition in sediments of a seasonally anoxic estuary chesapeake bay abstract a double spike method was used to obtain mo isotope data for sediments and waters of the seasonally anoxic chesapeake bay and its primary tributary the susquehanna river the dissolved mo distribution in the estuary is non conservative reflecting minor mo loss to the sediments although removal of mo to the sediments does not have a large influence on the isotopic composition of the water column the 98mo of dissolved mo in most of the estuary is dominated by seawater six samples with salinity 15 have an average 98mo 2 17 0 12 which agrees well with a 98mo value for the cass 4 seawater standard of 2 23 a single sample of susquehanna river water has a 98mo of 1 02 consistent with recent findings of positive 98mo in rivers worldwide susquehanna river sediments in contrast have 98mo 0 1 the difference between the river water and sediment values implies that isotopic fractionation occurs within the river basin the 98mo values for estuarine sediments are offset from values in the overlying water most samples deposited before 1925 have 98mo less than 0 similar to the susquehanna sediments subsequently there is an increase in the variability of 98mo with values ranging up to 0 8 the transition to increased variability coincides with the onset of authigenic mo deposition which was previously attributed to escalating summertime anoxia authigenic mo concentrations correlate poorly with 98mo in core samples suggesting that independent mechanisms influence the two parameters authigenic mo concentrations may be controlled by shifting pore water h2s levels while 98mo may be primarily affected by annual variations in mn refluxing

changes in marine productivity and redox conditions during the late ordovician hirnantian glaciation abstract changes in marine productivity and redox conditions during the end ordovician hirnantian glaciation and ordovician silurian transition were investigated through mo isotope and major and trace element analyses of the wangjiawan hubei province and nanbazi guizhou province sections from the yangtze platform of south china katian shales of the wufeng formation which yield the graptolites dicellograptus complanatus dicellograptus complexus and paraorthograptus pacificus were deposited under euxinic conditions at both localities as shown by high mo ef u ef and 98 mo values a major sea level regression during the hirnantian glaciation resulted in shallowing and a shift toward better oxygenated conditions within the yangtze sea as well as deposition of thin bedded siliceous sediments calcirudite debris flows and limestone turbidites of the kuanyinchiao formation the base of which correlates with the first phase of the end ordovician mass extinction the termination of the hirnantian glaciation at the top of the kuanyinchiao formation was associated with a major sea level transgression a rapid expansion of euxinia in the yangtze sea as documented by a return of high mo ef u ef and 98 mo values and the second phase of the mass extinction during which the cool adapted hirnantian fauna went extinct the long term cooling trend of the middle and late ordovician which culminated in the hirnantian glaciation was driven by enhanced burial of organic carbon as documented by 13 c carb 13 c org and 34 s py records increased organic carbon burial was linked to high rates of marine productivity as shown by high toc and biogenic ba concentrations especially at the deeper less restricted wangjiawan locale producing the hice hirnantian isotopic curve excursion 13 c carb excursion the locus of organic carbon burial during the hirnantian crisis shifted to deeper water environments that were located outside the study region the relatively rapid onset and termination of the hirnantian glaciation were probably due to crossing of tipping points in the late ordovician climatic oceanic system

molybdenum isotope variations in molybdenite vapor transport and rayleigh fractionation of mo molybdenum isotopes in 20 molybdenite samples dated by the re os method and representing a range of geologic settings show mass dependent fractionation spanning 0 63 per atomic mass unit amu previous mo isotope data for molybdenite reveal variations in fractionation of 0 5 amu interpretation of these data is hampered however by limited sample numbers in each study lack of a common standard for interlaboratory comparison and limited range of geologic settings here we show that mo isotope compositions of molybdenites do not correlate with crystallization temperature age geographic distribution or geologic conditions rather rayleigh distillation may explain variations of as much as 0 34 amu in a single molybdenite occurrence exceeding the proposed variability in average continental crust vapor transport and rapid precipitation of mo in propagating fractures may account for isotope fractionation of mo and perhaps other metals at very small scales if so the average isotopic composition of mo at each molybdenite occurrence may be representative of bulk crust our results suggest that the isotopic composition of mo delivered to the oceans is uniform geographically and through geologic time

arsenic in iron disulfides in a brown coal from the north bohemian basin czech republic arsenic in the coal studied is not bound to coal macerals it is concentrated in the inorganic part of coal specifically in the iron sulfides this paper reports the results of five crystal structure refinements that include natural 2 and synthetic 3 sulfides pyrite 3 and marcasite 2 powder 3 and single crystal 2 intensities used in the refinements were obtained by diffraction of x rays 4 and synchrotron radiation 1 the refined occupancy factors of sulfur and the unit cell parameters favor the possibility that as substitutes for s in both disulfides

determination of molybdenum isotope fractionation by double spike multicollector inductively coupled plasma mass spectrometry 1 molybdenum isotopic compositions are precisely determined by mc icp ms measurements using a mo double spike the double spike is added prior to chemical purification so that laboratory and instrumental mass fractionations are separated from natural mass dependent fractionation fractionation is determined on four mo mass ratios providing an internal consistency check the external standard reproducibility is at 0 06 per mil on the 98mo 95mo ratio 2 standard deviation using a normal microconcentric nebuliser with a cyclonic spray chamber the minimum quantity of mo is 1 g for high precision results a hydrothermal molybdenite shows fractionation of 0 3 per mil on the 98mo 95mo ratio relative to our standard johnson matthey 1000 g ml 0 3 icp standard solution lot 602332b fine grained sediments show fractionation of 0 1 and 0 3 per mil on the 98mo 95mo ratio the observed mo isotope fractionation is small but resolvable with the presented high resolution technique

molybdenum isotope evidence for mild environmental oxygenation before the great oxidation event abstract we use the molybdenum isotope paleoredox proxy to look for evidence of small amounts of o2 in the environment 50 ma before the great oxidation event goe in a high resolution profile from the 2 5 ga mt mcrae shale the molybdenum isotope compositions 98 95mo from samples throughout the sequence span a range from 0 99 to 1 86 all samples have heavier 98 95mo compared to average upper continental crust in addition the upper s1 and lower s2 black shale units within the mt mcrae shale exhibit systematic differences in average isotopic compositions and distinct patterns of 98 95mo variation heavier 98 95mo values occur in the s1 unit where 98 95mo correlates with mo enrichments in the s2 unit 98 95mo is not as heavy and is relatively invariant based on sedimentary fe proxies we infer that s1 sediments were deposited under euxinic conditions so that mo removal from bottom waters was likely quantitative thus 98 95mo in this interval likely records coeval seawater the lighter 98 95mo values in the s2 unit may indicate a less fractionated ocean mo inventory relative to the s1 unit however sedimentary fe proxies suggest that s2 sediments accumulated under a water column that was ferruginous rather than euxinic raising the possibility of non quantitative mo scavenging and hence an expressed 98 95mo fractionation relative to coeval seawater because any associated fractionations during this process would have favored the light isotope in sediments the lighter 98 95mo values in the s2 unit represent a lower limit on the value in contemporaneous seawater after evaluating a range of hypotheses we conclude that the isotopically heavy 98 95mo values seen throughout the mt mcrae shale likely reflect the effects of oxidative weathering and adsorption of mo to oxide mineral surfaces on land or in surface oceans the extent of environmental oxygenation in either unit is difficult to assess due to uncertainties in the global mo isotope budget because of the small ocean mo inventory in the late archean documented by low concentrations of mo and low mo toc the extent of oxygenation required to account for the observed fractionations is much smaller than in modern oceans however when juxtaposed against the record of 98 95mo through time our findings provide further evidence of the onset of environmental oxygenation before the goe

mineral deposits of canada a synthesis of major deposit types district metallogeny the evolution of geological provinces and exploration methods wayne d goodfellow editor 1 068 pp geological association of canada mineral deposits division special publication no 5 2007 hardcover isbn 13 978 1 897095 24 9 price members cdn 60 00 non members cdn 80 00 following in the footsteps of other landmark reviews of major ore producing countries such as australia hughes 1990 solomon and groves 1994 and south africa anhaeusser and maske 1986 this substantial 1 000 pages monograph is a great achievement that should be in every geologic research library in the world in many ways it sets a new standard most notably in that all figures and photographs are in color and that the entire volume is available in electronic form both as an included dvd and mostly on the gac website it is common in such compendia to have a spectacular cover photo or frontispiece to catch the reader s attention and this book does not disappoint the frontispiece photo is of a 61 8 kg sample from the dome mine timmins ontario and is stated to contain 20 wt percent gold at today s prices the gold alone would be worth 1 5 million dollars

paragenesis and composition of laurite from chromitites of othrys greece implications for os ru fractionation in ophiolitic upper mantle of the balkan peninsula os rich laurite and erlichmanite are the dominant pgm inclusions in chromitites of the othrys ophiolite complex close association of the pgm sulfides with enstatite na rich pargasite clinopyroxene phlogopite and cu ni sulfides indicates crystallization at high temperature in the presence of an alkali rich fluid phase under relatively high sulfur fugacity because of the predominance of ru os ir phases the pgm assemblage of othrys is similar to that of chromitites located in the mantle unit of other ophiolite complexes of the balkan peninsula vourinos skyros island rhodope although it is distinguished because of the os rich composition of laurite and the presence of erlichmanite comparison among literature data for these complexes indicates that the os ru ratios vary consistently in laurite and bulk chromitite with respect to the chondritic os ru value this suggests that fractionation between the two elements occurred being apparently registered in the composition of laurite inclusions among other factors fluctuation of sulfur fugacity during fractionation as well as variation of the os ru ratio in the parent melts of the chromitites might be invoked to explain the ru os decoupling

the lhasa terrane record of a microcontinent and its histories of drift and growth article i nfo the lhasa terrane in southern tibet has long been accepted as the last geological block accreted to eurasia before its collision with the northward drifting indian continent in the cenozoic but its lithospheric architecture drift and growth histories and the nature of its northern suture with eurasia via the qiangtang terrane remain enigmatic using zircon in situ u pb and lu hf isotopic and bulk rock geochemical data of mesozoic early tertiary magmatic rocks sampled along four north south traverses across the lhasa terrane we show that the lhasa terrane has ancient basement rocks of proterozoic and archean ages up to 2870 ma in its centre with younger and juvenile crust phanerozoic accreted towards its both northern and southern edges this finding proves that the central lhasa subterrane was once a microcontinent this continent has survived from its long journey across the paleo tethyan ocean basins and has grown at the edges through magmatism resulting from oceanic lithosphere subduction towards beneath it during its journey and subsequent collisions with the qiangtang terrane to the north and with the indian continent to the south zircon hf isotope data indicate significant mantle source contributions to the generation of these granitoid rocks e g 50 90 0 70 and 30 100 to the mesozoic magmatism in the southern central and northern lhasa subterranes respectively we suggest that much of the mesozoic magmatism in the lhasa terrane may be associated with the southward bangong nujiang tethyan seafloor subduction beneath the lhasa terrane which likely began in the middle permian or earlier and ceased in the late early cretaceous and that the significant changes of zircon ehf t at 113 and 52 ma record tectonomagmatic activities as a result of slab break off and related mantle melting events following the qiangtang lhasa amalgamation and india lhasa amalgamation respectively these results manifest the efficacy of zircons as a chronometer u pb dating and a geochemical tracer hf isotopes in understanding the origin and histories of lithospheric plates and in revealing the tectonic evolution of old orogenies in the context of plate tectonics

the isotopic signature of the global riverine molybdenum flux and anoxia in the ancient oceans despite important biological and biogeochemical consequences of extensive ocean anoxic events their identification is controversial the marine isotope geochemistry of molybdenum can help quantify the past oxygenation state of the ocean if the riverine input of mo isotopes is known analysis of a set of rivers that account for 28 of global river runoff suggests more variable mo isotopic ratios in rivers that are also isotopically enriched in the heavy isotopes suggesting near total anoxia in the proterozoic ocean and during mesozoic ocean anoxic events despite its important biological and biogeochemical consequences1 2 3 the identification of extensive oceanic anoxia in the geological record is controversial in particular global anoxia is difficult to distinguish from spatially restricted anoxia in the deep ocean or in tectonically isolated basins such as the modern black sea the marine isotope geochemistry of molybdenum mo can help quantify the past oxygenation state of the ocean4 5 6 7 8 9 10 11 12 13 14 because to first approximation under oxic conditions lighter isotopes of mo are preferentially removed to sediments whereas in euxinic conditions quantitative removal leads to no fractionation however the isotopic composition of the mo input from rivers the main contributor of mo to the oceans is poorly constrained and had been assumed to be isotopically comparable to the narrow range found in a small dataset of continental rocks4 5 6 7 8 9 10 11 12 13 14 here we present an isotopic analysis of mo in a set of rivers that together account for 22 of the global riverine water discharge we find a broad range of variability in the mo isotopic composition of these rivers with almost all samples enriched in the heavy isotopes compared with continental rocks our data remove key uncertainties associated with the marine mo isotope budget14 and strongly suggest near total anoxia in the mid proterozoic ocean8 as well as during mesozoic ocean anoxic events13

the miocene gangdese porphyry copper belt generated during post collisional extension in the tibetan orogen abstract the mid miocene gangdese orogenic belt in southern tibet contains porphyry cu deposits that developed after the indian asian continental collision in the early cenozoic field work confirms that these porphyry cu deposits are temporally and spatially associated with mid miocene monzogranitic and quartz monzonitic stocks which intruded mesozoic cenozoic gangdese granitoid batholiths and surrounding triassic tertiary volcano sedimentary sequences in the lhasa terrane and formed a 50 km wide 400 km long e w belt magmatism occurred during the interval 11 2 to 19 7 ma peaking at 16 ma for the porphyry stocks this is consistent with the age 10 to 18 ma of the east west extension and subsequent ns striking normal fault systems 13 5 ma in the tibetan orogen the stocks typically occur as multiple small diameter intrusions 50 km breakdown of hornblende in the juvenile lower crust source during melting is regarded as fundamental for the formation of the fertile adakite and porphyry cu systems in south tibet the gangdese belt contains four large and three intermediate and small sized porphyry cu mo deposits and shows a continuous spectrum from typical porphyry type cu mo to skarn type zn pb mineralization twenty three samples collected from four deposits yielded a limited range of molybdenite re os isochron ages from 15 2 to 16 0 ma similar to previously reported re os ages 13 8 to 14 9 ma for other porphyry cu mo deposits in the belt suggesting that cu mo mineralization in the belt occurred in a post collisional extension environment the characteristics of porphyry cu mo deposits in the collisional zone are similar in many aspects to those in arc settings i e mineralization style alteration zoning and metal association preliminary fluid inclusion studies indicate that the early hydrothermal fluids are preserved as high temperature 450 c high salinity 40 to 47 wt nacl equiv and high pressure 1100 to 1500 bar fluid inclusions these fluids are interpreted to represent an orthomagmatic fluid that boiled episodically due to fluid overpressuring and hydrofracturing resulting in potassic alteration and precipitation of chalcopyrite molybdenite assemblages on the basis of comparison with porphyry cu deposits in arc settings we proposed that melting of thickened newly formed basaltic crust resulted in generation of cu bearing magmatic systems in the tibetan collision zone and both orogen transverse normal faults and orogen parallel thrust zones during the miocene post collisional extension constrain the temporal and spatial localization of the porphyry cu systems in the collision zone

re os isotopic dating of molybdenites in the xiaoliugou w mo deposit in the northern qilian mountains and its geological significance abstract the xiaoliugou is a large scale w mo deposit newly explored in the northern qilian mountains caledonian fold belt northwestern china it is a vein and skarn type deposit genetically associated with the xiaoliugou caledonian granodiorite stock re os isotopic dating for the molybdenite in the deposit yields an isochron age of 462 13 ma 2 and model ages of 436 to 496 ma these results suggest that w mo mineralization occurred before the collision of plates and mineralized substances mainly originated from the crust

cenozoic volcanism in tibet evidence for a transition from oceanic to continental subduction geochronological k ar or ar ar major and trace element sr nd pb isotopic and mineral chemical data are presented for newly discovered cenozoic volcanic rocks in the western qiangtang and central lhasa terranes of tibet alkali basalts of 65 45ma occur in the western qiangtang terrane and represent primitive mantle melts as indicated by high mgnumbers 100 mg mg fe 54 65 cr 204 839 ppm and ni 94 218 ppm contents and relatively low ratios of sr sr 0 7046 0 7061 pb pb 18 21 18 89 pb pb 15 49 15 61 and pb pb 38 42 38 89 and high ratios of nd nd 0 5124 0 5127 in contrast younger volcanic rocks in the western qiangtang terrane 30ma and the central lhasa terrane 23 13 and 8ma are potassic to ultrapotassic and interpreted to have been derived from an enriched mantle source they are characterized by very high contents of incompatible trace elements negative ta nb and ti anomalies and radiogenic pb isotopic compositions pb pb 18 43 19 10 pb pb 15 64 15 83 pb pb 39 14 39 67 sr sr 0 7088 0 7092 and nd nd 0 5122 ratios of the western qiangtang terrane potassic lavas are similar to those of 45 29ma potassic volcanic rocks in the north central qiangtang terrane whereas sr sr 0 7167 0 7243 and nd nd 0 5119 ratios of central lhasa terrane lavas are similar to those of 25 16ma ultrapotassic volcanic rocks in the western lhasa terrane the 65 45ma alkali basalts in the western qiangtang terrane along with widespread calc alkaline volcanic rocks of this age in the lhasa terrane may be related to roll back of a previously shallow north dipping slab of tethyan oceanic lithosphere beneath tibet subduction as opposed to convective thinning of continental lithosphere is favored to explain potassic volcanism in tibet because of its occurrence in distinct east west trending belts 45 29ma in the qiangtang terrane 25 17ma in the northern lhasa terrane 16 8ma in the southern lhasa terrane and temporal and spatial relationships with major thrust systems

variation of mo isotopes from molybdenite in high temperature hydrothermal ore deposits measurable molybdenum isotope fractionation in molybdenites from different ore deposits through time provides insights into ore genesis and a new technique to identify open system behavior of re os in molybdenites molybdenite samples from six porphyry copper deposits one epithermal polymetallic vein deposit four skarns and three fe oxide cu au deposits were analyzed the 97mo where open image in new window for all samples varied from 1 34 0 09 to 0 26 0 04 this is the largest molybdenum isotopic variation in molybdenite from high temperature ore deposits recorded to date 97mo of molybdenite varies as a function of the deposit type and the rhenium and osmium concentrations of the samples isotope values for mo also vary within the individual deposits in general molybdenites from porphyry copper deposits have the lightest values averaging 0 07 0 23 1 molybdenites from the other deposit types average 0 49 0 26 1 the variations could be related to the fractionation of mo into different mineral phases during the ore forming processes a comparison of the mo isotope ratios and the re os ages obtained from the same aliquot may possess a geochronological evaluation tool samples that yielded robust ages have different mo isotopic compositions in comparison to samples that yielded geologically unreasonable ages another observed relationship between the re os and mo isotope data reveals a weak correspondence between re concentration and mo isotope composition molybdenites with higher concentrations of re correspond to lighter mo isotope values

variation of molybdenum isotopes in molybdenite from porphyry and vein mo deposits in the gangdese metallogenic belt tibetan plateau and its implications we present mo isotopic ratios of molybdenite from five porphyry molybdenum deposits chagele sharang jiru qulong and zhuonuo and one quartz molybdenite vein type deposit jigongcun along the gangdese metallogenic belt in the tibetan plateau these deposits represent a sequence of consecutive events of the india asia collision at different periods additional molybdenite samples from the henderson mo deposit usa the oceanic subduction related el teniente chile and bingham usa porphyry cu mo deposits were analyzed for better understanding the controls on the mo isotope systematics of molybdenite the results show that molybdenite from sharang jiru qulong and zhuonuo deposits have similar 97mo 0 in agreement with the values of the henderson mo deposit 0 10 in contrast samples from the changle and jigongcun deposit have 97mo of 0 85 to 0 88 and 0 48 respectively molybdenite from the el teniente and bingham deposits yields intermediate 97mo of 0 27 and 0 46 respectively the mo isotopes combined with nd isotope data of the ore bearing porphyries indicate that source of the ore related magmas has fundamental effects on the mo isotopic compositions of molybdenite our study indicates that molybdenite related to crustal and mantle derived magmas has positive or negative 97mo values respectively whereas molybdenite from porphyries formed by crust mantle mixing has 97mo close to 0 it is concluded that the mo isotope composition in the porphyry system is a huge source signature without relation to the tectonic setting under which the porphyry deposits formed

variations in the isotopic composition of molybdenum in freshwater lake systems variations in molybdenum isotopic composition spanning the range of similar to 2 3 parts per thousand in the terms of mo 97 mo 95 ratio have been measured in sediment cores from three lakes in northern sweden and north western russia these variations have been produced by both isotopically variable input of mo into the lakes due to mo isotopic heterogeneity of bedrock in the drainage basins and fractionation in the lake systems due to temporal variations in limnological conditions mo isotope abundances of bedrock in the lake drainage basins have been documented by analysis of mo isotope ratios of a suite of molybdenite occurrences collected in the studied area and of detrital fractions of the lake sediment cores the median delta mo 97 value of the investigated molybdenites is 0 26 parts per thousand with standard deviation of 0 43 parts per thousand n 19 whereas the median delta mo 97 value of detrital sediment fractions from two lakes is 0 40 parts per thousand with standard deviation of 0 36 parts per thousand n 15 the isotopic compositiori of mo in the sediment cores has been found to be dependent on redox conditions of the water columns and the dominant type of scavenging phases hydrous fe oxides have been shown to be an efficient scavenger of mo from porewater under oxic conditions oxidative precipitation of fe ii in the sediments resulted in co precipitation of mo and significant authigenic enrichment at the redox boundary in spite of a pronounced increase in mo concentration associated with fe oxides at the redox boundary the isotopic composition of mo in this zone varies insignificantly suggesting little or no isotope fractionation during scavenging of mo by hydrous fe oxides in a lake with anoxic bottom water a chironomid inferred reconstruction of o 2 conditions in the bottom water through the holocene indicates that increased o 2 concentrations are generally associated with low delta mo 97 mo 95 values of the sediments whereas lowered o 2 contents of the bottom water are accompanied by relatively high delta mo 97 mo 95 values thus confirming the potential of mo isotope data to be a proxy for redox conditions of overlying waters however it is pointed out that other processes including input of isotopically heterogeneous mo and mn cycling in the redox stratified water column can be a primary cause of variations in mo isotopic compositions of lake sediments less

molybdenum isotope evidence for global ocean anoxia coupled with perturbations to the carbon cycle during the early jurassic relatively brief periods of severe paleoenvironmental change during the jurassic and cretaceous were associated with the widespread accumulation of organic rich marine deposits termed oceanic anoxic events oaes these intervals involved abrupt global warming of 5 10 c higher rates of continental weathering elevated extinction rates and large scale perturbations to the global carbon cycle the major oaes also overlapped temporally the emplacement of large igneous provinces however despite being known as oaes the extent of seawater anoxia at those times is undefined and the causative processes remain unclear here we show how changes in seawater molybdenum isotope ratios a proxy for seawater anoxia during the toarcian early jurassic oae define the onset and expansion of oxygen deficient conditions our data also place constraints on the areal extent of marine anoxia during the event and demonstrate that anoxia expanded and contracted periodically broadly in line with precession driven changes in 13 corg despite their intermittent occurrence over geological history oaes have an important contemporary relevance because the magnitude and high rates of environmental change then were broadly similar to those occurring at the present day