coupled re os and u pb geochronology of the tonian chuar group grand canyon well preserved strata of the late tonian chuar group exposed in the grand canyon host fossil evidence for the development of eukaryotic predation the presence of unique biomarkers and large changes in c s and mo isotope chemostratigraphy despite the importance of this critical succession few radioisotopic age constraints are available to place these records into a global context here we couple high precision u pb chemical abrasion isotope dilution thermal ionization mass spectrometry ca id tims on zircon crystals with the rhenium osmium re os sedimentary and sulfide geochronometer to refine the temporal framework of this pivotal interval of earth history zircons recovered from a tuff within the uppermost walcott member of the kwagunt formation yield a weighted mean 206pb 238u age of 729 0 0 9 ma mean square of weighted deviates mswd 0 86 differing significantly from the previous air abrasion upper intercept age of 742 6 ma on zircons from this same horizon organic rich carbonates from the carbon canyon member of the galeros formation yield a model 1 re os age of 757 0 6 8 ma mswd 0 47 n 8 and an initial os isotope 187os 188os osi composition of 1 13 0 02 the radiogenic osi value from this horizon suggests that the basin was restricted from the open ocean during deposition of the carbon canyon member in agreement with sedimentological and stratigraphic data the re os geochronology of marcasite fes2 nodules from the awatubi member of the kwagunt formation yield a model 1 age of 751 0 7 6 ma mswd 0 37 n 5 with an osi of 0 44 0 01 this re os date is interpreted to constrain the growth of the marcasite nodules in the awatubi member during deposition the formation of sulfides and the less radiogenic osi value are consistent with an influx of sulfate laden seawater to the basin during deposition of the kwagunt formation attempts to apply the re os geochronometer to the walcott and tanner members of the chuar group failed to yield meaningful ages despite elevated re enrichments 20 ng g the re os data from these units yielded negative osi values which suggest disturbance to the re os system the low os abundances typically 100 pg g relative to the amount expected based on the elevated re abundances suggest leaching of os due to oxidative weathering on geologically recent time scales finally the carbon canyon member provides a useful case study for quantifying how input uncertainties in the re os geochronometer propagate into the resulting age uncertainty and we discuss the protocols that will yield the best improvement in age precision for future studies the u pb and re os geochronology presented here illustrates the power of coupling these systems and the importance of recent improvements in both methods our analysis suggests that for our data the most efficient way of reducing uncertainties in the presented re os dates is through improved precision of measured os values

petroleum source rock identification of united kingdom atlantic margin oil fields and the western canadian oil sands using platinum palladium osmium and rhenium implications for global petroleum systems this study demonstrates that petroleum and source rocks are enriched in pt and pd to the ppb level and that the 187os 188os composition coupled with the pt pd value permits the fingerprinting of petroleum to its source oils from the united kingdom atlantic margin sourced from the upper jurassic kimmeridge clay fm as well as source rock samples have been analysed for pt and pd when the pt pd value is compared with 187os 188os calculated at the time of oil generation osg the values from both the known source and the oils are similar demonstrating that they can be used as an oil to source fingerprinting tool this inorganic petroleum fingerprinting tool is particularly important in heavily biodegraded petroleum systems where traditional fingerprinting techniques e g biomarkers are severely hampered e g the world s largest oil sand deposit the west canadian oil sands wcos this has caused the source of the wcos to be hotly debated with no present day consensus between inputs from potential source units e g exshaw and gordondale fms 187os 188os and pt pd fingerprinting of the oil sands shows that the majority of the petroleum have similar 187os 188os and pt pd values supporting the hypothesis of one principal source analysis of the potential source rocks establishes that the principal source of the oil sands to be from the jurassic gordondale fm with a minor exshaw fm input thus the combination of previously pioneered re os petroleum geochronology with 187os 188os and pt pd values of petroleum permits both a temporal and spatial understanding of petroleum systems

the duration of ordinary chondrite metamorphism inferred from tungsten microdistribution in metal abstract precise ratios of w and re relative to ir determined by laser ablation icp ms reveal that matrix metal in equilibrated ordinary chondrites eoc exhibits a correlated variation of these ratios in unequilibrated ordinary chondrites uoc the w ir ratio varies by over two orders of magnitude w ir 0 003 0 6 and shows no correlation with any other siderophile element most matrix metal in uoc is depleted in w relative to metal in eoc thus w must enter metal during metamorphism the correlation between w ir and re ir is evident in type 4 chondrites this implies that the abundance and isotopic composition of w is set in ordinary chondrite metal by petrologic type 4 and that the reductant must be exhausted to limit further isotopic exchange as indicated by the 182 hf 182 w ages of ordinary chondrite metal lee and halliday science 274 1996 1876 1879 this offers a means of dating the onset of metamorphic heating of oc parent bodies a discrepancy in ages between 182 hf 182 w lee and halliday science 274 1996 1876 1879 and 207 pb 206 pb gopel et al earth planet sci lett 121 1994 153 171 or 129 i 129 xe brazzle et al geochim cosmochim acta 63 1999 739 760 dating is real and measures the interval of metamorphism the time difference between reduction of w during the onset of heating and isotopic closure of pb or xe by cooling e g t m 2 12 myr for h chondrites the 187 re 187 os and 182 hf 182 w ages are set by the same process metamorphic equilibration establishing an important link between an absolute chronometer t 1 2 187 re 41 6 billion years and a short lived radioisotope system t 1 2 182 hf 9 myr

the record of sea water 187os 186os variation through the cenozoic the variation of sea water 187os 186os during the cenozoic has been determined by analyzing the hydrogenous os released by acidic hydrogen peroxide leaching of layers in an abyssal north pacific pelagic clay core overall sea water 187os 186os has increased from 3 2 at 58 ma to the present day value of 8 6 this pattern is similar to the well known 87sr 86sr evolution of sea water the increase in the proportion of continental os 187os 186os 10 could be due to enhanced weathering rates of black shales associated with the uplift of the himalayas other elements associated with black shale weathering such as u and p should show effects in the sedimentary record

effects of black shale weathering on the mobility of rhenium and platinum group elements radiogenic os from the continents dominates the late cenozoic marine os budget a variety of proposed radiogenic sources includes organic rich sediments precambrian shields and re rich sulfides identifying the dominant sources of radiogenic os to the oceans has a strong impact on past climate models because weathering of silicates acts as a net sink of co 2 whereas weathering of organic matter acts as a source here we investigate the effects of black shale weathering on the integrity of the re os isotope system and release of re and platinum group elements time correlative pairs of fresh drill core and weathered outcrop black shales of late ordovician age utica shale magnafacies quebec were analyzed for re os ir pt and pd as well as total s n and c as c carb and c org the results indicate that 25 64 of the initial re budget 45 90 of the os budget 14 65 of the ir budget 60 77 of the pt budget 69 86 of the pd budget and 44 96 of the c org budget are lost during weathering we use positive correlations of os pt and pd with c org and n to calculate the respective platinum group element concentrations in the unweathered organic matter end member as 3 ng g os 9 ng g pt and 11 24 ng g pd although black shales make up

comprehensive evolution of a petroleum system in absolute time the example of brynhild norwegian north sea abstract petroleum systems are inherently complex comprising multiple components and processes which variably interact in space and time to form petroleum accumulations improved understanding of these complex systems requires a holistic approach of integrating diverse geological geophysical and organic and inorganic geochemical data here we present an applied and comprehensive re os geochronological and geochemical study on the brynhild petroleum system from the norwegian north sea essential components of this system include shale source rocks of the mandal and farsund formations reservoir sandstones of the ula formation and their bitumen extracts and produced brynhild crude oil rock eval trace metal and re os data reveal the excellent oil generation potential of the shaley source rocks high contents of organic matter containing large amounts of type i kerogens and constrain their depositional conditions anoxic bottom waters in a high productivity regime driven by enhanced supply of land derived nutrients seven re os shale ages between 146 and 134 ma are consistent with existing volgian ryazanian age estimates and constrain the initial 187os 188os of the shales to 0 52 in the lowermost farsund formation and 0 75 in the uppermost mandal formation solvent extracted reservoir rocks of the ula formation contain insoluble organic matter with type iii type iv kerogens likely supplied by erosion of older a precise 179 ma re os age with unrealistically low initial 187os 188os coal bearing sediments or organic rich shales the brynhild crude oil has relatively low 187os 188os and a generation age of 44 ma based on an asphaltene only re os isochron maltenes from the brynhild crude oil are isotopically affected by interaction with organic rich source rocks that represent the seal for the brynhild oil field compared with the crude oil bitumen from ula formation sandstones have contrasting re os properties high 187os 188os ratios and young generation ages between 8 and 0 ma based on asphaltene bitumen maltene re os triplets asphaltene only re os regressions and re os model ages for components with extremely high 187re 188os the 44 ma and 8 0 ma re os ages agree well with regional burial models that indicate oil generation from 44 ma to present day a genetic link between crude oil and bitumen is indicated by their similar alkane patterns v and ni contents and v ni and pristane phytane ratios modeling of 187os 188os for individual organic components through time shows that shales of the mandal formation developed 187os 188os ratios that match those of the crude oil and bitumen at 44 ma and 8 ma respectively and therefore confirm the source for both hydrocarbon phases we suggest that bitumen formed during in reservoir mixing of a 44 ma old early mature asphaltene poor oil brynhild crude oil with an 8 ma old asphaltene rich oil

variations of the187os 186os ratio of seawater over the past 28 million years as inferred from metalliferous carbonates abstract the os concentration and isotopic composition of metalliferous carbonates deposited on the east pacific rise over the past 28 ma are reported with complimentary sr isotope data variations in the os isotopic composition of these samples are interpreted as a record of past changes in the os isotopic composition of seawater these results are consistent with isotopic analyses of leachable os in pelagic clays which have also been interpreted as a record of the187os 186os ratio of seawater through time 1 the metalliferous carbonate record clearly shows that seawater os and sr isotope systems are partially decoupled from one another over the past 28 ma accelerated weathering of ancient organic rich sediments is suggested as a possible mechanism to account for this decoupling and the rapid increase in the187os 186os ratio of seawater over the past 15 ma this rapid increase suggests that the seawater os record can potentially be used as a stratigraphic tool in some neogene marine deposits

isotopic composition of osmium in terrestrial samples determined by accelerator mass spectrometry interest has revived in the rhenium osmium system due to significant advances in detection methods1 4 and because of its use for the identification of extraterrestrial material at the cretaceous tertiary boundary5 another perhaps more important application is its use as a tracer for the origin of crustal material this application is however severely restricted by the very low concentrations typical of crustal rocks we present here the first results for the isotopes 187os 188os and 189os measured in sub p p b parts per 109 level samples by accelerator mass spectrometry ams our first exploratory measurements on extraterrestrial and crustal material with os concentrations between 2 p p m parts per 106 and 0 006 p p b show a detection limit of 0 01 p p b and a precision of better than 10 the 187os 186os ratios measured for samples for the canyon diablo meteorite and from the east clearwater crater in quebec canada were close to 1 typical of extraterrestrial material in contrast ratios in samples from the ries crater in germany were around 10 which is evidence of predominantly crustal osmium in these rocks

osmium isotopic evidence against an impact at the frasnian famennian boundary two sections across the frasnian famennian boundary were analyzed for re and os concentrations and 187os 188os ratios to evaluate evidence for a meteoritic input coincident with this boundary and its associated mass extinction these sections are from a siltstone and shale sequence at irish gulf in new york us and a calcareous shale and ferromanganese oxide sequence at la serre in france the irish gulf section with an initial 187os 188os of about 0 49 does not show the characteristic meteoritic os imprint with an 187os 188os of about 0 13 the integrity of the section with regard to re and os retention is indicated by the construction of an isochron with an age of 388 41 ma consistent with independently determined ages for the frasnian famennian boundary although the la serre section with os concentrations as high as 33 ppb and re concentrations ranging from 1 4 to 7 4 ppb might be expected to show excellent evidence for a meteoritic contribution the highly radiogenic isotopic composition 187os 188os 2 42 3 61 instead suggests recent massive re loss or addition of radiogenic os these possibilities prevent the reconstruction of an initial 187os 188os value for the boundary for this site assuming reasonable re concentrations prior to loss the os isotopic composition is inconsistent with a large meteoritic component this inconsistency emphasizes that platinum group element pge concentrations are not reliable indicators of extraterrestrial addition

accretion rate of extraterrestrial particles determined from osmium isotope systematics of pacific pelagic clay and manganese nodules abstract pelagic clay and mn nodules from domes sites in the north pacific and a varved glacial lake deposit from connecticut were analysed for os concentration and isotopic composition by isotope dilution secondary ion mass spectrometry after treatment by nis fusion or oxalic acid leaching bulk pelagic clay from domes site c has 187 os 186 os 6 5 and os 0 14 ng g oxalic acid leaches of this same sediment and of mn nodules from domes sites a and c have more radiogenic 187 os 186 os ratios which average 8 3 bulk glacial lake hitchcock sediment has 187 os 186 os 12 5 and os 0 06 ng g the total os flux to north pacific pelagic clay is 7 to 10 ng os cm2 106 y lake hitchcock sediment provides an integrated value for the local crustal 187 os 186 os ratio the oxalic acid leaches are assumed to attack hydrogenous phases selectively a simple model in which the only sources of os to the ocean are continental crust with the isotopic composition of lake hitchcock 187 os 186 os 12 5 and extraterrestrial particles with 187 os 186 os 1 1 results in a cosmic flux of osmium to the sediment of 4 9 ngos cm2 106 y of which 20 is hydrogenous a model in which the sources of os to the ocean are continental crust with an 187os 186os ratio of 30 from the model of palmer and turekian 1986 oceanic mantle or crust with 187 os 186 os 1 04 and extraterrestrial particles with 187 os 186 os 1 1 results in a cosmic flux of os to the sediment of 5 7 ngos cm2 106 y of which none is hydrogenous these extraterrestrial os fluxes correspond to maximum c 1 chondrite accretion rates of between 4 9 104 and 5 6 104 tonnes y

copper zinc chromium and osmium isotopic compositions of the tepla barrandian unit black shales and implications for the composition and oxygenation of the neoproterozoic cambrian ocean abstract two neoproterozoic cambrian shale suites that consist of normal nbs and metal rich hmbs black shales from the tepla barrandian unit bohemian massif czech republic are studied in terms of their cu zn cr and re os isotopic compositions to improve our knowledge of elemental and isotopic mass balance of these elements in earth s oceans in the past and the extent of surface oxygenation at the neoproterozoic cambrian boundary the rock compositions indicate that the inputs of cu and zn have been controlled by variable proportions of metal rich authigenic and low metal terrigenous sources the latter having exceptionally low 65cu and partially 66zn in this respect our data confirm previous studies conclusions that organic rich sediments with high a terrigenous flux play an important role in the sinking of light zn in the oceans and provide new evidence that these types of rocks also represent the currently unidentified burial of very light cu in the ocean the chromium isotopic composition reveals a complex history of cr uptake and fractionation through the dominant cr input from different terrigenous sources with variable 53cr followed by cr fractionation that was controlled by redox states nbs on the other hand mixing and or continuous equilibrium isotopic exchange between seawater and hydrothermal cr was the dominant process for the hmbs the re os contents of the nbs were controlled by hydrogenous components which yield a poorly defined re os age for the least disturbed samples of 555 60 ma indicating an open system behavior while the hmbs re os composition was largely influenced by hydrothermal fluids during deposition the calculated authigenic 65cu which is similar to that in the present day ocean and highly positive 53cr values of the hmbs suggest high levels of surface oxygenation during the neoproterozoic cambrian transition furthermore the authigenic 66zn which is indistinguishable from that in the present day ocean may imply a constant zn isotopic composition of the oceans from the neoproterozoic because of the well balanced cycle of phosphates which were strongly adsorbed by fe hydroxides the radiogenic nature of the initial 187os 188os 0 6 although with a high associated error seems to not confirm previous indications of an abrupt increase of seawater 187os 188os during the late neoproterozoic due to the large scale radiogenic os flux into the ocean

further evaluation of the re os geochronometer in organic rich sedimentary rocks a test of hydrocarbon maturation effects in the exshaw formation western canada sedimentary basin abstract re os isotopic analyses of a single organic rich sedimentary rock unit ors of known depositional age and at three levels of regional hydrocarbon maturity show that hydrocarbon maturation does not affect the ability the 187re 187os chronometer to yield a depositional age for such rocks we present re os isotope analyses from the late devonian exshaw formation in the subsurface of the western canada sedimentary basin alberta and obtain a re os isochron age of 358 10 ma 2 model 3 1 666 10 11 a 1 for samples ranging from hydrocarbon immature to overmature this age is within uncertainty of the established absolute age for the exshaw formation hydrocarbon immature and mature plus overmature samples show no significant age differences if regressed individually indicating that hydrocarbon maturation did not greatly disturb the re os isotope system in the exshaw formation as such we propose that the re os geochronometer may be used as a reliable tool for measuring the depositional ages of ors regardless of their level of hydrocarbon maturity we find that minimizing natural variation in the initial 187os 188os ratio is more important than avoiding hydrocarbon maturation in obtaining precise re os ages in particular the exshaw formation appears to contain a nonhydrogenous component of unradiogenic os in addition to the hydrogenous os load a subset of exshaw formation samples with 5 total organic carbon toc which should best reflect the hydrogenous os load alone yields a very well fitted isochron having a depositional age of 358 9 ma 2 1 666 10 11 a 1 with an initial 187os 188os ratio of 0 59 0 05 model 3 mean square of weighted deviates mswd 1 8 the initial 187os 188os ratio of this regression may provide an estimate of the os isotopic composition of local seawater at the time of deposition

re os isotope systematics in black shales from the lesser himalaya their chronology and role in the 187os 188os evolution of seawater abstract re and os abundances and os isotope systematics have been measured in a number of black shales sampled from outcrops and two underground phosphorite mines maldeota and durmala in the lesser himalaya the re and os concentrations in these samples exhibit wide range 0 2 to 264 ng g and 0 02 to 13 5 ng g respectively with a mean re os of 25 the 187 os 188 os of these samples also show a broad range 1 02 to 11 6 with many of them far more radiogenic than the currently eroding continental crust the black shales from the maldeota and durmala mines collected a few meters above the krol tal pc c boundary and occurring in the same stratigraphic horizon yield 187 re 187 os isochron ages of 554 16 and 552 22 ma respectively consistent with fossil evidences and those assigned for the pc c boundary at various other locations these results indicate closed system behaviour of re and os in these mine samples and reaffirm the validity of 187 re 187 os pair to date organic rich sediments the age of these mine samples from the outer belt seems to be a few hundred millions of years younger than the preliminary re os age of 839 138 ma for black shales from theog collected from the inner belt these initial results lean toward the hypothesis that the inner belt sediments were deposited earlier than the outer belt however more analyses of black shales are needed to confirm this the role of weathering black shales from the himalaya in contributing to the os isotope evolution of seawater over the past 25 ma was assessed using a simple budget model for seawater os and assuming values for os fluxes and 187 os 188 os based on the available limited data on os concentration and its 187 os 188 os in rivers and oceans these calculations indicate that the required contributions from black shale weathering to account for the entire increase in oceanic 187 os 188 os over the past 16 ma is difficult to satisfy by varying only the os flux from htp rivers 187 os 188 os kept constant at 1 324 or their 187 os 188 os 188 os flux constant at today s value 131 moles yr the requirements to balance os isotope budget in ocean through weathering of black shales however is easier to accommodate if both the os flux from htp himalayan tibetan plateau rivers and their 187 os 188 os are allowed to vary measurements of os abundance in htp rivers and its isotopic composition are needed to test the validity of the model results

re os age and depositional environment for black shales from the cambrian ordovician boundary green point western newfoundland chemical and isotopic signatures for black shales serve as potential proxies for reconstruction of paleoenvironmental conditions here we bring rock eval major and trace element and re os isotopic data together to examine the environmental record at the cambrian ordovician global stratotype section and point gssp at green point in western newfoundland canada the green point shales are oil mature and contain type ii organic material of marine origin a re os isochron for the shales provides the first radiometric age for shale deposition at the gssp at 484 16 ma with an initial 187os 188os ratio of 0 74 0 05 model 3 age mswd 21 n 13 2 uncertainties factor analysis of the geochemical data set shows association of most trace elements with total organic carbon toc and s contents ensuring an authigenic origin for most elements and hence their validity for evaluating the paleo redox state relatively high enrichment factors for redox sensitive elements e g re u and mo compared to average shale but comparatively low enrichment compared to modern black sea sediments suggest deposition in anoxic but not euxinic waters comparison of lower ordovician shale geochemistry data sets at a global scale leads us to suggest that anoxic conditions and warm oceanic regimes were restricted to the margins of laurentia and baltica whereas depositional basins with colder waters e g avalonia and gondwana were less reducing these outcomes underscore the important role of paleogeography in regulating oceanic conditions and marine life

evaluation of the rhenium osmium geochronometer in the phosphoria petroleum system bighorn basin of wyoming and montana usa rhenium osmium re os geochronometry is applied to crude oils derived from the permian phosphoria formation of the bighorn basin in wyoming and montana to determine whether the radiogenic age reflects the timing of petroleum generation timing of migration age of the source rock or the timing of thermochemical sulfate reduction tsr the oils selected for this study are interpreted to be derived from the meade peak phosphatic shale and retort phosphatic shale members of the phosphoria formation based on oil oil and oil source rock correlations utilizing bulk properties elemental composition 13c and 34s values and biomarker distributions the 34s values of the oils range from 6 2 to 5 7 with oils heavier than 2 interpreted to be indicative of tsr the re and os isotope data of the phosphoria oils plot in two general trends 1 the main trend n 15 oils yielding a triassic age 239 43 ma with an initial 187os 188os value of 0 85 0 42 and a mean square weighted deviation mswd of 1596 and 2 the torchlight trend n 4 oils yielding a miocene age 9 24 0 39 ma with an initial 187os 188os value of 1 88 0 01 and a mswd of 0 05 the scatter high mswd in the main trend regression is due in part to tsr in reservoirs along the eastern margin of the basin excluding oils that have experienced tsr the regression is significantly improved yielding an age of 211 21 ma with a mswd of 148 this revised age is consistent with some studies that have proposed late triassic as the beginning of phosphoria oil generation and migration and does not seem to reflect the source rock age permian or the timing of re migration late cretaceous to eocene associated with the laramide orogeny the low precision of the revised regression 21 ma is not unexpected for this oil family given the long duration of generation from a large geographic area of mature phosphoria source rock and the possible range in the initial 187os 188os values of the meade peak and retort source units effects of re migration may have contributed to the scatter but thermal cracking and biodegradation likely have had minimal or no effect on the main trend regression the four phosphoria sourced oils from torchlight and lamb fields yield a precise miocene age re os isochron that may reflect the end of tsr in the reservoir due to cooling below a threshold temperature in the last 10 m y from uplift and erosion of overlying rocks the mechanism for the formation of a re os isotopic relationship in a family of crude oils may involve multiple steps in the petroleum generation process bitumen generation from the source rock kerogen may provide a reset of the isotopic chronometer and incremental expulsion of oil over the duration of the oil window may provide some of the variation seen in 187re 188os values from an oil family

disequilibrium induced initial os isotopic heterogeneity in gram aliquots of single basaltic rock powders implications for dating and source tracing abstract the re os isotopic heterogeneity of mantle derived rocks has been well documented however it is unclear whether and how the os isotopic heterogeneity of a mantle source can influence re os isotopic dating and source tracing of mantle derived melts here we report that replicate analyses of gram aliquots of single basaltic powders one of reference material bhvo 2 and three of the hatu basalts from the western junggar region china show large variations in both os concentrations and isotopic ratios more importantly these replicate data define good apparent re os isochron correlations yielding ages significantly older than their formation ages and display remarkable correlations between the 187 os 188 os ratio and the reciprocal of the common os concentration i e 1 192 os this indicates that the initial os isotopic composition in a basaltic magmatic system may be heterogeneous and cannot be homogenized by pulverizing theoretical and mathematical deduction demonstrates that the observed apparent re os isochron correlations are the result of binary mixing without complete isotopic equilibrium at the time of formation primarily due to limited diffusional exchange of os isotopes between refractory os bearing inclusions and host minerals under mantle conditions the regressed initial os isotopic composition may bias the true value of the mantle source pulsed mantle melting and magma mixing during ascent are potential processes responsible for such initial os isotopic heterogeneity in basaltic rock systems thus when using the re os isotopic system to date and to trace the source of basaltic rocks or other rocks with relatively low os concentrations it is necessary to consider whether the initial os isotopic composition was heterogeneous or whether it had reached complete isotopic equilibrium

sources of osmium isotopes in manganese nodules abstract we have measured the 187 os 186 os and os concentrations of ferromanganese crusts forming on serpentinized peridotites from the atlantic ocean and also report major element data for these samples and six manganese nodules previously analyzed for os variations in the 187 os 186 os ratios of manganese nodules are the result of two processes operating on different spatial scales the large scale variations result from the impression of intense local os inputs from continental and oceanic sources on a generally homogeneous oceanic 187 os 186 os ratio fine scale variations may be understood as the result of the mixing of a constant fine grained debris flux of meteoritic os imposed on varying amounts of os precipitated from seawater

linear model describing three components of flow in karst aquifers using 18o data the stable isotope of oxygen 18o is used as a naturally occurring ground water tracer time series data for 18o are analyzed to model the distinct responses and relative proportions of the conduit intermediate and diffuse flow components in karst aquifers this analysis also describes mathematically the dynamics of the transient fluid interchange between conduits and diffusive networks conduit and intermediate flow are described by linear systems methods whereas diffuse flow is described by mass balance methods an automated optimization process estimates parameters of lognormal pearson type iii and gamma distributions which are used as transfer functions in linear systems analysis diffuse flow and mixing parameters also are estimated by these optimization methods results indicate the relative proximity of a well to a main conduit flowpath and can help to predict the movement and residence times of potential contaminants the three component linear model is applied to five wells which respond to changes in the isotopic composition of point recharge water from a sinking stream in the madison aquifer in the black hills of south dakota flow velocities as much as 540 m d and system memories of as much as 71 years are estimated by this method also the mean median and standard deviation of traveltimes time to peak response and the relative fraction of flow for each of the three components are determined for these wells this analysis infers that flow may branch apart and rejoin as a result of an anastomotic or channeled karst network

rhenium and osmium isotopes in black shales and ni mo pge rich sulfide layers yukon territory canada and hunan and guizhou provinces china rhenium and osmium abundances and osmium isotopic compositions were determined by negative thermal ionization mass spectrometry for samples of devonian black shale and an associated ni enriched sulfide layer from the yukon territory canada the same composition information was also obtained for samples of early cambrian ni mo rich sulfide layers hosted in black shale in guizhou and hunan provinces china this study was undertaken to constrain the origin of the pge enrichment in the sulfide layers samples of the ni sulfide layer from the yukon territory are highly enriched in re os and other pge with distinctly higher re 192os but similar pt re compared to the black shale host re os isotopic data of the black shale and the sulfide layer are approximately isochronous and the data plot close to reference isochrons which bracket the depositional age of the enclosing shales samples of the chinese sulfide layers are also highly enriched in re os and the other pge re 192os are lower than in the yukon sulfide layer re os isotopic data for the sulfide layers lie near a reference isochron with an age of 560 ma similar to the depositional age of the black shale host the osmium isotopic data suggest that re and pge enrichment of the brecciated sulfide layers in both the yukon territory and in southern china may have occurred near the time of sediment deposition or during early diagenesis during the middle to late devonian and early cambrian respectively

preservation of re os isotope signatures in pyrite throughout low t high p eclogite facies metamorphism pyrite in lt hp eclogites from the western tianshan orogenic belt yields a re os age of 378 1 8 9 ma which is 30 70 ma older than ages previously obtained for the same rocks using the rb sr sm nd ar ar u pb and lu hf isotope systems the tianshan lt hp eclogite experienced temperatures of up to 570 c combined with pressures of up to 2 1 gpa during metamorphism these conditions are below the transition of pyrite to pyrrhotite which defines both pyrite stability and possibly its closure temperature for re os pyrite can preserve re os signatures through eclogite facies peak metamorphic conditions and thus allow determination of the formation age of pyrite in the protolith

application of the 187re 187os system to black shale geochronometry the decay of 187re to 187os provides a tool for determining depositional ages of black shales re and os concentrations and os isotopic compositions of whole rock samples of the bakken shale a mississippian devonian boundary black shale yield a whole rock isochron with an age of 354 49 ma this age is in agreement with the accepted age of the bakken shale 360 ma the initial 187os186os ratio of the isochron is 6 2 3 3 this value is indistinguishable from the 187os186os ratios observed in modern black sea sediments the concentration of common os in bakken shale samples is strongly correlated with total nitrogen indicating that a large fraction of the os in these samples is associated with a hydrogenous component which overwhelms any os supplied to the sediment in association with detrital material or cosmic dust the dominance of the hydrogenous component imparts a relatively homogeneous initial 187os186os ratio to the sediment at the time of deposition the degree of scatter about the isochron exceeds the degree of scatter expected from either analytical error or from the estimated degree of initial isotopic heterogeneity the pattern of scatter is consistent with postdepositional mobilization of re and or os on a small spatial scale we suggest that this mobilization may be a consequence of petroleum formation and migration in the bakken shale

a complete os excursion across a terrestrial cretaceous paleogene boundary at the west bijou site colorado with evidence for recent open system behavior abstract the few previously reported values of 187os 188os ratios from non marine k pg boundary sections are distinctly higher than the range of 187os 188os ratios measured in chondrites and the range of ratios predicted by models of physical mixing between chondrites and upper crust here re os data from the west bijou continental k pg boundary site located within the denver basin are used to better constrain the os isotopic composition of fallout from the chicxulub ejecta plume for the first time full vertical profiles of 187os 188os ratios and re and os concentrations across a continental k pg boundary section are reported within this section of lignite the lowest measured 187os 188os ratio 0 182 coincides with the k pg boundary interval as previously determined by palynology and the distribution of shocked quartz in a nearby outcrop however sediments with elevated os concentrations and measured 187os 188os below 0 23 extend over a 30 cm interval from 5 cm above the clay rich boundary interval 5 cm thick to 25 cm below maximum ir and os concentrations occur 3 cm and 10 cm below the k pg boundary respectively demonstrating greater diagenetic mobility of os relative to ir low 187os 188os above the k pg boundary suggests that accumulation of impact derived os at this site persisted after the impact event perhaps due to redistribution of impact debris in the surrounding area importantly calculated initial 187os 188os ratios throughout most of the section are impossibly low and require open system behavior likely in the form of re addition within the last 10 million years within the boundary interval re concentrations are among the lowest measured at bowring pit and calculated initial 187os 188os ratios are very similar to those previously reported from the western interior of the united states k pg boundary material 0 14 suggesting super chondritic 187os 188os is characteristic of the chicxulub ejecta plume beyond implications for our understanding of os as an impact tracer this study emphasizes the dramatic effect diagenesis can have on the re os system in organic rich environments especially through post depositional addition of re

role of river incision in enhancing deformation many active compressional belts contain examples of transverse rivers intersecting anticlines at their highest structural and topographic position this unusual association between rivers and doubly plunging anticlines at relatively small scales is usually explained by some form of antecedence or superposition in this article i suggest an alternative explanation i e that river erosion unloads the crust and that this process causes local deformation to be enhanced in the vicinity of rivers i show the plausibility of this hypothesis with the aid of a coupled three dimensional mechanical surface process mathematical model the conclusion is that river incision can have a major influence on deformation of the surrounding crust if incision occurs at the same time that the crust is deforming plastically in response to regional compression in this case incision amplifies background deformation at a relatively small scale leading to the formation of noncylindrical folds with culminations coinciding with river incision in the absence of regional deformation the response of the crust to river incision is small and of long wavelength because it is governed by flexural isostasy of relatively rigid elastic crust thus whether rivers exert an influence on local deformation depends critically on the timing between river incision and regional deformation this point may explain why in some cases rivers appear to have had no significant influence on local deformation whereas in other cases they have