pronounced zonal heterogeneity in eocene southern high latitude sea surface temperatures paleoclimate studies suggest that increased global warmth during the eocene epoch was greatly amplified at high latitudes a state that climate models cannot fully reproduce however proxy estimates of eocene near antarctic sea surface temperatures ssts have produced widely divergent results at similar latitudes with ssts above 20 c in the southwest pacific contrasting with ssts between 5 and 15 c in the south atlantic validation of this zonal temperature difference has been impeded by uncertainties inherent to the individual paleotemperature proxies applied at these sites here we present multiproxy data from seymour island near the antarctic peninsula that provides well constrained evidence for annual ssts of 10 17 c 1 sd during the middle and late eocene comparison of the same paleotemperature proxy at seymour island and at the east tasman plateau indicate the presence of a large and consistent middle to late eocene sst gradient of 7 c between these two sites located at similar paleolatitudes intermediate complexity climate model simulations suggest that enhanced oceanic heat transport in the south pacific driven by deep water formation in the ross sea was largely responsible for the observed sst gradient these results indicate that very warm ssts in excess of 18 c did not extend uniformly across the eocene southern high latitudes and suggest that thermohaline circulation may partially control the distribution of high latitude ocean temperatures in greenhouse climates the pronounced zonal sst heterogeneity evident in the eocene cautions against inferring past meridional temperature gradients using spatially limited data within given latitudinal bands

stress state in the cuu long and nam con son basins offshore vietnam abstract the results presented in this paper are the first published estimates of the complete stress tensor in the cuu long and nam con son basins offshore vietnam we analysed in situ stress and pore pressure fields in the sedimentary formations using data from petroleum exploration and production wells to evaluate the stress state in these basins the data were obtained from the seafloor to 4300 m burial depth and include both hydrostatic and overpressured sections minimum horizontal stresses were obtained from extended leak off tests and mini fracture tests maximum horizontal stresses were estimated from drilling induced fracture parameters and borehole breakout widths in twelve wells using rock properties measured in the laboratory or estimated empirically from wireline logs seven data points are located in sediments and seventeen data points in igneous basement rocks at depths greater than 3000 m the estimated magnitudes of h are 70 110 of the v magnitudes considering the errors in the stress magnitude estimates their relative magnitudes suggest that a borderline normal strike slip stress regime presently exists in normally pressured sequences of the nam con son and cuu long basins of the twenty four data points twenty have effective stress ratios at a critical stress state for faulting on the assumption that there are faults present that are optimally oriented for failure with friction coefficients of 0 5 the results suggest that the stress state in these basins is generally critical

temperature limits for preservation of primary calcite clumped isotope paleotemperatures abstract solid state reordering of c o bonds in the calcite lattice can alter the clumped isotope composition of paleotemperature archives such as fossil brachiopod shells without inducing significant changes in shell microstructure and trace element concentrations metrics commonly used to gauge preservation quality to correctly interpret the paleoenvironmental significance of clumped isotope derived paleotemperatures it is necessary to understand the temperature time domain in which solid state c o bond reordering is important we address this question using a combination of laboratory and natural geological experiments on paleozoic brachiopod shells the laboratory experiments involve heating fossil brachiopod calcite at different temperatures and times to directly observe rates of 13 c 18 o bond reordering the resulting arrhenius parameters are indistinguishable from values previously determined for an optical calcite with similar trace element compositions we develop an alternative kinetic model for reordering that accounts for non first order reaction progress observed during the initial several hundred minutes of laboratory heating experiments and show that the simplified first order approximation model passey and henkes 2012 predicts reaction progress equally well for temperatures and timescales relevant to sedimentary basins we evaluate our laboratory based rate predictions by studying brachiopod calcite from several sedimentary basins with independently constrained burial temperature histories specifically we use the laboratory derived arrhenius parameters to predict the evolution of brachiopod calcite clumped isotope compositions during successive one million year time steps reflecting the burial and exhumation temperature paths of each basin while this exercise is limited by the relatively large uncertainties in the temperature histories of these basins we find general correspondence within error between predicted and observed clumped isotope values we present simplified temperature time diagrams for calcite showing domains where primary clumped isotope compositions will be preserved partially reordered and fully reordered in conclusion calcite samples dwelling at 100 c or lower for 10 6 10 8 year timescales should not be affected by solid state c o bond reordering

high archean climatic temperature inferred from oxygen isotope geochemistry of cherts in the 3 5 ga swaziland supergroup south africa new and compiled oxygen isotope data combined with the results of geological and sedimentological studies demonstrate that enclaves of synsedimentary to very early diagenetic cherts are widely preserved in the 3 5 3 2 ga swaziland supergroup barberton greenstone belt south africa the low 1 8 o values of these cherts indicate extremely high ocean temperatures of 55 85 c previously the large depletion in 1 8 o shown by all barberton cherts relative to their phanerozoic counterparts has been attributed to low 1 8 o in archean oceans chert formation during late diagenesis wholesale loss of 1 8 o during alteration and or regional silicification of sediments around hot springs these alternative explanations are not compatible with the new results cherts in the onverwacht group display an isotopic stratigraphy that is inversely repeated in conglomerates in the overlying fig tree and moodies groups demonstrating that the chert 8 0 o values were fixed prior to archean uplift and erosion which started at 3 26 ga the maximum 1 8 o value in barberton cherts 22 is lower than the minimum values 23 in phanerozoic bedded cherts precluding late diagenesis as the explanation of the overall low 1 8 o values regional metamorphic hydrothermal or long term resetting of original 1 8 o values is also precluded by preservation of 1 8 o values across different metamorphic grades and by systematic 1 8 o differences among interbedded chert types stratigraphic units and conglomerate clasts the 7 1 8 o variation of these archean cherts is similar to that of phanerozoic deep sea cherts formed when opal converted to microquartz during burial but the actual archean values are 10 lower marine opal was apparently converted to microquartz during burial to depths of 1 km cherts with 1 8 o 15 reflect conversion during deepest burial or in local areas of enhanced geothermal gradient and or hydrothermal activity cherts with higher 1 8 o values formed during early diagenesis and indicate an extremely hot archean ocean and surface environment

facies stratigraphy and evolution of a middle ediacaran carbonate ramp khufai formation sultanate of oman the khufai formation is the oldest carbonate platform of the cryogenian to lowermost cambrian huqf supergroup a stratigraphic characterization of this unit includes detailed facies descriptions a sequence stratigraphic interpretation and evaluation of lateral heterogeneity and overall ramp evolution the khufai formation comprises one and one half depositional sequences with a maximum flooding interval near the base of the formation and a sequence boundary within the upper peritidal facies most of the deposition occurred during highstand progradation of a carbonate ramp facies tracts include outer ramp and midramp mudstones and wackestones ramp crest grainstone shoal deposits and extensive inner ramp microbially dominated peritidal deposits outcrops in the oman mountains are deep water deposits including turbiditic grainstone and wackestone interbedded with siliciclastic rich siltstone and crinkly laminite facies patterns and parasequence composition are variable both laterally across the outcrop area and vertically through time because of a combination of ramp morphology siliciclastic supply and possible syndepositional faulting the lithostratigraphic boundary between the khufai formation and the overlying shuram formation is gradational and represents significant flooding of the carbonate platform the stratigraphic characterization presented here along with the identification of key facies and diagenetic features will help further future exploration and production of hydrocarbons from the khufai formation

massive recrystallization of low mg calcite at high temperatures in hydrocarbon source rocks implications for organic acids as factors in diagenesis we document massive recrystallization of low mg calcite lime mudstone source rocks at moderately high temperatures in the smackover formation of mississippi this process was driven by organic acids produced during kerogen maturation and holds the implications for studies of primary migration of hydrocarbons secondary porosity generation in reservoirs and global environmental change this interpretation is based on contrasting the following petrographic and bulk rock geochemical characteristics of organic poor vs organic rich lime mudstones

evaluating formation fluid models and calibrations using clumped isotope paleothermometry on bahamian dolomites abstract the use of stable oxygen isotopes to understand the mechanisms of dolomite formation has been hampered by the inability to precipitate well ordered dolomite under normal earth surface conditions several studies have attempted to address this problem either by precipitating high temperature ordered dolomites and extrapolating the data to low temperatures or by using more disordered very high mg calcites as a proxy for low temperature dolomites the result is eight equations that disagree significantly from each other by as much as 3 6 in the 18o value of the precipitating fluid at 25 c and produce differences which can greatly affect the interpretation of the formation mechanisms for low temperature dolomites however by combining the recently developed clumped isotope paleothermometer an independent isotopic measurement 47 that directly relates to the temperature of formation to late miocene to pleistocene aged dolomites from the bahamas with a well constrained thermal and fluid history we have attempted to narrow down the viable equations used to interpret the 18o values of dolomites the clumped isotope temperatures measured on the bahamian dolomites 16 37 c agrees with the range of temperatures expected in the bahamas pairing these temperatures with geological and mineralogical arguments we favor the equation suggested by matthews and katz 1977 as it is the only one that produces realistic 18o fluid values across the range of clumped isotope temperatures both the clumped isotope temperatures and 18o values of the precipitating fluid show a strong positive covariance that we have interpreted as reflecting the mixing of surface brines that have undergone varying amounts of evaporation and normal seawater the different mechanisms driving these fluids included formation by normal marine seawater driven by the compensatory flow of the mixing zone bank wide kohout convection and evaporative brine reflux

geologic evolution of the cuu long and nam con son basins offshore southern vietnam south china sea rifting and regional subsidence characterize the cuu long and nam con son basins offshore southern vietnam initial rifting began in the eocene early oligocene followed by the uplift and rotation of the crustal blocks in the late oligocene the erosion of the uplifted blocks marked the transition from rifting to regional subsidence in the cuu long basin a second phase of rifting began in the nam con son basin lasting until the late miocene parts of the nam con son basin experienced inversion in the middle to late miocene the synrift and postrift units in the cuu long basin consist of nonmarine deposits and paralic to shallow marine sediments respectively the synrift deposits in the nam con son basin can be divided into the early synrift unit corresponding to the initial rifting phase and the late synrift unit deposited during the second rifting phase the early synrift and late synrift units consist of nonmarine sediments and nonmarine to shallow marine sediments respectively the postrift unit is composed of shelf and deeper marine deposits the data compiled from the published reports suggest that the cuu long basin is oil prone with the oil reservoired mainly in fractured basement highs whereas the nam con son basin is generally gas prone with the gas trapped in miocene sands and late miocene carbonates these distinct trends may be attributed to differences in timing of trap formation and the disruption of trap integrity caused by prolonged rifting and inversion in the nam con son basin gwang h lee is associate professor at kunsan national university korea his research interests include application of seismic reflection to basin research and sequence stratigraphy he received his b s and m s degrees in oceanography from seoul national university korea in 1981 and 1983 respectively and a ph d in geological geophysical oceanography from texas a m university in 1990 from 1991 to 1994 he worked for shell offshore inc in new orleans keumsuk lee received a b s degree in mathematics 1994 and an m s degree in geological oceanography 1999 from kunsan national university kunsan korea he is currently attending florida atlantic university boca raton florida his main research interest is application of geophysical methods to various geological and environmental problems joel s watkins is the earl f cook professor department of geology and geophysics texas am co chief scientist on dsdp leg 66 middle america trench and project director manager and vice president with gulf oil 1977 1985 he is the author or co author of more than 130 scientific publications and senior editor of aapg memoirs 29 34 and 53 his interests are structure and stratigraphy of small ocean basins and seismic reservoir characterization

siderite clumped isotope thermometry a new paleoclimate proxy for humid continental environments abstract clumped isotope measurements can be used to exploit the paleoclimatic potential of pedogenic siderite feco3 however the applicability of this method is held back by the lack of clumped isotope calibrations of mineralogies other than calcite and aragonite here we present an inorganic calibration of siderites grown in the laboratory between 21 and 51 c linear regression of 47 values and temperature 106 t2 k yields the following relationship r2 0 997 47 rf 0 0356 0 0018 10 6 t 2 0 172 0 019 we demonstrate that this calibration is indistinguishable from calcite at current levels of analytical precision our observations suggest that there is likely no large systematic bias in the clumped isotope acid fractionation factors between the two different carbonate minerals we also present clumped isotope measurements of a natural siderite collected from holocene sediments of the mississippi river delta we find that siderites record warm season marsh water temperatures instead of mean annual temperatures as it has long been presumed this finding has important implications for the accuracy of siderite stable isotope and clumped isotope based climate reconstructions

evolution of a terminal neoproterozoic carbonate ramp system buah formation sultanate of oman effects of basement paleotopography the buah formation is a carbonate unit of late neoproterozoic age exposed in the jabal akhdar of northern oman and the huqf region of central oman the buah formation is interpreted as a distally steepened storm dominated ramp containing inner ramp tidally influenced oolitic shoal and back shoal lagoon fades and storm dominated mid ramp facies a slope break separates mid ramp facies from outer ramp facies characterized by accumulation of redeposited carbonates on gently inclined slopes 1 2 degrees combined facies stacking patterns and outcrop correlation via 1 3 c profiles suggest that buah carbonates formed as a highstand systems tract characterized by a general upward shallowing of facies and strong lateral progradation on a regional scale buah facies distributions across oman were controlled by the presence of basement highs defining areas of reduced subsidence which promoted lateral progradation of the buah carbonate ramp for tens of kilometers while the faster subsiding areas became sites of deep water deposition

carbonate platform growth and demise offshore central vietnam effects of early miocene transgression and subsequent onshore uplift abstract miocene carbonate platforms cover a large part of the central vietnamese south china sea margin early carbonate deposition took place on two regional platforms separated by a narrow depression developed along the trace of the east vietnam boundary fault zone west of the east vietnam boundary fault zone the tuy hoa carbonate platform fringes the continental margin between da nang and nha trang here platform growth initiated during the early miocene and continued until middle miocene time when regional uplift led to subaerial exposure termination of platform growth and karstification east of the fault zone the triton carbonate platform was also initiated during the early miocene carbonate growth thrived during early and part of middle miocene time and a thick clean lower and middle miocene carbonate succession cover the triton horst and the qui nhon ridge during the middle miocene partial drowning resulted in the split up of the triton carbonate platform repeated partial drowning events throughout the middle and late miocene resulted in westwards retreat of platform growth and eventual platform drowning and termination of carbonate deposition modern carbonate growth continues on isolated platforms hosting the paracel islands farther seawards the onset of widespread carbonate deposition largely reflects the early miocene transgression of the area linked with early post rift subsidence and the opening of the south china sea the mid neogene shift in carbonate deposition is interpreted as a consequence of regional uplift and denudation of central and south indochina starting during middle miocene time when the tuy hoa carbonate platform became subaerially exposed stressed carbonate growth conditions on the triton carbonate platform probably resulted from increased inorganic nutrient input derived from the uplifted mainland possibly enhanced by deteriorated climatic conditions and rapid sea level fluctuations promoting platform drowning

depositional facies and platform architecture of microbialite dominated carbonate reservoirs ediacaran cambrian ara group sultanate of oman intrasalt carbonates of the ediacaran cambrian ara group constitute a significant reservoir element of the intrasalt stringer play in oman in which dolomitic carbonates are encased in salt at depths of 3 to 7 km 1 9 to 4 3 mi these reservoir carbonates have significant microbial influences although ara group reservoirs are mostly latest precambrian the models developed here may be applicable to younger microbially dominated carbonate reservoirs in basins of higher salinity when higher organisms are excluded in lacustrine settings where calcified invertebrates are not a significant source of carbonate or after periods of mass extinction before faunal recovery a broad range of carbonate facies provides the context in which to understand the origin of the microbialite dominated reservoirs developed across both ramp and rimmed shelf profiles major facies associations include carbonate evaporite transition zone deep ramp and slope subtidal microbialites clastic textured carbonates and restricted peritidal carbonates microbialites are subdivisible into a number of facies that all have significance in terms of understanding environmental history as well as reservoir properties and that help in predicting the location of reservoir fairways microbially influenced facies include shallow subtidal thrombolites with massive clotted textures and very high initial porosities 50 shallow subtidal pustular laminites with cm scale variability of lamina morphology deeper subtidal crinkly laminites that show mm scale variability of lamina morphology and intertidal tufted laminates that show mm to cm scale tufted textures other reservoir facies are more conventional grainy carbonates including ripple cross stratified grainstone packstone hummocky cross stratified grainstone packstone flat pebble conglomerate ooid and intraclast grainstone packstone and cloudina grainstone packstone these facies are almost invariably dolomitized and all have moderate to excellent reservoir quality these facies comprise carbonate platforms broken up during salt tectonics that range up to 160 m 525 ft in thickness and extended laterally prior to halokinesis for tens to over 50 km 31 mi the distribution of reservoir facies follows sequence stratigraphic predictions with microbialites occurring in every accommodation profile late highstand and early transgressive systems tracts favor greater lateral extent of thrombolite build ups whereas later transgressive to early highstand system tracts favor greater lateral discontinuity and compartmentalization of buildup reservoir facies pustular laminites occur in close association with thrombolite buildups but form laterally extensive sheets in late transgressive to late highstand periods crinkly laminites form during late transgressive to early highstand systems tracts and may represent maximum flooding intervals when the flux of carbonate sediment was greatly reduced allowing pelagically derived organics to accumulate

high temperature environments of human evolution in east africa based on bond ordering in paleosol carbonates many important hominid bearing fossil localities in east africa are in regions that are extremely hot and dry although humans are well adapted to such conditions it has been inferred that east african environments were cooler or more wooded during the pliocene and pleistocene when this region was a central stage of human evolution here we show that the turkana basin kenya today one of the hottest places on earth has been continually hot during the past 4 million years the distribution of 13c 18o bonds in paleosol carbonates indicates that soil temperatures during periods of carbonate formation were typically above 30 c and often in excess of 35 c similar soil temperatures are observed today in the turkana basin and reflect high air temperatures combined with solar heating of the soil surface these results are specific to periods of soil carbonate formation and we suggest that such periods composed a large fraction of integrated time in the turkana basin if correct this interpretation has implications for human thermophysiology and implies a long standing human association with marginal environments

polyphase thermal evolution in the infra cambrian ara group south oman salt basin as deduced by maturity of solid reservoir bitumen petrographic and organic geochemical analyses on solid reservoir bitumen from the late precambrian to early cambrian ara group indicate polyphase thermal evolution in the south oman salt basin sosb the ara group constitutes a complex petroleum system in the deep subsurface 3 5 km of interior oman salt diapirs encase isolated partly highly overpressured carbonate bodies intra salt stringers which represent a predominantly self charging hydrocarbon system a large number of stringer cores show that reservoir quality is decreased by the presence of solid reservoir bitumen by using different microscopy techniques this solid reservoir bitumen has been identified within pores pore throats and microfractures of the carbonates solid bitumen reflectance measurements brr were converted to vitrinite reflectance vrr using a new improved calibration vitrinite reflectance geothermometry shows that maximum paleo temperatures have a highly heterogeneous distribution paleo temperatures of 380 c were obtained from coke like solid reservoir bitumen which most likely formed from thermal cracking of oil in our model this process is related to hydrothermal fluids deriving from deeper pre salt strata of the sosb which entered the intra salt carbonate stringers during times of basement tectonic activity via hydrofractures this caused the formation of high maturities pyrobitumens in close vicinity to the fractures and precipitation of migrabitumens with increasing distance to the ht source which is supported by the geochemical composition of the solid reservoir bitumens the influx of these fluids into the carbonate stringers is considered to represent a major contribution to their strong overpressures 2007 elsevier ltd all rights reserved

finite extension across the south vietnam basins from 3d gravimetric modelling relation to south china sea kinematics abstract we derive a crustal thickness map over the south vietnam basins from a 3d inversion of gravity data that takes into account the sedimentary infill and its density variation with depth this map is used to estimate the total amount of stretching across these basins that varies from 190 km to the east at 111 e to 30 km to the west at 107 e comparison with south china sea kinematics amount and timing of oceanic opening implies large decoupling with respect to the indochina block and supports the hypothesis of formation of the south china sea in upper oligocene to lower miocene by southward subduction of the proto south china sea

compilation and time series analysis of a marine carbonate δ18o δ13c 87sr 86sr and δ34s database through earth history abstract the sr s o and c isotope database of marine carbonates contains over 55 000 published isotope values of low mg calcite from diagenetically little altered phanerozoic fossil shells as well as samples of whole rocks and calcite cements of ordovician to archean age carbon and oxygen isotope data for the shell material are divided into habitat subsets high mid low latitude and deep sea and whole rock data are separated by mineralogy into calcite dolomite subsets trend correlation wavelet and spectral analyses on gaussian filtered isotope records were applied to detect and quantify similarities and patterns in temporal records with the following results 1 oxygen isotope trends from the high latitude and deep sea habitats are almost indistinguishable through the last 115 ma consistent with the existence of the oceanic conveyor belt throughout this interval 2 all oxygen isotope habitat records show a strong coherent 30 45 ma 38 ma cyclicity throughout the cretaceous and the cenozoic 3 up to 70 of the multi million year variability in the 18o record of the last 115 ma can be simulated by the following equation 18 o 0 64 sin 2 t 120 ma 0 9 x sin 2 t 38 3 ma 1 1 with x ranging from 0 4 0 6 for the low high latitude and deep sea habitats to 0 8 for the mid latitude realm 1 a 120 20 ma cycle occurs in the paleozoic and neoproterozoic 18o record consistent with paleoclimate variability as interpreted from sedimentological and faunal records 2 the offset of 13c values between deep water and high latitude vs surficial habitats at lower latitudes is consistent with the operation of a biological pump in the oceans since at least the cretaceous 3 sr and s isotope records exhibit a 60 70 ma cyclicity throughout the phanerozoic

geochemical evidence for an early cambrian origin of the q oils and some condensates from north oman abstract the q family of oils from oman was previously recognized as highly unusual and distinct from the more prevalent huqf oil family by having an extraordinarily high c27 c29 sterane ratio and 13c values near 30 a re evaluation of the hydrocarbon constituents of the q oils using gc ms ms analyses resulted in identification of other useful geochemical discriminators that include gammacerane hopane ratios between 0 5 and 0 9 c24t c23t 0 7 combined with c22t c21t cheilanthane ratios although we were unable to identify a source facies within the sediments of the south oman salt basin that convincingly correlated with the hydrocarbons of the q oils the geochemistry of q oils provided valuable clues about their origin sterane and terpane patterns indicated that the q source rock is most likely a marine shale deposited under intermittently anoxic and hypersaline conditions the absence of a carbon isotopic ordering anomaly for normal alkanes and isoprenoids points to a cambrian age for the q oils moreover trends in the patterns of norsteranes in south oman carbonate stringer oils suggest the q oil source originates from one of the upper units of the ara carbonate and evaporite sequence more specifically our results point to a siliciclastic source rock lying stratigraphically above the a6 carbonates from the dhahaban formation the high relative abundances of 24 isopropylcholestanes in q oils likely originate from demosponges and we hypothesize that the 17 methylpentatriacontane which is so abundant in q oils is a biomarker for early arthropods that inhabited the salt basins of oman at the very beginning of the cambrian period

latitudinal temperature gradients and high latitude temperatures during the latest cretaceous congruence of geologic data and climate models a major challenge in paleoclimatology is disagreement between data and models for periods of warm climate data generally indicate equable conditions and reduced latitudinal temperature gradients while models generally produce colder conditions and steeper latitudinal gradients except when using very high co2 here we show congruence between temperature indicators and climate model output for the cool greenhouse interval of the latest cretaceous maastrichtian using a global database of terrestrial and marine indicators and fully coupled simulations with the community climate system model version 3 in these simulations we explore potential roles of greenhouse gases and properties of pre anthropogenic liquid clouds in creating warm conditions our model simulations successfully reproduce warm polar temperatures and the latitudinal temperature gradient without overheating the tropics best fits for mean annual temperature are simulations that use 6 preindustrial levels of atmospheric co2 or 2 preindustrial levels of atmospheric co2 and liquid cloud properties that may reflect pre anthropogenic levels of cloud condensation nuclei the siberian interior is problematic but this may relate to reconstructed elevation and the presence of lakes data and models together indicate tropical sea surface temperatures 5 c above modern an equator to pole temperature difference of 25 30 c and a mid latitudinal temperature gradient of 0 4 c per 1 latitude similar to the eocene modified liquid cloud properties allow successful simulation of maastrichtian climate at the relatively low levels of atmospheric co2 indicated by proxies and carbon cycle modeling this supports the suggestion that altered properties of liquid clouds may be an important mechanism of warming during past greenhouse intervals

clumped isotope fractionation during phosphoric acid digestion of carbonates at 70 c the application of clumped isotopes 47 in carbonate minerals as a sensitive temperature proxy in paleo environments depends on a well constrained clumped isotope fractionation for the necessary step of phosphoric acid digestion of the carbonate mineral to produce co2 published estimates for clumped isotope fractionations vary and the effect of different carbonate mineralogies is still under debate differences in the sample preparation design and sample digestion temperatures are potential sources for varying acid fractionations and could be a source for discrepant 47 temperature calibrations observed in different laboratories to evaluate the clumped isotope acid fractionation at 70 c and simultaneously account for a potential cation effect we analyzed a set of eight carbonate minerals calcite aragonite dolomite and magnesite that were driven to a stochastic isotope distribution by heating them to temperatures of 1000 c our study reveals significant cation and mineral specific differences for the 47 acid fractionation of carbonate minerals digested at 70 c or 100 c the 47 acid fractionation at 70 c for calcite is 0 197 0 002 for aragonite 0 172 0 003 whereas dolomite has a significantly larger acid fractionation of 0 226 0 002 for magnesite digested at 100 c we observed a 47 acid fractionation of 0 218 0 020 projected to an acid digestion at 25 c our acid fractionation for calcite of 0 260 is statistically indistinguishable from existing studies we further show that the 47 of the calcite standards eth 1 and eth 2 of 0 265 and 0 267 respectively are in the range of the determined acid fractionation projected to 25 c suggesting that they have an identical and near stochastic isotope distribution the observed differences in the 47 acid fractionation between calcite and aragonite 47 0 025 and between calcite and dolomite 47 0 029 does not correlate with the phosphoric acid fractionation of oxygen isotopes but rather depends on the radius of the cation as well as on the mineral structure our results reveal that the acid fractionation of dolomite at 70 c is significantly distinct from the one of calcite but at 90 c the two are within error of each other due to the different acid fractionation temperature dependence of calcite and dolomite thus it is necessary to use a mineral specific 47 acid fractionation factor for dolomite to avoid differences in the final 47 signal from dolomites digested at 90 c and dolomites digested at lower temperatures similar effects may apply also to other carbonates such as magnesite and siderite however their mineral specific 47 acid fractionation at digestion temperatures around 90 c might be also similar to the one of calcite so that potential differences could be within the range of the analytical error

carbonate clumped isotope bond reordering and geospeedometry carbonate clumped isotope thermometry is based on the preference of 13c and 18o to form bonds with each other at elevated temperatures such bond ordering is susceptible to resetting by diffusion of c and o through the solid mineral lattice this type of bond reordering has the potential to obscure primary paleoclimate information but could also provide a basis for reconstructing shallow crustal temperatures and cooling rates we determined arrhenius parameters for solid state reordering of c o bonds in two different calcites through a series of laboratory heating experiments we find that the calcites have different susceptibilities to solid state reordering reaction progress follows a first order rate law in both calcites but only after an initial period of non first order reaction that we suggest relates to annealing of nonequilibrium defects when the calcites are first heated to experimental temperature we show that the apparent equilibrium temperature equations or closure temperature equations for carbonate clumped isotope reordering are analogous dodson s equations for first order loss of daughter isotopes for each calcite the sensitivity of apparent equilibrium temperature to cooling rate is sufficiently high for inference of cooling rates within a factor of 5 or better for cooling rates ranging from tens of degrees per day to a few degrees per million years however because the calcites have different susceptibilities to reordering each calcite defines its own cooling rate apparent equilibrium temperature relationship the cooling rates of carrara marble inferred from carbonate clumped isotope geospeedometry are 10 6 10 3 degrees per annum and are in broad agreement with rates inferred from thermochronometric methods cooling rates for 13c depleted calcites from the late neoproterozoic doushantou cap carbonates in south china are on the order of 102 104 degrees per annum consistent with rapid cooling following formation of these calcites by a short lived hydrothermal event bristow et al 2011 nature v 474 p 68 71 most of the uncertainty in these estimates relates to uncertainty in arrhenius parameters for different calcites thus while the carbonate clumped isotope geospeedometer shows promise for recording cooling rates in settings and lithologies where other geospeedometers may not be applicable the uncertainty in cooling rate will be large without independent knowledge of the reordering kinetics of each study material thus the full potential of the method will only be realized if reordering kinetics can be accurately determined for each study material or predicted on the basis of mineral composition texture or other observable parameters

carbon oxygen and strontium isotopes in paleozoic carbonate components an evaluation of original seawater chemistry proxies abstract brachiopods trilobites cements and whole rock matrix material were evaluated for their reliability as proxies of original seawater carbon oxygen and strontium isotope chemistry in this process coeval material was evaluated from individual horizons of formations spanning the permian to cambrian unaltered shells of low mg calcite articulated brachiopods retain original seawater oxygen carbon and strontium isotope compositions as old as late ordovician assessments of older specimens are hampered by a lack of suitable material coeval brachiopod whole rock sets a definitive assessment of cement marine chemistry is difficult due to the paucity of material but despite this caveat cements hold some promise for retaining original carbon and possibly strontium isotope seawater values in contrast the potential of whole rock material as a proxy of original seawater chemistry is quite complex in some but not all instances the carbon isotopic composition of whole rock after detailed scrutiny and evaluation appears to represent an original seawater chemistry signal in a few instances their oxygen isotope compositions reflect original seawater values unlike the stable isotope compositions the strontium isotopes of all studied whole rock material permian to upper cambrian appear not to reflect original seawater chemistry values thus the potential for retaining original seawater isotope chemistry and serving as specific proxies in order of decreasing reliability are 1 unaltered low mg calcite brachiopods c o and sr isotopes 2 pristine marine cements c and sr isotopes and 3 whole rock material c isotopes carbon oxygen and strontium isotope compositions of ordovician trilobites mirror those of coeval unaltered brachiopods cambrian trilobites hold significant promise as an important proxy of original seawater isotope chemistry but further studies are needed to ascertain their full potential the survey of isotopes in some ordovician and cambrian intermediate low mg calcite trilobites demonstrates their potential as an important proxy of original seawater chemistry

microbial communities and their primary to early diagenetic mineral phases the record from neoproterozoic microbialites of qarn alam oman

the clumped isotope geothermometer in soil and paleosol carbonate we studied both modern soils and buried paleosols in order to understand the relationship of temperature t c 47 estimated from clumped isotope compositions 47 of soil carbonates to actual surface and burial temperatures carbonates from modern soils with differing rainfall seasonality were sampled from arizona nevada tibet pakistan and india t c 47 obtained from these soils shows that soil carbonate forms in the warmest months of the year in the late morning to afternoon and probably in response to intense soil dewatering t c 47 obtained from modern soil carbonate ranges from 10 8 to 39 5 c on average t c 47 exceeds mean annual temperature by 10 15 c due to summertime bias in soil carbonate formation and to summertime ground heating by incident solar radiation secondary controls on t c 47 are soil depth and shading site mean annual air temperature maat across a broad range 0 30 c of site temperatures is highly correlated with t c 47 from soils following the equation maat c 1 20 t c 47 0 21 72 r 2 0 92 where t c 47 0 is the effective air temperature at the site estimated from t c 47 the effective air temperature represents the air temperature required to account for the t c 47 at each site after consideration of variations in t c 47 with soil depth and ground heating the highly correlated relationship in this equation should now permit mean annual temperature in the past to be reconstructed from t c 47 in paleosol carbonate assuming one is studying paleosols that formed in environments generally similar in seasonality and ground cover to our calibration sites t c 47 0 decreases systematically with elevation gain in the himalaya following the equation elevation m 229 t c 47 0 9300 r 2 0 95 assuming that temperature varied similarly with elevation in the past this equation can be used to reconstruct paleoelevation from clumped isotope analysis of ancient soil carbonates we also measured t c 47 from long sequences of deeply buried 5 km paleosol carbonate in the himalayan foreland in order to evaluate potential diagenetic resetting of clumped isotope composition we found that paleosol carbonate faithfully records plausible soil t c 47 down to 2 5 4 km burial depth or 90 125 c deeper than this and above this temperature t c 47 in paleosol carbonate is reset to temperatures 40 c we observe 40 c as the upper limit for t c 47 in modern soils from soil depths 25 cm and therefore that t c 47 40 c obtained from ancient soil carbonate indicates substantially warmer climate regimes compared to the present or non primary temperatures produced by resetting during diagenesis if representative this limits the use of t c 47 to reconstruct ancient surface temperature to modestly buried 3 4 km paleosol carbonates despite diagenetic resetting of 47 values 18 o and 13 c values of the same deeply buried paleosol carbonate appear unaltered we conclude that solid state reordering or recrystallization of clumping of carbon and oxygen isotopes can occur in the absence of open system exchange of paleosol carbonate with significant quantities of water or other phases

determining the δ47 acid fractionation in dolomites abstract this paper reports the fractionation of 47 during the digestion of dolomite in phosphoric acid between 25 c and 90 c using five different samples including three of pliocene age from the bahamas one from the jurassic in the middle east and one obtained from the national institute of standards nist 88b the composition of the dolomites analyzed varied from ca0 56mg0 44co3 to ca0 50mg0 50co3 fractionation values were also compared between the common acid bath and sealed vessel techniques at various temperatures no statistically significant differences were observed either between these two methods or as a function of the dolomite s stoichiometry these data produce a difference in fractionation of 0 153 0 011 for dolomite samples digested at 90 c compared to those reacted at 25 c a value higher and statistically different to previously published values utilization of this value in a study of dolomites from a core drilled on the island of san salvador in the bahamas yielded temperatures and 18ofluid values which agree with previous interpretations on the formation of these dolomites application of this value to other published studies produces lower estimates of temperature and 18ofluid values for the dolomitization process that are more consistent with the geologic models suggested for these studies

shallow burial alteration of dolomite and limestone clumped isotope geochemistry carbonate clumped isotope paleothermometry is a promising method for paleoclimate reconstructions and understanding diagenetic processes although clumped isotope compositions measured as 47 values can be altered by recrystallization and thermal resetting several studies have investigated the effects of deep burial and exhumation on 47 values we present 47 values of samples from an 4500 m long drill core from andros island bahamas which represent the spectrum from shallow to deep burial conditions these limestones and dolomites originally formed under near surface temperature conditions which are reflected by 27 c 47 temperatures in samples buried to 1 3 km depth below this depth calculated 47 temperatures increase by 10 c indicating a shift from preserved near surface temperatures to diagenetically modified values importantly this shift is not accompanied by a change in 18o and 13c values or cathodoluminescence and non uniform micrometer scale crystallization is observed in both 47 altered and unaltered rocks similar 47 temperatures recorded by each carbonate phase suggest that mineral specific differences are minor fine grained dolomites and calcites are viable materials for recording surface temperature conditions and both are susceptible to alteration of their primary clumped isotope abundances during burial diagenesis our results demonstrate that original 47 values of fine grained carbonates can be altered under mild diagenetic conditions

climate model and proxy data constraints on ocean warming across the paleocene eocene thermal maximum article constraining the greenhouse gas forcing climatic warming and estimates of climate sensitivity across ancient large transient warming events is a major challenge to the palaeoclimate research community here we provide a new compilation and synthesis of the available marine proxy temperature data across the largest of these hyperthermals the paleocene eocene thermal maximum petm this includes the application of consistent temperature calibrations to all data including the most recent set of calibrations for archaeal lipid derived palaeothermometry this compilation provides the basis for an informed discussion of the likely range of petm warming the biases present in the existing record and an initial assessment of the geographical pattern of petm ocean warming to aid interpretation of the geographic variability of the proxy derived estimates of petm warming we present a comparison of this data with the patterns of warming produced by high pco2 sim ulations of eocene climates using the hadley centre atmosphere ocean general circulation model aogcm hadcm3l on the basis of this comparison and taking into account the patterns of intermediate water warming we estimate that the global mean surface temperature anomaly for the petm is within the range of 4 to 5 c

carbonate deposition and hydrocarbon reservoir development at the precambrian cambrian boundary the ara group in south oman abstract the ediacaran early cambrian ara group in the south oman salt basin consists of six evaporite carbonate cycles a0 a1 to a6 that record tectono eustatic sea level changes the a4 cycle developed at the precambrian cambrian boundary 542 ma it forms a single depositional sequence with evaporites deposited in a lowstand systems tract lst overlying carbonates represent an open marine shallowing upward ramp succession that developed in transgressive tst and highstand systems tracts hst the low energy carbonate ramp occupied a relatively protected site between a large shelf and an exposed paleogeographical high the tst facies include sulfates evaporite carbonate laminites and organic rich carbonate laminites that record initial flooding deepening of the basin and establishment of an outer ramp depositional environment carbonate sediment flux was low and the environment was partly subject to cyclically elevated salinity subsequent hst facies comprise mostly fine grained clastic carbonates and stromatolites that formed in middle and inner ramp settings these facies show evidence of shoaling and establishment of a carbonate factory that probably operated over most of the middle and inner ramp sediment was redistributed in suspension by muddy turbidity currents muddy debris flows storm and shallow water currents during the late hst carbonate facies were affected by elevated salinity and recorded the gradual transition to the overlying lst evaporite unit a combination of strong tectonic subsidence and transient flooding caused significant shallow water evaporite deposition to occur not only down dip but also on top of the former carbonate platform where several hundreds of meters of evaporites accumulated the transgressive carbonate laminites are the main reservoir facies and thus represent a relatively unusual reservoir unit the presence of organic material and the relative scarcity of carbonate mud influenced diagenesis and reservoir properties distribution of organic material and carbonate mud can be linked to specific environmental conditions low physical and biogenic disturbance of sediment and stratified water mass and the sequence stratigraphic position low flux of fine grained carbonate during tst in contrast diagenetic evaporite formation has largely degraded reservoir quality in porous shallow water facies near the top of the a4c

calibrating the coevolution of ediacaran life and environment the rise of animals occurred during an interval of earth history that witnessed dynamic marine redox conditions potentially rapid plate motions and uniquely large perturbations to global biogeochemical cycles the largest of these perturbations the shuram carbon isotope excursion has been invoked as a driving mechanism for ediacaran environmental change possibly linked with evolutionary innovation or extinction however there are a number of controversies surrounding the shuram including its timing duration and role in the concomitant biological and biogeochemical upheavals here we present radioisotopic dates bracketing the shuram on two separate paleocontinents our results are consistent with a global and synchronous event between 574 0 4 7 and 567 3 3 0 ma these dates support the interpretation that the shuram is a primary and synchronous event postdating the gaskiers glaciation in addition our re os ages suggest that the appearance of ediacaran macrofossils in northwestern canada is identical within uncertainty to similar macrofossils from the conception group of newfoundland highlighting the coeval appearance of macroscopic metazoans across two paleocontinents our temporal framework for the terminal proterozoic is a critical step for testing hypotheses related to extreme carbon isotope excursions and their role in the evolution of complex life

development and controlling factors of miocene carbonate platform in the nam con son basin southwestern south china sea miocene carbonate platforms are located on intrabasinal structural highs and along the southern margin of the nam con son basin also referred to as the wanan basin by chinese southwestern south china sea these isolated platforms together cover a gross area of over 25 000 km 2 we map the platforms reconstruct their evolution and evaluate the controls on platform growth and demise within the regional geological setting using available seismic and well data the platforms initiated in the late early miocene and reached their widest extent during the middle miocene the platform margins were controlled by synsedimentary faults associated with carbonate slope failure deposits and or reef talus the platforms formed as isolated platform platform growth history involves six phases start up second start up keep up exposure renewal and drowning phases quantitative analysis of the basin evolution indicates that tectonism eustasy the supply of both terrigenous sediment and nutrients were the dominant controls on platform development and demise c 2013 elsevier ltd all rights reserved

burial and thermal history of proterozoic source rocks in oman abstract a geological and thermal history of the proterozoic sedimentary basin in oman was reconstructed to determine the time of hydrocarbon generation from the proterozoic huqf group source rocks data from 97 exploration wells and supplementary seismic reflection profiles were used to establish the burial graphs for the source rocks at all 97 locations the overburden removed during formation of regional unconformities was estimated from regional geological data compaction trends and fission track analyses the thermal history was reconstructed on the basis of present day temperature data in the wells heat flow models and the palaeo surface temperature history the calculated present day surface heat flow map shows very low values 35 40 mw m 2 over the basin axis while on the edges the values are in the range 55 65 mw m 2 the results of the maturity calculations show that in northwest oman oil generation occurred mainly during the mesozoic and that probably a large proportion of the traps in which reserves have been discovered was formed just before the last oil generation phase however in the central and southeastern part of the country hydrocarbon generation stopped about 400 ma ago this is due to the maximum burial temperature being reached at around that time considering the fact that almost all traps in which reserves have been located are significantly younger than the time of oil generation one has to invoke processes of remigration to explain the oil occurrences the geological data from oman show that the eastern margin of the country presently facing the arabian sea has been a high for most of its phanerozoic history the data on quantities of eroded and deposited sediments lend support for the theory that the margin was formed by a transform fault

temperatures and oxygen isotopic composition of phanerozoic oceans abstract the temperature of ancient oceans is an important constraint for understanding the climate history of our planet the classical oxygen isotope paleothermometry on fossil shells while very proficient when applied to the younger cenozoic portion of the geologic record is believed to yield only unreliable results for the phanerozoic deep time either because the empirically well documented secular trend to more negative 18 o values with increasing age was generated by post depositional recrystallization processes or if primary implies ecologically unpalatable hot early oceans here we present a compilation of 18 o measurements for 58 532 low mg calcite marine shells that cover almost the entire phanerozoic eon argue that the secular decline of about 6 is primary propose that it reflects the changing oxygen isotopic composition of sea water and define a new baseline trend for 18 o of paleo sea water the latter providing a new template for calculation of ambient habitat temperatures of fossil specimens the resulting pattern for fossil taxa foraminifera brachiopods belemnites and bivalves mimics their modern counterparts in temperature ranges and modes this conceptual framework enables application of actualistic concepts to ambient habitat temperatures of fossils and provides us with a long overdue tool for interpretation of deep time geologic history

heat transport deep waters and thermal gradients coupled simulation of an eocene greenhouse climate for the first time a coupled general circulation model with interactive and dynamical atmospheric oceanic and sea ice components is used to simulate an eocene 50 ma greenhouse climate we introduce efficient ocean spin up methods for coupled paleoclimate modeling sea surface temperatures ssts and salinities evolve unconstrained producing the first proxy data independent estimates for these eocene climate parameters tropical and extratropical model predicted ssts are warmer than modern values by 3 and 5 c respectively salinity driven deep water formation occurs in the north atlantic and tethys the zonal average overturning circulation is weaker than modern eocene ocean heat transport is 0 6 pw less than modern in the northern hemisphere and 0 4 pw greater in the southern hemisphere the model predicted near modern vertical and meridional eocene temperature gradients imply that the dominant theory for maintaining low gradients increased ocean heat transport is incorrect or incomplete and other mechanisms should be explored

clumped isotope geochemistry the study of naturally occurring multiply substituted isotopologues clumped isotope geochemistry is concerned with the state of ordering of rare isotopes in natural materials that is it examines the extent to which rare isotopes d 13 c 15 n 18 o etc bond with or near each other rather than with the sea of light isotopes in which they swim abundances of isotopic clumps in natural materials are influenced by a wide variety of factors in most cases their concentrations approach within ca 1 relative the amount expected for a random distribution of isotopes deviations from this stochastic distribution result from enhanced thermodynamic stability of heavy isotope clumps slower kinetics of reactions requiring the breakage of bonds between heavy isotopes the mass dependence of diffusive and thermo gravitational fractionations mixing between components that differ from one another in bulk isotopic composition biochemical and photochemical fractionations that may reflect combinations of these simpler physical mechanisms and in some cases other processes we do not yet understand although clumped isotope geochemistry is a young field several seemingly promising applications have already emerged most importantly it appears that proportions of 13 c 18 o bonds in carbonate minerals are sensitive to their growth temperatures independent of bulk isotopic composition thus clumped isotope analysis of ancient carbonates can be used as a quantitative paleothermometer that requires no assumptions about the 18 o of waters from which carbonates grew this approach has been used to reconstruct marine temperatures across the phanerozoic reaching back to the silurian terrestrial ground temperatures across the cenozoic thermal histories of aqueously altered meteorites among other applications clumped isotope geochemistry is also placing new constraints on the atmospheric budget and stratospheric photochemistry of co 2 and should be capable of placing analogous new constraints on the budgets of other atmospheric gases finally this field could be extended to encompass sulfates volatile hydrocarbons organic moieties and other materials

temperature evolution and the oxygen isotope composition of phanerozoic oceans from carbonate clumped isotope thermometry abstract surface temperature is among the most important parameters describing planetary climate and habitability and yet there remains considerable debate about the temperature evolution of the earth s oceans during the phanerozoic eon 541 million years ago to present the time during which complex metazoan life radiated on earth here we critically assess the emerging record of phanerozoic ocean temperatures based on carbonate clumped isotope thermometry of fossil brachiopod and mollusk shells and we present new data that fill important gaps in the late paleozoic record we evaluate and reject the hypothesis that solid state reordering of 13c 18o bonds has destroyed the primary clumped isotope temperature signal of most fossils during sedimentary burial at elevated temperatures the resulting phanerozoic record which shows a general coupling between tropical seawater temperatures and atmospheric carbon dioxide co2 levels since the paleozoic indicates that tropical temperatures during the icehouse climate of the carboniferous period were broadly similar to present 25 30 c and suggests that benthic metazoans were able to thrive at temperatures of 35 40 c during intervals of the early and possibly the latest paleozoic when co2 levels were likely 5 10 higher than present day values equally important there is no resolvable trend in seawater oxygen isotope ratios 18 o over the past 500 million years indicating that the average temperature of oxygen exchange between seawater and the oceanic crust has been high 270 c since at least the early paleozoic which points to mid ocean ridges as the dominant locus of water rock interaction over the past half billion years

origin of petroleum in the neoproterozoic cambrian south oman salt basin abstract the south oman salt basin sosb is host to the world s oldest known commercial deposits most of the south oman oils have been proven to be associated with the source rocks of the neoproterozoic to cambrian huqf supergroup but the assignment of oils to specific huqf intervals or facies has been hampered by the geochemical similarity of the organic matter across the entire huqf sequence possibly as a consequence of limited change in the local palaeoenvironment and biota over the time of its deposition this study was conducted to establish improved correlations between organic rich rock units and reservoir fluids in the sosb through detailed molecular and isotopic analysis of the huqf supergroup with special emphasis directed towards understanding the ara carbonate stringer play unusual biomarkers tentatively identified as a norsteranes show distinctive patterns among carbonate stringer oils and rocks different from those observed in nafun sediments and ara rocks from the athel basin these putative a norsteranes form the basis for new oil source correlations in the sosb and provide for the first time geochemical evidence of a self charging mechanism for the carbonate stringer play the paucity of markers specific to the nafun group shuram buah and masirah bay formations confounds attempts to quantify their respective contributions to huqf oil accumulations nafun inputs can only be determined on the basis of subtle differences between nafun and ara biomarker ratios the most useful geochemical characteristics delineating nafun group organic matter from ara group intra salt source rocks included low relative abundance of mid chain monomethyl alkanes x compounds low relative abundance of gammacerane 28 30 dinorhopane 25 28 30 trinorhopane and 2 methylhopanes low c 22 t c 21 t and high c 23 t c 24 t cheilanthanes ratio values based on these parameters molecular evidence for major contributions of liquid hydrocarbons from nafun group sediments shuram buah and masirah bay formations is lacking our results suggest that the majority of sosb hydrocarbon accumulations originate from within the ara group either from the carbonate stringers or from the package of sediments that comprises the thuleilat athel silicilyte and u shale formations subtle aspects of the composition of some carbonate stringer and post salt huqf oils could suggest some degree of sourcing from the nafun rocks but stronger evidence is needed to confirm this

erosion of northern hemisphere blanket peatlands under 21st century climate change peatlands are important terrestrial carbon stores particularly in the northern hemisphere many peatlands such as those in the british isles sweden and canada have undergone increased erosion resulting in degraded water quality and depleted soil carbon stocks it is unclear how climate change may impact future peat erosion here we use a physically based erosion model pesera peat driven by seven different global climate models gcms to predict fluvial blanket peat erosion in the northern hemisphere under 21st century climate change after an initial decline total hemispheric blanket peat erosion rates are found to increase during 2070 2099 2080s compared with the baseline period 1961 1990 for most of the gcms regional erosion variability is high with changes to baseline ranging between 1 27 and 21 63 t ha 1 yr 1 in the 2080s these responses are driven by effects of temperature generally more dominant and precipitation change on weathering processes low latitude and warm blanket peatlands are at most risk to fluvial erosion under 21st century climate change

paleoclimate reconstruction using carbonate clumped isotope thermometry carbonate clumped isotope thermometry is a relatively new paleotemperature proxy based on measurements of the degree of ordering of 13 c and 18 o into bonds with each other making the 13 c 18 o 16 o 2 2 ion group in lattices of carbonate minerals this technique has several unusual properties that complement existing methods of paleoclimate reconstruction most importantly it is based on a homogeneous isotope exchange equilibrium and thus constrains temperature independent of the isotopic composition of waters from which carbonates grew this method also appears to be generally insensitive to vital effects that compromise many other paleothermometers based on the chemical properties of biominerals or organic matter at least for those organisms that have been subjected to systematic study to date corals and foraminifera however discrepancies among some calibrations particularly at low temperatures may point toward the existence of vital effects in mollusks and other organisms this review discusses the principles and calibrations of the technique its uses in combination with conventional stable isotope measurements to constrain the 18 o of past waters preservation of paleotemperatures in ancient materials as well as current problems in our understanding of calibrations and interlaboratory data comparisons

a 600 million year carbonate clumped isotope record from the sultanate of oman carbonate clumped isotope thermometry is a promising technique that has the potential to help decode the significance of the variability of both physical and geochemical compositions of ancient carbonate rocks this study utilizes a 600 million year record of marine carbonate rocks from the subsurface and surface of the sultanate of oman to explore how burial and exhumation affected the carbonate clumped isotope thermometer samples span 6 km of burial depth and include calcite and dolomite mineralogies and a range of carbonate rock textures we find evidence for two broad patterns in the physical and geochemical behavior of carbonate rocks during burial the first group of carbonates yield water 18 o vsmow compositions slightly enriched or equal to an expected ice free seawater composition of 1 2 and display good to fair textural preservation suggesting that cementation and lithification occurred within tens of meters of the sediment water interface temperatures from the second group sit on the present day geotherm yield highly enriched water 18 o vsmow compositions and display fair to poor textural preservation we find no evidence for solid state reordering in paired analyses of calcites and dolomites our results contribute to a growing body of work that indicates that the seawater 18 o vsmow composition has not changed significantly over 600 myr and was not 6 in the ediacaran

temperature dependence of oxygen and clumped isotope fractionation in carbonates a study of travertines and tufas in the 6 95 c temperature range conventional carbonate water oxygen isotope thermometry and the more recently developed clumped isotope thermometer have been widely used for the reconstruction of paleotemperatures from a variety of carbonate materials in spite of a large number of studies however there are still large uncertainties in both 18o and 47 based temperature calibrations for this reason there is a need to better understand the controls on isotope fractionation especially on natural carbonates in this study we analyzed oxygen carbon and clumped isotopes of a unique set of modern calcitic and aragonitic travertines tufa and cave deposits from natural springs and wells together these samples cover a temperature range from 6 to 95 c travertine samples were collected close to the vents of the springs and from pools and tufa samples were collected from karstic creeks and a cave the majority of our vent and pool travertines and tufa samples show a carbonate water oxygen isotope fractionation comparable to the one of tremaine et al 2011 with some samples showing higher fractionations no significant difference between the calcite water and aragonite water oxygen isotope fractionation could be observed the 47 data from the travertines show a strong relationship with temperature and define the regression 47 0 044 0 005 106 t2 0 205 0 047 the ph of the parent solution mineralogy and precipitation rate do not appear to significantly affect the 47 signature of carbonates compared to the temperature effect and the analytical error the tufa samples and three biogenic calcites show an excellent fit with the travertine calibration indicating that this regression can be used for other carbonates as well this work extends the calibration range of the clumped isotope thermometer to travertine and tufa deposits in the temperature range from 6 c to 95 c

the enigma of neoproterozoic giant ooids fingerprints of extreme climate geologists have documented at least fourteen occurrences of giant ooids a geologically rare type of carbonate allochem in neoproterozoic successions at low paleo latitudes recent experiments a

calcite cement in permian deep water sandstones delaware basin west texas origin distribution and effect on reservoir properties calcite cement is the dominant control on reservoir quality in turbidite sandstones of the upper permian bell canyon formation delaware basin these well sorted very fine grained arkoses were deposited in a basin floor setting by channel levee systems terminating in broad lobes calcite cement distribution in the east ford and geraldine ford fields was mapped using core log and thin section data calcite is concentrated in tightly cemented zones that are mostly less than 1 ft 0 3 m thick areas that have high percentages of calcite cemented sandstone 20 occur along the margins of the sandstone bodies in overbank and lobe deposits where sandstone pinches out into siltstone areas that have the lowest percentage of calcite cemented sandstone 10 occur where the sandstone is thickest in the channel facies isotopic composition of the calcite 13c 1 8 to 3 0 relative to the peedee belemnite pdb 18o 4 6 to 6 3 pdb is consistent with the source of calcium carbonate being from dissolution of detrital carbonate rock fragments and marine skeletal debris because internal sources of calcite were apparently insufficient to account for the cement volume cement components are interpreted as having been transported into the sandstones from organic rich basinal siltstones and limestones feldspars buffered acidic formation waters near where they entered the sandstone resulting in calcite concentrated near the sandstone margins the calcite formed near maximum burial depths of 4800 ft 1 5 km and temperatures of 104f 40c from marine pore waters with 18o of approximately 0 relative to standard mean ocean water most of the calcite cemented zones are interpreted as being concretions that extend no more than a few meters laterally production data and geophysical log correlations suggest that some cemented zones are laterally continuous at least 1000 ft 300 m and cause vertical reservoir compartmentalization laterally extensive calcite layers may be associated with the base of turbidite deposits

geological development of the central and south vietnamese margin implications for the establishment of the south china sea indochinese escape tectonics and cenozoic volcanism abstract the vietnamese margin forms a key region to the understanding of escape tectonics and the development of the south china sea scs the existing geological reconstructions of the region are restricted to studies of single basins are based on limited amounts of geophysical data or analysis of onshore geological features these models are critically assessed on the basis of interpretation of the most comprehensive 2 d digital seismic database published to date within the area combined with a thorough analysis of existing literature and a new model is presented the vietnamese margin is underlain by a series of paleogene rift basins established through southeastward extrusion of indochina the east vietnam boundary fault evbf forms the almost 1000 km long seaward continuation of the left lateral ailao shan red river shear zone asrrsz toward the southern half of the phu khanh basin the evbf breaks up into discrete segments and splays into the se directed tua hoa fault zone paleogene faults splayed from the evbf and the mae ping shear zone and accommodated the coeval motion of these two major left lateral structural lineaments during the late oligocene basin inversions offshore occurred contemporaneously with initial right lateral inversion along the mae ping shear zone and the onset of major uplift of the metamorphic core complexes along the asrrsz it is suggested that a dramatic change of the regional stress pattern occurred in response to the northward movement of india and the effective coupling of the west burma block and india the later resulting in broadening of the indenting continental mass after the mid oligocene left lateral movements across the offshore evbf decreased and eventually ceased later onshore sinistral movements were accommodated by internal shortening and local clockwise block rotations within the shan thai terrain renewed rifting offshore south vietnam resulted from the jump of the scs spreading axis and subsequent neogene southwestward propagation of continental break up the neogene opening of the scs is viewed as a consequence of a slab pull associated with subduction of the proto scs underneath borneo as offshore neogene escape tectonism had virtually ceased during this phase of rifting right lateral transtension is inferred along n to nw oriented fault zones in the phu khanh and the nam con son basins rifting and by inference seafloor spreading continued until the end of middle miocene time although at significantly reduced rates during the final 5 10 ma termination of seafloor spreading is marked by a distinct latest middle miocene unconformity in the nam con son and the southern phu khanh basins neogene volcanism resulted in the build up of several magmatic structures across the central and south vietnamese margin and induced reactivation of older faults in the phu khanh basin the offshore magmatism heralded widespread volcanism onshore southern indochina associated with a latest neogene uplift and denudation event the uplift led to significantly increased siliciclastic accumulation rates offshore which repressed widespread carbonate deposition

late precambrian cambrian sediments of huqf group sultanate of oman the huqf group is the oldest known sedimentary sequence overlying crystalline basement in the sultanate of oman it crops out on a broad regional high the huqf axis which forms a dominating structural element on the southeastern edge of the arabian peninsula subsurface and outcrop evidence within and outside of oman suggests that the sediments of the huqf group lie within the age span of late precambrian to early middle cambrian the huqf group is subdivided into five formations corresponding to an alternation of clastics abu mahara and shuram formations and carbonates khufai and buah formations deposited in essentially shallow marine to supratidal or fluviatile conditions and terminated by an evaporitic sequence ara formation evaporites are absent on the huqf axis but they are thickly developed to the west over a large part of southern and central oman where they acted as the major structure former of most of oman s oil fields and even locally pierced up to the surface in the subsurface the huqf group has been reached by the drill mainly in southern oman where its lithostratigraphy resembles that defined in the type area in central oman the oldest sediments exposed in the core of the oman mountains may be correlative with the huqf group regional correlations suggest that the predominantly carbonate evaporitic facies of the huqf group was widely distributed in late precambrian early cambrian time the huqf basin is tentatively considered part of a belt of evaporitic basins and intervening carbonate platforms which stretched across the pangea landmass from the indian subcontinent salt range of pakistan through south yemen oman and saudi arabia into the gulf states and iran hormuz series and carbonate platform north of the zagros

chemostratigraphic and sedimentological framework of the largest negative carbon isotopic excursion in earth history the neoproterozoic shuram formation nafun group oman abstract oman records in its neoproterozoic nafun group huqf supergroup an essentially complete carbonate rich ediacaran succession the nafun group overlies the presumed marinoan rift related fiq member ca 635 ma and ends just below the precambrian cambrian boundary 542 ma tectonic subsidence caused by thermal contraction following fiq aged rifting allowed the preservation of about 1 km of postrift stratigraphy with no major stratigraphic breaks the nafun group above the marinoan cap carbonate hadash formation represents two siliciclastic to carbonate grand cycles both initiated by significant transgressions these cycles comprise the masirah bay khufai formations and the shuram buah formations the khufai shuram boundary is associated with the start of a major carbon isotope perturbation the uppermost ramp carbonates of the khufai formation record a smooth decrease in 13c from about 4 to values around 0 followed by two descending steps across which values plunge to a nadir of 12 in the overlying red siltstones and shales interbedded with thin limestones of the shuram formation this fall in isotopic values is temporally rapid and coincident in both shallow and deep water sections in the time span of a single parasequence the 13c nadir is then followed by 50 million years of monotonic recovery the shuram shift represents the largest 13c inorganic carbon negative excursion in earth history although the snowball earth theory links periods of depleted carbon isotopic ratios with periods of global glaciation the non glaciated context of the shuram formation suggests that the causal relationship between global glaciation and negative carbon isotopic excursions is non unique although the precise mechanism driving this major perturbation of the carbon cycle remains enigmatic the long term remineralization of an isotopically depleted organic carbon reservoir in ocean water is a promising candidate

a paired apatite and calcite clumped isotope thermometry approach to estimating cambro ordovician seawater temperatures and isotopic composition the secular increase in 18 o values of both calcitic and phosphatic marine fossils through early phanerozoic time suggests either that 1 early paleozoic surface temperatures were high in excess of 40 c tropical mat 2 the 18 o value of seawater has increased by 7 8 vsmow through paleozoic time or 3 diagenesis has altered secular trends in early paleozoic samples carbonate clumped isotope analysis in combination with petrographic and elemental analysis can deconvolve fluid composition from temperature effects and therefore determine which of these hypotheses best explain the secular 18 o increase clumped isotope measurements of a suite of calcitic and phosphatic marine fossils from late cambrian to middle late ordovician aged strata the first paired fossil study of its kind document tropical sea surface temperatures near modern temperatures 26 38 c and seawater oxygen isotope ratios similar to today s ratios

depositional environment and reservoir quality of miocene sediments in the central part of the nam con son basin southern vietnam shelf abstract the nam con son basin is a rift basin that formed offshore southern vietnam at the time of opening of the east vietnam sea south china sea the cenozoic stratigraphy in the basin is subdivided into four megasequences based on the main tectonic stages of basin evolution syn rift 1 inter rift syn rift 2 and post rift this study investigates the depositional environment and reservoir quality of the miocene sediments in the central part of the basin and thus discusses the later part of the inter rift the second syn rift and the post rift megasequences we focus on seismic interpretation sediment core analysis biostratigraphy and well log analysis the lower miocene depositional succession is dominated by stacked coarsening upward progradational packages possibly related to the interplay between high sediment supply and fluctuating sea levels the depositional environment is fluvio deltaic to paralic the middle miocene depositional succession is characterized by an upward deepening trend which seems related to northeast southwest rift propagation during this time several intra rift packages demonstrate increasing rift forming activities that resulted in deposition of footwall derived turbidite deposits in the central grabens half grabens and non deposition erosion on structural highs shallow marine facies dominated in the west while the deep marine settings occurred in most of the eastern part of study area carbonate platforms were initiated and widely developed on the structural highs in the southeast and north as a result of overall marine transgression and backstepping of the clastic shoreline toward the west the upper bounding surface of this succession is a regional unconformity marking the boundary between the syn rift 2 and the post rift megasequences during the late miocene deep marine facies extended across the entire study area with extensive submarine fan deposits and submarine channels downcutting w e and s ne which extended across the shelf and slope the miocene sandstones comprise mostly fine to very fine grained feldspathic litharenite to lithic arkose deep marine turbidite sandstones of the upper miocene succession exhibit the best reservoir qualities both porosity and permeability of all the sedimentary facies examined paralic sandstones of the lower miocene succession and footwall derived turbidite sandstones of the middle miocene succession have similar reservoir qualities relatively good reservoir quality sandstones of the middle and upper miocene successions were deposited as thick massive turbidites however parallel laminated turbidites and slumps debris flows often show poor to moderate reservoir qualities precipitation of carbonate cement during burial diagenesis has destroyed the reservoir quality of the miocene sandstones

stratigraphy and environmental conditions of the terminal neoproterozoic cambrian period in oman evidence from sulphur isotopes terminal neoproterozoic and cambrian evaporite rocks worldwide record a marked sulphur isotope excursion to very heavy 34 s isotopes that reflect a period of significant burial of reduced sulphur new 34 s data from anhydrite and pyrite of the ara group in oman extend this record to arabia depositional history of the ara group spans c 8 ma across the terminal neoproterozoic cambrian boundary therefore these rocks provide a detailed record of sulphur isotopic evolution in this important time interval ara group sulphur isotope values include a mean 34 s anhydrite of 39 4 2 6 1 range 32 4 46 4 n 61 and a mean 34 s pyrite of 1 4 7 3 1 range 10 8 to 11 4 n 12 the isotope signatures were not altered significantly during diagenesis and are representative of the isotopic composition of parent waters in the basin marine bromine concentrations in halite and marine fossils in associated carbonate rocks indicate that these waters had a marine origin bacterial sulphate reduction was the dominant process leading to the segregation between isotopically heavy sulphur incorporated in evaporite rocks and isotopically light sulphur buried in pyrite and organic matter strong sulphate reduction operated in a hypersaline and partly anoxic basin these environmental conditions were also conducive to the preservation of organic material and make the ara group a prolific hydrocarbon province significant variation of the observed values is attributed to the inherent variability of bacterial sulphate reduction including partially closed system behaviour disproportionation processes limited diagenesis and possibly secular variation of sulphur isotopes within the basin ara group 34 s anhydrite values overlap with data from other terminal neoproterozoic to cambrian basins but the mean 34 s anhydrite is highest in oman this observation cannot be attributed solely to the specific anoxic conditions and strong bacterial sulphate reduction in oman because such conditions were widespread in most evaporite basins of the terminal neoproterozoic cambrian periods instead slight age differences between these basins can introduce a bias in the sulphur isotope curve excellent preservation of ara group deposits and in particular the precise age constraints make the ara group representative for the seawater sulphur isotopic composition at the terminal neoproterozoic cambrian boundary as a result of the inherent variability of bacterial sulphate reduction 34 s values at the lower end of the spectrum should be most representative for the global signal based on results of this study the global signal is estimated to be approximately 35 40

cenozoic deep sea temperatures and global ice volumes from mg ca in benthic foraminiferal calcite a deep sea temperature record for the past 50 million years has been produced from the magnesium calcium ratio mg ca in benthic foraminiferal calcite the record is strikingly similar in form to the corresponding benthic oxygen isotope 18o record and defines an overall cooling of about 12 c in the deep oceans with four main cooling periods used in conjunction with the benthic 18o record the magnesium temperature record indicates that the first major accumulation of antarctic ice occurred rapidly in the earliest oligocene 34 million years ago and was not accompanied by a decrease in deep sea temperatures

depositional and diagenetic controls on the reservoir quality of lower cretaceous pendencia sandstones potiguar rift basin brazil the quality of the reservoirs of the lower cretaceous pendencia formation of the potiguar basin northeastern brazil is directly controlled by depositional facies related carbonate cementation and compaction the study of the interplay of these processes in the reservoirs offers an opportunity to unravel the diagenetic patterns of clastic sequences in interior rifts and in particular the role of carbonate cementation in poorly understood continental systems the pendencia formation is a thick sequence of fan deltaic fluvial deltaic turbiditic and lacustrine sandstones conglomerates and shales deposited during the rift stage of the basin the sandstones are predominantly arkoses average q49f40l11 with subordinate plutonic and volcaniclastic feldspathic litharenites compaction and cementation had similar importance in the destruction of porosity with a dominance of cementation in the turbidites and of compaction in the fluvial deposits carbonate cementation in pendencia reservoirs increases progressively with depth and is facies controlled eodiagenetic nonferroan calcite i d18opdb 10 7 to 4 0 d13cpdb 17 5 to 8 5 mesodiagenetic rhombohedral ferroan dolomite ankerite d18opdb 9 3 to 3 9 d13cpdb 1 7 to 1 1 and ferroan calcite ii d18opdb 17 2 to 6 8 d13cpdb 13 6 to 2 3 were precipitated at three distinct temperature intervals calculated from the d18o values 21 to 58 c 70 to 79 c and 85 to 150 c respectively according to the d13c values dissolved carbonate for calcite i was derived from oxidation and methanogenic fermentation of organic matter and from methane oxidation ferroan mesogenetic cements were derived from thermal decarboxylation of organic matter the shales were a major source of dissolved begin page 1720 carbonate as indicated by the isotopic similarity between their calcite d13cpdb 0 2 to 1 8 87sr 86sr 0 719 and most cements in the sandstones and by the peripheral cementation along the contacts of interbedded sandstones as a result of this cementation pattern thin turbiditic and deltaic sandstone beds are pervasively cemented the best reservoir quality potential is encountered in the partially cemented fluvial sandstones at moderate depths deltaic and turbiditic sandstones are more pervasively cemented by carbonate derived from the interbedded shales alluvial fan conglomerates and sandstones were flushed by telogenetic meteoric waters close to the borders of the basin and to the proximity to the postrift unconformity however porosity enhancement was very limited due to the precipitation of kaolinite and the intense compaction related to the compositionally immature detrital framework

rock buffered recrystallization of marion plateau dolomites at low temperature evidenced by clumped isotope thermometry and x ray diffraction analysis abstract much debate exists on the extent to which early dolomites recrystallize and preserve the signature of their primary diagenetic setting here we combine clumped isotopes thermometry with x ray diffraction and thin section petrography to study dolomite recrystallization under shallow burial

present day stress and pore pressure fields in the cuu long and nam con son basins offshore vietnam abstract knowledge of the in situ or contemporary stress field is vital for planning optimum orientations of deviated and horizontal wells reservoir characterization and a better understanding of geodynamic processes and their effects on basin evolution this study provides the first documented analysis of in situ stress and pore pressure fields in the sedimentary formations of the cuu long and nam con son basins offshore vietnam based on data from petroleum exploration and production wells in the cuu long basin the maximum horizontal stress is mainly oriented in nnw sse to n s in the northern part and central high in the nam con son basin the maximum horizontal stress is mainly oriented in ne sw in the northern part and to n s in the central part of the basin the magnitude of the vertical stress has a gradient of approximately 22 2 mpa km at 3500 m depth minimum horizontal stress magnitude is approximately 61 of the vertical stress magnitude in normally pressured sequences the effect of pore pressure change on horizontal stress magnitudes was estimated from pore pressure and fracture tests data in depleted zone caused by fluid production and an average pore pressure stress coupling ratio s h p p obtained was 0 66 the minimum horizontal stress magnitude approaches the vertical stress magnitude in overpressured zones of the nam con son basin suggesting that an isotropic or strike slip faulting stress regime may exist in the deeper overpressured sequences