nucleation crystal growth and the thermal regime of cooling magmas crystallization at the margin of a quiet cooling magma has been studied numerically taking into account the kinetics of crystallization the variables are the latent heat value the growth and nucleation functions the initial magma temperature and the thermal contrast between magma and country rock we have investigated a wide range of values for these parameters corresponding to natural conditions we show that after a highly transient stage crystallization tends toward an equilibrium between heat production latent heat release and heat loss given the small diffusivity of country rocks latent heat release is the main factor controlling the temperature evolution in order to minimize the latent heat release crystallization occurs at a temperature where nucleation is small this can be close to either the liquidus or the solidus depending on the initial conditions the main process controlling crystallization is nucleation and not crystal growth nucleation occurs as a series of sharp pulses followed by longer periods of crystal growth the nucleation pulses give birth to thermal oscillations these oscillations can be sustained if the interior magma temperature is above the liquidus independently of the heat loss mechanism we show that the phenomenon occurs on the scale of a few centimeters which corresponds to the inch scale layering of many ultrabasic complexes the model allows us to calculate crystal sizes which are in good agreement with geological observations the crucial parameters which determine crystal size variations near the margins of igneous bodies are the initial thermal conditions as well as the nucleation and growth functions in the main cooling regime close to the liquidus significant size variations can be created by small thermal disturbances

stable organic carbon isotope stratigraphy across oceanic anoxic event 2 of demerara rise western tropical atlantic ocean drilling program odp leg 207 recovered expanded sections of organic carbon rich laminated shales on demerara rise western tropical atlantic high resolution organic carbon isotope and total organic carbon toc records are presented which span the cenomanian turonian boundary interval ctbi including the oceanic anoxic event oae 2 from four sites oriented along a nw striking depth transect these records represent the first high resolution carbon isotope records across oae 2 from the south american margin of the tropical atlantic due to the scarcity of age significant fossils the main purpose of this study was to develop a detailed carbon isotope stratigraphy in order to correlate the ctbi across the depth transect and to tie this to biostratigraphically well defined sections in the western interior basin pueblo usa boreal shelf seas eastbourne england and western tethys oued mellegue tunisia all four sections studied document a 6 increase of 13corg values at the base of the ctbi which is followed by an interval of elevated 13corg values and a subsequent decrease our results supply an important stratigraphic base for subsequent paleoceanographic studies on late cenomanian to early turonian sediments from demerara rise and elsewhere

impressions of algal mats from the middle proterozoic belt supergroup northwestern montana u s a irregular low relief bedding plane markings which probably represent impressions of thin wrinkled algal mats have recently been detected in mudstones from the 1100 m y old snowslip formation belt supergroup glacier national park montana algal mat impressions are rarely reported from ancient strata yet algal mats are common in certain modern environments originating primarily in moist settings and in relatively quiescent shallow water settings such structures may be of some value in interpreting ancient depositional environments

the cooling kinetics of plagioclase feldspar as revealed by electron microprobe mapping in this study we have used electron microprobe mapping to investigate plagioclase compositional evolution due to cooling kinetics we re analyzed five run products from a prior study iezzi et al 2011 crystallized by cooling a natural andesitic melt from 1300 to 800 c at 25 12 5 3 0 5 and 0 125 c min under atmospheric pressure and air redox state as the cooling rate decreases the texture of large plagioclases changes from skeletal to hollow to nearly equant in this study we use x ray map data to obtain a database of 12 275 quantitative chemical analyses the frequency of an rich plagioclases showing disequilibrium compositions substantially increases with increasing cooling rate at 25 and 12 5 c min the distribution is single mode and narrow at 0 5 and 0 125 c min is single mode but very broad whereas at the intermediate cooling rate of 3 c min two distinct plagioclase populations are present this intermediate cooling rate is fast enough to cause departure from equilibrium for the crystallization of the an rich population but also sufficiently slow that an poor plagioclases nucleate from the residual melt we interpret our findings in the context of time temperature transformation ttt diagrams and infer the crystallization kinetics of plagioclase in the experiments compositional trends and our inferences regarding ttt systematics are consistent with two discrete nucleation events that produced separate populations of plagioclase i e an rich and an poor populations at 3 c min using plagioclase melt pairs as input data for the thermometric reaction between an and ab components we find that plagioclase mirrors very high near liquidus crystallization temperatures with increasing cooling rate these results have important implications for the estimate of post eruptive solidification conditions lava flows and intrusive bodies from centimeters to a few meters thick are characterized by a short solidification time and a significant thermal diffusion under such circumstances it is possible to crystallize plagioclases with variable and disequilibrium chemical compositions simply by cooling a homogeneous andesitic melt x ray element maps enrich the study of plagioclase compositional variations generated under conditions of rapid cooling

crystallization of interstitial liquid and latent heat buffering in solidifying gabbros skaergaard intrusion greenland new compositional profiles across plagioclase grains from the layered series ls marginal border series mbs and upper border series ubs of the skaergaard intrusion are used to understand the mechanisms of cumulate rock solidification and the fate of the interstitial liquid the data show that plagioclase crystals display three types of compositional profile over the whole intrusion as follows 1 grains with normal zoning which dominate the mbs and ubs these are interpreted as having formed at the top of a crystal mush and then buried in the cumulate pile crystallization of the interstitial melt resulted in liquid differentiation and produced normally zoned rims on plagioclase cores 2 unzoned crystals which dominate the upper part of the ls also crystallized at the top of the mush and were then buried in mush with a low interstitial liquid fraction or one experiencing convective movements that kept the liquid to a constant composition 3 crystals with a mantle of decreasing an content followed by a rim of constant composition grains showing this complex zoning mostly occur in the lower parts of the ls depending on the stratigraphic position within the intrusion the composition of the rim can be an56 an51 or an40 in the main magma body these compositions an contents correspond to those of plagioclase primocrysts e g cores at the appearance of cumulus clinopyroxene an56 fe ti oxides an51 and apatite an40 compositional buffering of plagioclase rims is interpreted as being a consequence of enhanced release of latent heat of crystallization at the appearance of new interstitial phases in the crystal mush when a new phase saturates the latent heat contribution to the global enthalpy budget of the system becomes sufficiently high to keep the interstitial melt at its liquidus temperature for a period of time that could exceed thousands of years under these conditions equilibrium adcumulus growth together with diffusion and possibly advection of chemical components result in the formation of plagioclase rims of constant composition an content efficient thermal buffering of the mush liquid depends on the porosity i e fraction of liquid within the mush and the degree of compositional homogeneity of the mush in a heterogeneous and highly porous mush saturation of the new phase occurs in the coldest part of the mush and the enhanced latent heat release at the saturation of this phase is quickly dissipated to the whole volume of liquid including the warmest part that is not yet saturated in a new phase as a consequence no thermal buffering occurs and interstitial crystallization produces grains with normal zoning the distribution of the various types of plagioclase grains throughout the skaergaard intrusion can therefore be used to infer the spatial variability in the physical properties of the crystal mush such as the residual porosity both at an intrusion wide scale and at a millimetre to centimetre scale

carbon sequestration activated by a volcanic co 2 pulse during ocean anoxic event 2 ninety four million years ago during ocean anoxic event 2 there was a marked increase in the burial of organic carbon in marine sediments measurements of stomata in fossil leaves show that the two main pulses of carbon burial were associated with a decline in atmospheric co2 levels of up to 26 the cretaceous ocean anoxic event 2 about 94 million years ago is thought to be linked to extensive volcanism which triggered a biogeochemical chain of events that eventually led to widespread marine anoxia and a remarkable increase in carbon burial in marine sediments1 2 3 it has been suggested that the event was accompanied by a substantial decrease in atmospheric co2 concentrations4 but the quantification of the drawdown remains controversial5 6 here we reconstruct atmospheric co2 concentrations throughout the ocean anoxic event from counts of the stomata in fossil leaves and use terrestrial carbon isotopes to link the reconstruction to marine records of the event7 8 we find that before the onset of ocean anoxia atmospheric co2 concentrations increased by 20 over background levels of 370 100 70 ppm this was part of a long term rise in atmospheric co2 levels presumably caused by volcanism which reached a peak of 500 400 180 ppm however two pulses of extensive carbon burial during the ocean anoxic event as indicated by positive carbon isotope excursions are associated with decreased atmospheric co2 concentrations we conclude that the sequestration of marine organic carbon led to a decrease in atmospheric co2 concentration of up to 26 during ocean anoxic event 2

nd isotopic excursion across cretaceous ocean anoxic event 2 cenomanian turonian in the tropical north atlantic late cretaceous fish debris from demerara rise exhibits a dramatic positive excursion of 8 nd units during ocean anoxic event 2 oae2 that is superimposed on extremely low nd t values 14 to 16 5 observed throughout the rest of the studied interval the oae2 nd excursion is the largest yet documented in marine sediments and the majority of the shift is estimated to have occurred over nd values on demerara rise are explained as the nd isotopic signature of the south american craton whereas eruptions of the caribbean large igneous province or enhanced mixing of intermediate waters in the north atlantic could have caused the excursion

geochemical and isotopic zoning patterns of plagioclase megacrysts in gabbroic dykes from the gardar province south greenland implications for crystallisation processes in anorthositic magmas chemical and sr isotopic zoning patterns in plagioclase megacrysts from gabbroic dykes in the gardar province can be used to elucidate magma chamber and emplacement processes the megacrysts occur either as single crystals or assembled as anorthosite xenoliths the size of the megacrysts varies from 1 cm to 1 m they consist of a large core with variable zonation an58 39 and a relatively small 600 m normally zoned rim an62 27 the contact between core and rim is sharp and marked by a sharp increase in anorthite content which can reach 11 mol an this gap is interpreted as having formed during dyke emplacement due to a sudden pressure release some of the megacryst cores show a fairly constant composition whereas others exhibit an unusual wavy oscillatory zoning which has not been reported elsewhere to our knowledge the oscillatory zoning has wavelengths of up to 2 500 m and a maximum amplitude of 7 mol an it is interpreted as reflecting movements of the crystals in the magma reservoir the sr isotopic composition of one crystal shows a radiogenic inner core 87sr 86sr i 0 7044 and a less radiogenic outer core 87sr 86sr i 0 7039 0 7036 the lack of a significant change between outer core and rim 87sr 86sr i 0 7037 is consistent with formation of the more an rich rim due to pressure release variations in the core may be related to movements of the crystal and or magma mixing a trace element profile across a megacryst shows a small increase in sr and small decreases in ba and la contents of the recalculated melt composition across the core rim boundary whereas p ce nd and eu remain constant melt compositional changes upon emplacement are therefore considered to be of minor importance constant ratios of incompatible trace elements in the megacryst cores indicate a dominant influence of a lower crustal source on trace element budgets

sedimentary mercury enrichments as a marker for submarine large igneous province volcanism evidence from the mid cenomanian event and oceanic anoxic event 2 late cretaceous oceanic anoxic event 2 oae 2 during the cenomanian turonian transition 94 ma was the largest perturbation of the global carbon cycle in the mid cretaceous and can be recognized by a positive carbon isotope excursion in sedimentary strata although oae 2 has been linked to large scale volcanism several large igneous provinces lips were active at this time e g caribbean high arctic madagascan ontong java and little clear evidence links oae 2 to a specific lip the mid cenomanian event mce 96 ma identified by a small 1 positive carbon isotope excursion is often referred to as a prelude to oae 2 however no underlying cause has yet been demonstrated and its relationship to oae 2 is poorly constrained here we report sedimentary mercury hg concentration data from four sites three from the southern margin of the western interior seaway and one from demerara rise in the equatorial proto north atlantic ocean we find that in both areas increases in mercury concentrations and hg toc ratios coincide with the mce and the oae 2 however the increases found in these sites are of a lower magnitude than those found in records of many other mesozoic events possibly characteristic of a marine rather than atmospheric dispersal of mercury for both events combined the new mercury data presented here are consistent with an initial magmatic pulse at the time of the mce with a second greater pulse at the onset of oae 2 possibly related to the emplacement of lips in the pacific ocean and or the high arctic

microchemical and sr isotopic investigation of zoned k feldspar megacrysts insights into the petrogenesis of a granitic system and disequilibrium crystal growth k feldspar megacrysts kfm are used to investigate the magmatic evolution of the 7ma monte capanne mc monzogranite elba italy dissolution and regrowth of kfm during magma mixing or mingling events produce indented resorption surfaces associated with high ba contents diffusion calculations demonstrate that kfm chemical zoning is primary core to rim variations in ba rb sr li and p support magma mixing i e high ba and p and low rb sr at rims but more complex variations require other mechanisms in particular we show that disequilibrium growth related to variations in diffusion rates in the melt may have occurred as a result of thermal disturbance following influx of mafic magma in the magma chamber initial 87 sr 86 sr ratios isr obtained by microdrilling decrease from core to rim inner core analyses define a mixing trend extending towards a high isr rb sr melt component whereas the outer cores and rims display a more restricted range of isr but a larger range of rb sr lower isr at the rim of one megacryst suggests mixing with high k calc alkaline mantle derived volcanics of similar age on capraia trace element and isotopic profiles suggest 1 early megacryst growth in magmas contaminated by crust and refreshed by high isr silicic melts as seen in the inner cores and 2 later recharge with mafic magmas as seen in the outer cores followed by 3 crystal fractionation with possible interaction with hydrothermal fluids as seen in the rim the model is compatible with the field occurrence of mafic enclaves and xenoliths

mercury deposition through the permo triassic biotic crisis abstract a 6 7 million year record of marine sedimentation through the permo triassic biotic crisis shows notable shifts in mercury concentrations that varied over an order of magnitude 0 002 to 0 116 g g mercury concentrations correlate strongly with total organic carbon showing both parallel increasing and decreasing trends over geologic time scales results suggest that changes in bioproductivity strongly influence mercury sequestration into marine sediment this may provide insight to potential marine response to modern anthropogenic hg loading and supports models that suggest enhanced bioproductivity that due to recent climate has increased hg sequestration over time

on the interaction between convection and crystallization in cooling magma chambers abstract we investigate the interaction of thermal convection and crystallization in large aspect ratio magma chambers because nucleation requires a finite amount of undercooling crystallization is not instantaneous for typical values of the rates of nucleation and crystal growth the characteristic time scale of crystallization is about 10 3 10 4 s roof convection is characterized by the quasi periodic formation and instability of a cold boundary layer its characteristic time scale depends on viscosity and ranges from about 10 2 s for basaltic magmas to about 10 7 s for granitic magmas hence depending on magma viscosity convective instability occurs at different stages of crystallization a single non dimensional number is defined to characterize the different modes of interaction between convection and crystallization using realistic functions for the rates of nucleation and crystal growth we integrate numerically the heat equation until the onset of convective instability we determine both temperature and crystal content in the thermal boundary layer crystallization leads to a dramatic increase of viscosity which acts to stabilize part of the boundary layer against instability we compute the effective temperature contrast driving thermal convection and show that it varies as a function of magma viscosity and hence composition in magmas with viscosities higher than 10 5 poise the temperature contrast driving convection is very small hence thermal convection is weak in low viscosity magmas convective breakdown occurs before the completion of crystallization and involves partially crystallized magma the convective regime is thus characterized by descending crystal bearing plumes and bottom crystallization proceeds both by in situ nucleation and deposition from the plumes we suggest that this is the origin of intermittent layering a form of rhythmic layering described in the skaergaard and other complexes we show that this regime occurs in basic magmas only at temperatures close to the liquidus and never occurs in viscous magmas this may explain why intermittent layering is observed only in a few specific cases

observations of plagioclase zoning using interference imaging abstract interference imaging techniques laser interference microscopy in transmitted light and nomarski differential interference contrast in reflected light have been used to study different types of zoning in magmatic plagioclase crystals samples studied come from a wide range of rock types and geological environments analysis of zoning profiles for individual unit zones shows that a saw tooth pattern in which an initially high an decreases as growth proceeds is the most common type of zoning configuration we recognize 2 major types of zoning type 1 small zones usually less than 10 microns thick with compositional amplitudes up to 10 an and type 2 zones up to50 microns thick with large compositional amplitudes of up to 35 an detailed analysis of zoning patterns shows that oscillatory zoning is not actually oscillatory in the sense of a sine wave it is discontinuous unit zones are characteristically bounded by discontinuities this common pattern is consistent with alternating periods of growth and periods of dissolution reaction and lack of growth or possibly very slow growth our observations firmly establish that dissolution and magmatic reaction involving both growth and dissolution are common during growth of the magmatic plagioclase which we have studied type 1 zonation appears consistent with perturbations of local conditions in a diffusion controlled boundary layer around the growing crystal type 2 zoning is probably due to large scale conditions faceted planar growth surfaces appear to be the rule in magmatic crystallization although in some instances rounded or irregular convolute zonation can occur the repetitive nature of many of the features we have observed is consistent with and suggestive of some form of self organization

an investigation of disequilibrium growth processes of plagioclase in the system anorthite albite water by methods of numerical simulation compositional zoning of plagioclase is useful as a recorder of dynamic geological conditions if the mechanisms of crystal growth are known although the present lack of quantitative information on specific kinetic processes limits their accuracy numerical simulations of phenoycryst plagioclase growth are useful both for identifying the most influential kinetic processes for example diffusion that should receive priority in experimental measurements and for designing informative growth experiments the interaction of kinetic processes at a crystal face is so complex that the overall result cannot be assessed intuitively a primary purpose of these papers is to explore this interaction in the plagioclase system as quantitatively as data permit

the osmium isotopic composition change of cenozoic sea water as inferred from a deep sea core corrected for meteoritic contributions a detailed study was made of the oceanic 187os 186os variation through the cenozoic by using a hydrogen peroxide leaching procedure on a pelagic clay core from the north pacific long lines 44 gpc3 a 6 h2o2 solution was used the range of 187os 186os obtained by this procedure was between 2 and 8 2 a milder leach 0 15 h2o2 in three out of four samples yielded a slightly higher 187os 186os value than the stronger leach implying that the stronger leach released some meteoritic os with 187os 186os of 1 using published 3he concentrations in gpc3 and cosmic dust 3he and os fluxes to deep sea sediments the extraterrestrial os concentration was estimated for each core segment and subtracted to yield corrected values of 187os 186os the results based on the milder leaching protocol and the 3he correction protocol yield similar values the corrected ocean water 187os 186os pattern for the past 25 million years is similar to that obtained by other workers and is compatible with other results for the entire cenozoic the variation with time in gpc3 uniquely provides a statigraphic signature for the paleogene

unusual magma storage conditions at mt etna southern italy as evidenced by plagioclase megacryst bearing lavas implications for the plumbing system geometry and summit caldera collapse at mt etna volcano the emission of plagioclase megacryst bearing lavas known locally as cicirara has occurred rarely and generally in association with unusual volcanological phenomena in this work we interpret the magma chamber processes and the structural features of the plumbing system that led to the production of these peculiar volcanic rocks based on a detailed study of plagioclase megacrysts including their oscillatory zoning sieve textures and fluid inclusions patchy zoning suggests limited ascent in the deep levels of the plumbing system based on the plagioclase nucleation threshold and the volatile saturation depth at intermediate water undersaturated levels of the plumbing system ascent is faster as indicated by crystals with coarse sieve textures storage at shallow water saturated levels less than 6 km deep is associated with oscillatory zoning with very small changes in an slightly larger an variations coupled with different wavelengths provide evidence of convection of crystals across distinct zones of the chamber stripes of melt inclusions formed at steps of magma ascent and volatile loss whereas layers of fluid inclusions may be related to episodes of volatile flushing into the magma chamber in contrast strongly sieve textured envelopes with an increase and constant feo may be related to mixing with more volatile rich magmas of similar composition we interpret the repeated occurrence of cicirara lavas as evidence that the shallow portion of the plumbing system underwent a progressive coalescence of a complex network of dykes and sills in response to increasing rates of magma supply from depth major magma withdrawals from this larger reservoir may be linked to episodes of summit instability associated with major caldera collapses

cretaceous oceanic anoxic event 2 triggered by a massive magmatic episode oceanic anoxic events oaes were episodes of widespread marine anoxia during which large amounts of organic carbon were buried on the ocean floor under oxygen deficient bottom waters oae2 occurring at the cenomanian turonian boundary about 93 5 myr ago is the most widespread and best defined oae of the mid cretaceous although the enhanced burial of organic matter can be explained either through increased primary productivity or enhanced preservation scenarios the actual trigger mechanism corresponding closely to the onset of these episodes of increased carbon sequestration has not been clearly identified it has been postulated that large scale magmatic activity initially triggered oae2 refs 4 5 but a direct proxy of magmatism preserved in the sedimentary record coinciding closely with the onset of oae2 has not yet been found here we report seawater osmium isotope ratios in organic rich sediments from two distant sites we find that at both study sites the marine osmium isotope record changes abruptly just at or before the onset of oae2 using a simple two component mixing equation we calculate that over 97 per cent of the total osmium content in contemporaneous seawater at both sites is magmatic in origin a approximately 30 50 fold increase relative to pre oae conditions furthermore the magmatic osmium isotope signal appears slightly before the oae2 as indicated by carbon isotope ratios suggesting a time lag of up to approximately 23 kyr between magmatism and the onset of significant organic carbon burial which may reflect the reaction time of the global ocean system our marine osmium isotope data are indicative of a widespread magmatic pulse at the onset of oae2 which may have triggered the subsequent deposition of large amounts of organic matter

the early cretaceous barents sea sill complex distribution 40ar 39ar geochronology and implications for carbon gas formation abstract mafic igneous rocks of cretaceous age 80 130 ma scattered around the arctic ocean are commonly referred to as the high arctic large igneous province halip we have mapped out the distribution of halip igneous rocks in the barents sea region over the past decade based on integrated seismic gravity magnetic interpretation field work review of publications and analyses of new and vintage borehole and field samples the mapping reveals abundant igneous rocks in the northern and eastern barents sea covering an area of 900 000 km2 with a conservative volume estimate of 100 000 to 200 000 km3 of intrusions the igneous province is dominated by sheet intrusions injected into triassic and permian sedimentary rocks hydrothermal vent complexes are rare and only two potential vent complexes have been identified on seismic data in the eastern barents sea we have further done extensive radiometric dating of the igneous samples in the barents sea region new 40ar 39ar dating of thirteen samples from svalbard reveal ages of crystallization and alteration the large age span 60 140 ma for the raw ages is likely due to partial or complete overprint of the k ar system in plagioclase and the age of the magma emplacement is better represented by u pb tims ages only one of our 40ar 39ar analyses of plagioclase yielded a statistically valid age that is in line with the recently published u pb tims ages of 122 125 ma the new data clearly document that relying on published data from the k ar system can lead to erroneous conclusions on the age of crystallization in this province without a careful use of additional 40ar 39ar degassing data i e k ca we propose that the magmatism on svalbard and franz josef land represents a distinct magmatic event near the barremian aptian boundary 125 ma in the barents sea this early cretaceous barents sea magmatism resulted in the formation of the bssc barents sea sill complex bssc age rocks are also present in arctic canada sverdrup basin and on bennett island new siberia islands the massive injection of hot magma into potentially organic rich sediments in the eastern and northern barents basin caused rapid organic matter maturation and formation of thermogenic gas and oil in contact aureoles we estimate that up to 20 000 gt of carbon were potentially mobilized corresponding to 175 trillion barrels of oil equivalent the production rates and fate of the carbon gases are uncertain however we speculate that rapid release of aureole greenhouse gases methane may have triggered the oceanic anoxic event 1a oae1a and the associated negative 13c excursion in the early aptian some of the methane may also be trapped in the vast hydrocarbon gas accumulations found in the east barents basin

deciphering textural and chemical zoning of k feldspar megacrysts from mt amiata volcano southern tuscany italy insights into the petrogenesis and abnormal crystal growth abstract this study reports the complex textural and chemical features of k feldspar megacrysts up to 5 cm long hosted in trachydacitic lava flows lava domes and coulees from mt amiata volcano tuscan magmatic province central italy backscattering and cathodoluminescence imaging coupled with core to rim major and trace elements patterns reveal complex zoning and resorption surfaces associated with sharp chemical variations e g sr and ba these zoning patterns originated by disequilibrium and re equilibration events related to the repeated influx of mafic magmas or convective motions in the trachydacitic magma reservoir multiple mafic magma refilling occurences are also supported by the field record of abundant microgranular magmatic enclaves in the studied products our results highlight that the abnormal dimension of the studied k feldspars originates by the interplay between petrological and kinetic processes involving i extensive dissolution ii heterogeneous nucleation iii alternation of spasmodic growth events in disequilibrium and near equilibrium crystallization the repeated influx of hotter magmas and reheating can determine the thermal condition to the growth of few large k feldspar megacrysts also the strong textural and chemical similarities observed in the k feldspar megacrysts from mt amiata volcanic rocks and mt capanne monzogranite elba island central italy support the hypothesis of a phenocrystic origin of intrusive k feldspar megacrysts

the trace metal content of recent organic carbon rich sediments implications for cretaceous black shale formation organic carbon rich sediments are enriched in several redox sensitive and stable sulfide forming trace metals tm and form an important sink in global tm cycles in today s ocean such sediments are deposited in coastal upwelling areas like those in the gulf of california off peru or off the namibian coast and euxinic basins like the black sea in an attempt to distinguish both environments by their specific tm patterns some important conclusions may be drawn 1 the tm enrichment seen in both environments broadly is rather similar 2 upwelling sediments are often enriched in cd and p and depleted in co and mn 3 sapropels have a tendency towards higher enrichments in ba and mo s re as cu ni sb and fe reflecting the strong sulfidation in an anoxic water column 4 upwelling systems cover a broad range of environmental settings where the steepness of the slope the proximity of h2s to the sediment seawater interface and the intensity of bio accumulation and regeneration play an important role for tm accumulation 5 the tm content of anoxic basins is mainly controlled by tm availability in the water column and sedimentation rate 6 enhanced bio productivity is the main switch turning an oxygenated into an anoxic environment cretaceous black shales oae 2 exhibit tm signatures of both coastal upwelling areas and sapropels the strong enrichments in cd mo tl v cu ni bi and sb demonstrate that bio accumulation and presence of h2s in the water column and associated sulfidation processes persisted during this time interval in large parts of the proto atlantic the usefulness of ba as a paleoproductivity proxy is obscured by diagenesis the extreme accumulation in ag and zn requires either an additional tm source for instance hydrothermal input or a different tm seawater composition during the cretaceous the geochemical data suggest that the major driving force for the widespread occurrence of c t black shales seems to be the increase in volcanic activity and associated co2 input throughout the cretaceous the ocean atmosphere system operated in a mode different from today during this time interval after conversion of the nutrient co2 into organic matter the system switched back into the normal operational mode

water mass circulation on demerara rise during the late cretaceous based on nd isotopes abstract circulation in the north atlantic during the late cretaceous has implications for poleward heat transport and nutrient distribution during an extreme greenhouse interval with episodes of ocean anoxia nd isotopes of fossil fish teeth and debris represent one of the few water mass tracers that can be used to reconstruct deep ocean circulation we present nd isotopic data interpreted as bottom water values for 290 samples from three ocean drilling program sites on demerara rise sites 1258 1260 and 1261 along with 102 analyses from four other north atlantic sites cape verde goban spur bermuda rise and blake nose that provide additional geographic and bathymetric control our results confirm the presence of a water mass with low end values 14 to 17 that are believed to be influenced by continental material during local water mass formation at low latitudes this demerara bottom water dbw is the primary water mass in the region from the cenomanian to coniacian and from the late campanian through early maastrichtian following a hiatus of 10 my a positive 8 end unit excursion occurs during ocean anoxic event 2 oae2 that cannot be explained by changes in weathering inputs diagenesis or magmatic sources of nd instead it appears to represent an influx of bottom waters sourced from the tethys or north atlantic this replacement of dbw during oae2 argues for decreased production of dbw or enhanced production of tethys north atlantic waters during peak greenhouse conditions from the late campanian through early maastrichtian dbw becomes the only water mass recorded at demerara rise and it appears to expand to abyssal depths at cape verde in the campanian this water mass is ultimately replaced by waters that appear to be sourced from the north atlantic starting in the late maastrichtian observed variations in circulation in the tropical north atlantic during the late cretaceous can account for extensive deposition of black shales in the region prior to the hiatus as well as local warming during a global cooling event in the maastrichtian

minor and trace element zoning in plagioclase implications for magma chamber processes at parinacota volcano northern chile textural and compositional zoning in plagioclase phenocrysts in a sample from parinacota volcano chile was investigated using backscattered electron images and electron microprobe analysis of major and trace elements large 2 mm oscillatory zoned crystals type i with resorption surfaces of moderate an discontinuities 10 an and decreasing trace element contents sr mg ti towards the rim reflect melt differentiation and turbulent convection in the main magma body early recharge with a low sr mafic magma is seen in the core small scale sr variations in the core indicate limited diffusion and thus residence and differentiation times of the magma shorter than a few thousand years smaller crystals type ii with low trace element an ratio reflect the influence of an h2o rich melt probably from a differentiated boundary layer closed system in situ crystallisation mafic magma recharge and the role of a water rich differentiated boundary layer can be distinguished from the an trace element relationships crystals apparently move relatively freely between different parts and regimes in the magma chamber evidence for convective crystal dispersion high sr type ii crystals indicate an earlier input of sr rich mafic magma recharge of two distinct mafic magma types is thus identified high sr and low sr which must have been present at increasing recharge rates with time in the plumbing system throughout the volcano s history

peralkaline volcanicity in the arctic basin the kap washington volcanics petrology and palaeotectonics the kap washington group volcanic rocks occur on the north coast of greenland and were extruded at or just before the cretaceous tertiary boundary the suite is strongly bimodal with basaltic lavas comendites and comenditic ash flow tuffs predominating the basic lavas are of transitional basalt type but have characteristically alkaline minor element contents the riebeckite bearing comendites have strong light ree enrichment and large negative eu anomalies as commonly found in continental peralkaline suites as well as the comendites there are other rhyolite lavas and minor intrusions of distinctly different chemistry which are thought to have originated by crustal refusion the peralkaline nature of the siliceous rocks is in keeping with the extensional tectonic environment suggested by an intense alkali dolerite dyke swarm which immediately preceded the extrusive activity association with the development of the makarov basin in cretaceous times is suggested

foraminiferal and nannofossil paleoecology and paleoceanography of the cenomanian turonian eagle ford shale of southern texas article i nfo the uppercretaceous of central texas isdominated by a broad shallow carbonate platformcalled thecomanche platform that occupies an important gateway between the epeiric western interior seaway wis of north america to the open marine gulf of mexico tethys we investigated the cenomanian turonian eagle ford shale on and adjacent to the comanche platform to determine whether the eagle ford shale has an affinity with the western interior and if so determine where the transition from western interior to open ocean is located we were also interested in the relationship if any between the organic rich facies of the eagle ford and oceanic anoxic event 2 oae2 our work is based on quantitative foraminiferal population counts and associated sedimentary particles including inoceramid prisms sand glauconite and pyrite grains calcareous nannofossil assemblages carbon isotopes and total organic carbon toc from three sites across a range of paleowater depths an outcrop in lozier canyon in terrell county west of langtry tx an outcrop at bouldin creek outside of austin tx and swift energy s fasken a 1h core in webb county tx the highest toc intheeagle ford occurs beforethe onset of oae2 6 at loziercanyon 7 atboth bouldincreek and the fasken core and then declines steadily through the rest of the section except for a small increase at the end of oae2 at lozier and a fairly large post oae2 increase at bouldin creek nannofossil paleoproductivity indicators zeugrhabdotusand biscutum track tocatbouldincreekandinthefaskencoreanddisplaysimilar trends to those observed inthe western interior seawayto the north benthic foraminiferalabundances increase astoc decreasesand the lithology shifts from laminatedblack shale to bioturbatedlight gray shale low oxygen tolerant infaunal neobulimina spp appear first and gradually increase in abundance epifaunal benthics appear soon after this oxygenation trend continues through the oae2 interval and the upper eagle ford contains a diverse epi and infaunal benthic foraminiferal assemblage and macrofossil assemblage this trend of decreasing toc and nannofossil paleoproductivity indicators coupled with increasing benthic foraminiferal abundance and diversity and seafloor oxygenation corresponds to rising sea level based on foraminiferal and nannofossil events toc trends and changes in lithology both platform sites have a strong affinity with the western interior with lozier canyon being the most similar the fasken core bears all the characteristics of an open ocean site except for the fact that peak toc occurs before oae2 this suggests that the oceanographic boundary between wis and tethys can be placed on the edge of the comanche platform productivity was likely driven by bathymetry induced upwelling caused by restriction between the wisand tethys during times of low sea level as sea level rose upwelling diminished and productivity decreased this explains why the fasken core adjacent to the platform margin and in the center of this upwelling zone displays the same toc trends as the platform sites organic carbon content in the seaway was controlled by stratification and enhanced preservation but this was also reduced by rising sea level which is why the two areas show parallel trends

magmatic crystal stratigraphy and constraints on magma chamber dynamics laser interference results on individual phenocrysts this work reports progress in current studies of zoning of magmatic crystals from basalts and andesites a simple law of normal growth is tested using zoning profiles of olivine and plagioclase crystals and is shown to be compatible with the zoning profiles of some olivines and parts of complexly zoned plagioclases using a convenient linearizing technique in which the ratio of compositional end members is plotted against volume we can identify those parts of the zoning profile which fit a simple normal growth law this technique permits easy identification of those parts of a complexly zoned crystal which require a more complex law of growth calculations used in this modeling are similar to those previously used for olivine pearce 1984c 1987 and are now extended to plagioclase it is concluded that it is both theoretically possible and practically feasible to make inferences about the liquid in the local system from which a crystal grew by examining the detailed zoning pattern of the crystal

plagioclase xenocrysts and mafic magmatic enclaves in some granitoids of the sierra nevada batholith california plagioclase phenocrysts from mafic magmatic enclaves and plagioclase crystals from host granitoids of some plutons of the central part of the sierra nevada batholith are complexly zoned and commonly divided into three neatly distinct parts an oscillatory locally patchy zoned andesine or more calcic core a ring with dusty calcic plagioclase and a normally zoned rim of sodic plagioclase although aspect of the calcic rings and width and zoning of the rims may slightly vary from the enclaves to the hosts cores of both phenocrysts and large plagioclase crystals show similar zoning and composition the andesine or more calcic cores are interpreted to have crystallized in the felsic or the mafic magma respectively and been incorporated into the coeval magma when the two magmas mixed introduction of the xenocrystic cores into a magma where they were not in equilibrium resulted in partial dissolution development of abundant patchy zoning and coating with dusty calcic plagioclase in both granitoids and mafic magmatic enclaves composition and zoning contrast between cores and rims of the plagioclase crystals reflect drastic changes in conditions of crystallization before and after the mechanical mixing event mixing of two magmas with contrasted compositions is suggested to be the major mechanism for generating complexly zoned plagioclase xenocrysts in granitoids and mafic magmatic enclaves this hypothesis is consistent with many recent models in which mixing of two contrasting components is proposed to play a fundamental part in the generation of calc alkaline granitoids and mafic magmatic enclaves of the sierra nevada batholith plagioclase xenocrysts may also provide information on the timing of the different mixing processes and on the magmatic evolution of the plutons

petrologic evolution of large failed rifts in the eastern pacific petrology of volcanic and plutonic rocks from the mathematician ridge area and the guadalupe trough

structure and dynamics of the laacher see magma chamber eifel germany from major and trace element zoning in sanidine a cathodoluminescence and electron microprobe study microtextures and zoning patterns in sanidine phenocrysts from the phonolitic laacher see tephra germany were investigated in order to constrain processes occurring in the magma chamber before eruption the laacher see tephra unit is chemically zoned and has been inferred to represent the product of eruption of an inverted layered magma chamber samples from various levels in the deposit were investigated we used a combination of textural studies optical microscopy and back scattered electron bse imaging electron microprobe emp analysis of major minor and trace elements ca na k al si ba sr fe and ti and element mapping the samples studied contain two feldspar phases and the ternary composition of the sanidine thus constrains the temperature of crystallization whereas its trace element content reflects the melt composition the large diversity in textures found in the sanidine crystals can be classified into three types composite c type pseudooscillatory po type and resorbed patchy r type trace elementpoor lamellar composite alkali feldspars c type are found in samples inferred to represent the top and the middle part of the magma chamber they grew as composite crystals from the melt at temperatures as low as 650 c in a highly differentiated and volatilerich boundary layer at the magma chamber roof or wall pseudooscillatory zoning with resorption surfaces po type is found in sanidinesfromsamplesinferredtorepresentthemiddlepartandthebase of the magma chamber repeated large an variations 1 4 mol reflect temperature variations of 100 300 ca ssociated with changes in water content variations of minor and trace elements ba sr and ti in sanidine decoupled from the pseudo oscillations of the major elements reflect chemical changes in the melt and are damped by chemicaldiffusioninthemelt bothmajorandminorelementvariations inpo typecrystalsareinterpretedastheprogressiveinfluenceofamore mafic hotter melt this may be partly explained by the settling of crystals through the thermal and chemical gradient existing in the magma chamber however the additional role of magma recharge may be required to explain the large temperature variations resorbed patchy zoned crystals r type found mainly in samples corresponding to the middle part of the magma chamber reflect early growth in a differentiated boundary layer followed by resorption and overgrowthinthemainmagmabody manyofthelaacherseesanidine crystals did not crystallize for the most part in the melt in which they were erupted in the presence of preserved major and trace element zonation in the magma this observation indicates crystal dispersion within a layered magma chamber without large scale mixing and overturn

application of cathodoluminescence to magmatic quartz in a tin granite case study from the schellerhau granite complex eastern erzgebirge germany a model of the cooling history of tin bearing granitic magma forming the schellerhau granites eastern erzgebirge germany is shown on the basis of quartz textures similar grain size similar grain habit and correlatable growth textures of phenocrysts in different granite varieties give proof of a common crystallization history before the melts of the schellerhau granite varieties were intruded four nucleation events occurred during crystallization in different crustal levels between about 20 and 1 km depth the parental melt of the schellerhau granites is interpreted to have contained 2 5 wt h2o originally the water content of the melt during the subvolcanic intrusion stage amounted to more than 5 wt and characterizes highly evolved residual melts that enable the formation of tin deposits this study contributes to a better understanding of the development and behaviour of fractionated tin bearing granitic melts and links quartz cathodoluminescence cl with microanalytical studies

nannofossils and superplumes the early aptian nannoconid crisis a group of calcareous nannoplankton named nannoconids experienced a crisis in the early aptian and recovered only later in the late aptian after a period of virtual absence although no extinctions occurred the widespread nature of the nannoconid crisis suggests a global causal factor this crisis is recorded within the chiastozygus litterarius nannofossil and globigerinelloides blowi planktonic foraminiferal zones postdates magnetic chronozone m0 by approximately 300 kyr and precedes the oceanic anoxic subevent 1a and associated 13c anomaly by some 40 100 kyr selective dissolution and anoxia cannot explain the crisis because nannoconids are dissolution resistant forms and their crisis clearly precedes the deposition of anoxic sediments at least 1 m y prior to the nannoconid crisis the onset of a nannoplankton speciation event may be the response of nannofloras to a major rise in relative sea level the nannoconid crisis seems to be synchronous with the early aptian volcanic eruptions in the pacific ocean hence calcareous nannoplankton were severely affected by the superplume volcanic episode the coccolithophorid bloom nannoconid crisis was possibly induced by the excessive co2 levels in the atmosphere and or caused by changes in nutrient content of oceanic surface waters fertility was enhanced by rapid turnover of nutrients due to the abnormal volcanic activity and accelerated transfer of nutrients from the continents into the oceans under warm and humid conditions of the mid cretaceous greenhouse climate the nannoconid crisis may represent a competition between phytoplankton groups for nutrients or more likely competition between different calcareous nannoplankton the biologic affinity and mode of life of nannoconus are unknown because there is no modern analog of this genus however comparison of lower cretaceous nannofossil assemblages with modern nannoplankton cummunities suggests that nannoconids like extant florisphaera profunda possibly inhabited the lower photic zone concentrations of nutrients in the upper euphotic zone may have triggered blooms of coccolithophorids and nannoconid depletion this model implies that the nannoconid crisis is the result of an abrupt major change in the structure of surface waters caused directly or indirectly by the superplume the adjustments of the biosphere to the new paleoceanographic and climatic conditions required some 40 100 kyr before changing into abnormally high primary productivity and deposition of organic carbon rich sediments with dinoflagellates outcompeting nannoplankton

magma ascent and crustal accretion at ultraslow spreading ridges constraints from plagioclase ultraphyric basalts from the arctic mid ocean ridge plagioclase ultraphyric basalts pubs with up to 54 plagioclase phenocrysts were dredged in the rift valley and adjacent flanks of the ultraslow spreading mohns and knipovich ridges the pubs show large variations in crystal morphologies and zoning the large variations suggest that single basalt samples contain a mixture of plagioclase crystals that aggregated at different levels in the magma conduits resorbed crystals and repeated reverse zones suggest that the magma reservoirs were replenished and heated several times thin concentric zones with melt inclusions and sharp reductions in the anorthite content of 3 7 are common between the reverse zones these zones and skeletal crystals with distinctly lower anorthite contents than massive crystals are interpreted to be the result of rapid crystalliztion during strong undercooling the changes between short periods of cooling and longer periods with reheating are explained by multiple advances of crystal rich magma into cool regions followed by longer periods of gradual magma inflow and temperature increase the porphyritic basalts are characterizd by more depleted and more fractionated compositions than the aphyric basalts with lower la sm n k 2 oa nd mg numbers this relationship and the observation that pubs are sampled only close to segment centres along these ridges suggests that the pubs formed by higher degrees of melting and evolved in more long lived magma reservoirs we propose that the zoning patterns of plagioclase crystals and crystal morphologies of these pubs reflect the development and flow of magma through a stacked sill complex like conduit system whereas the aphyric equivalents represent later flow of magma through the conduit the formation of voluminous higher degree melts may trigger the development of the magma conduits and explain the generally depleted compositions of pub magmas

the record of magma chamber processes in plagioclase phenocrysts at thera volcano aegean volcanic arc greece lavas and pyroclastic rocks throughout the volcanic stratigraphy of the tertiary quaternary volcanic complex of thera in the aegean island arc display inhomogenous plagioclase populations and phenocryst resorption textures interpreted as indicative of magma mixing plagioclase zoning characteristics studied by nomarski and laser interferometry techniques establish three main categories of plagioclase i inherited plagioclase nucleated in endmember prior to initial mixing event ii in situ plagioclase nucleated in mixed or hybrid magma and iii xenocrystic plagioclase nomarski contrast images and linearized compositional zoning profiles reveal striking differences between calcic and sodic plagioclases depending on the composition of the lava in which they are hosted these differences reflect the contrasting effects of changes in physical chemical parameters in basic vis a vis more acidic melts during magma mixing and or influx of new magma into the subvolcanic magma chamber as well as the influence of magma chamber dynamics on plagioclase equilibration variations in bulk major and trace element abundances of thera volcanic products reflect the dominant overprint of crystal fractionation but decoupling between major and trace element fractionation models and variations in incompatible trace element distributions are all indicative of magma mixing processes consistent with compositional and textural zoning in plagioclases

the influence of amphibole fractionation on the evolution of calc alkaline andesite and dacite tephra from the central aleutians alaska petrologic studies of tephra from kanaga adak and great sitkin islands indicate that amphibole fractionation and magma mixing are important processes controlling the composition of calc alkaline andesite and dacite magmas in the central aleutians amphibole is ubiquitous in tephra from kanaga and adak islands whereas it is present only in a basaltic andesite pumice from great sitkin dacitic tephra from great sitkin do not contain amphibole hornblende dacite tephra contain hb plag ox opx cpx phenocrysts with simple zoning patterns suggesting that the dacites evolved in isolated magma chambers andesitic tephra from adak contain two pyroxene and hornbelende populations and reversely zoned plagioclase indicating a more complex history involving mixing and fractional crystallization mass balance calculations suggest that the andesitic tephra may represent the complements of amphibole bearing cumulate xenoliths both formed during the evolution of high al basalts the presence of amphibole in andesitic and dacitic tephra implies that aleutian cale alkaline magmas evolve in the mid to lower crust under hydrous 4 wt h2o and oxidizing ni nio conditions amphibole bearing andesites and pyroxene bearing dacites from great sitkin indicates fractionation at several levels within the arc crust despite its absence in many calc alkaline andesite and dacite lavas open system behavior involving amphibole fractionation can explain the trace element characteristies of lavas found on adak island neither open nor closed system fractionation involving a pyroxene bearing assemblage is capable of explaining the trace element concentrations or ratios found in the adak suite we envision a scenario where amphibole was initially a liquidus phase in many calc alkaline magmas but was later replaced by pyroxenes as the magmas rose to shallow levels within the crust the mineral assemblage in these evolved lavas reflects shallow level equilibration of the magma whereas the trace element chemistry provides evidence for a earlier amphibole bearing mineral assemblage

disequilibrium trace element partitioning in jurassic sparry calcite cements implications for crystal growth mechanisms during diagenesis sparry calcite cements from middle jurassic limestones in central england contain complex non concentric zoning patterns produced by a combination of sector zonation and a sector specific lamellar or polygonal zonation electron microprobe analyses of individual zones within crystals document 1 a sympathetic covariation of fe mg and sr between two non equivalent sectors and 2 episodic further increase of sr contents coupled with exclusion of fe mg and mn within the more enriched sectors comparison of results from three different localities demonstrates the regional consistency of this pattern although the magnitude of the differential trace element partitioning varies from combined petrographic and geochemical data the trace element variation in the crystals can be shown to bear no simple relationship with either 1 the chemical evolution of the 9bulk9 precipitating porefluid or 2 the relative overall growth rates of the different crystal faces previous sector zoning models based on crystal surface configurations and internal structure are unable to account directly for the geochemical patterns observed in this study differences between growth mechanisms on the crystal faces of the studied spars are likely to have exerted a significant influence on trace element partitioning in particular they offer a plausible explanation for the geometric and compositional characteristics of the sector specific episodic zoning on the most enriched crystal faces in general crystal morphology and composition will be intimately linked by the growth mechanisms operating on different faces and by their response to changes in the diagenetic environment the validity of diagenetic interpretations from bulk geochemical analysis of sparry calcite cements thus rests upon a detailed analysis of any zonation that they contain

the cenomanian turonian oceanic anoxic event ii palaeoceanographic controls on organic matter production and preservation correlation of the 13c spike with the well dated occurrences of strata rich in organic carbon detailed in schlanger et al this volume indicates that a global episode of intense organic carbon orgc burial took place during the latest cenomanian earliest turonian oceanic anoxic event oae a plenus through i labiatus macrofossil zones and upper r cushmani trz through w archecretacea prz foraminiferal zones over a period of no more than 1 million years m y the shape of the 13c curve indicates that rates of orgc burial gradually increased in the early part of the late cenomanian increased more rapidly in the later cenomanian and levelled off at peak values in latest cenomanian early turonian time during the maximum rate of orgc burial the 13c values decreased nearly to pre late cenomanian levels in the early to middle turonian the decrease in 13c reflects decreasing rates of orgc burial following the cenomanian turonian oceanic anoxic event as well as the probable oxidation and return of significant amounts of orgc to the oceans following regression and re oxygenation of much of the deeper water masses in contact with the seafloor

the cenomanian turonian eagle ford group of south texas insights on timing and paleoceanographic conditions from geochemistry and micropaleontologic analyses abstract the interbedded organic rich marls and limestones of the eagle ford group of south texas were deposited on the shelf of the central texas platform during the upper cenomanian through the turonian micropaleontological analyses of thin sections and residue samples from subsurface cores taken in atascosa and karnes counties yielded 13 biostratigraphic datums which were integrated with calcareous nannofossil datums stable carbon isotopic and bulk inorganic geochemical analysis to gain an understanding of the paleoceanographic conditions of the study area and their relationship to regional and global events the paired thin section residue sampling was necessitated by poor recovery of planktonic foraminifera in washed samples which were however abundant in most thin sections lower eagle ford marls were deposited under euxinic conditions produced by a stratified water column periodic enhanced water column mixing increased oxygen levels and surface water primary productivity which promoted calcite diagenesis and generation of limestones containing calcispheres and radiolaria an oxygenated bottom water mass entered the basin in the uppermost cenomanian prior to the onset of oceanic anoxic event oae 2 causing a spike in benthic foraminiferal diversity and decreasing preservation of organic matter although the lower portion of the upper eagle ford is age equivalent to oae2 as indicated by positive shift in 13corg it contains less organic matter and evidence of more oxygen than the lower eagle ford so deposition of the eagle ford black shales is not contemporaneous to oae2

the end of the cretaceous sharp boundary or gradual transition evidence indicates that the cretaceous tertiary boundary is very sharp and within the limits of resolution it is apparently synchronous at the various boundary localities arguments to the contrary particularly those of officer and darke are shown to invalid

numerical simulations of crystallization processes of plagioclase in complex melts the origin of major and oscillatory zoning in plagioclase numerical simulations of the growth of a large crystal face of plagioclase in response to an instantaneous undercooling below the equilibrium temperature are presented for model granodiorite and basalt melts with varying water contents the simulations suggest that the anorthite content of plagioclase decreases uniformly from the composition in equilibrium with the bulk melt as undercooling is increased and that the water content in the melt has little influence on this result comparison of the simulations with sharp compositional changes in natural profiles suggests that undercoolings of tens of degrees c can be rapidly imposed on plutonic phenocrysts large changes of undercooling most likely result from chilling of the magma and local convection around growing crystals the observation in experiments that growth rate does not increase rapidly with increasing water content in the starting melting composition can be attributed to the concentration of water at the crystal face during growth the action of water to reduce liquidus temperature and undercooling has a greater effect on growth rate than its action to increase transport rates even at large undercooling there is no significant increase in temperature at the interface caused by the release of heat of crystallization

origin of limestone marlstone cycles astronomic forcing of organic rich sedimentary rocks from the cenomanian to early coniacian of the cretaceous western interior seaway usa abstract we present an integrated multidisciplinary study of limestone marlstone couplets from a continuously cored section including parts of the upper buda limestone the entire eagle ford group boquillas formation and lower austin chalk from the shell iona 1 research borehole texas usa which provides a 8 million year myr distal clastic sediment starved intrashelf basin record of the early cenomanian to the earliest coniacian stages results show that despite variable yet minimal diagenetic overprints several unambiguous primary environmental signals are preserved and support greater water mass ventilation and current activity promoting increased silica carbonate productivity during the deposition of limestone beds compared to deposition of marlstone beds which reflect greater organic matter productivity and preservation furthermore our astronomical analyses demonstrate that the limestone marlstone couplets in the iona 1 core reflect climatic forcing driven by solar insolation resulting from integrated milankovitch periodicities in particular we propose that obliquity and precession forcing on the latitudinal distribution of solar insolation may have been responsible for the observed lithological and environmental variations through the cenomanian turonian and coniacian in this mid latitude epicontinental sea setting our data also suggests that rhythmic lithological alternations deposited in greenhouse periods in general may simply reflect climate driven cycles related to earth sun dynamics without the need to invoke significant sea level variations

tropical warming and intermittent cooling during the cenomanian turonian oceanic anoxic event 2 sea surface temperature records from the equatorial atlantic oceanic anoxic event 2 oae 2 occurring during the cenomanian turonian c t transition is evident from a globally recognized positive stable carbon isotopic excursion and is thought to represent one of the most extreme carbon cycle perturbations of the last 100 myr however the impact of this major perturbation on and interaction with global climate remains unclear here we report new high resolution records of sea surface temperature sst based on tex86 and 18o of excellently preserved planktic foraminifera and stable organic carbon isotopes across the c t transition from black shales located offshore suriname french guiana demerara rise ocean drilling program leg 207 site 1260 and offshore senegal cape verde basin deep sea drilling project leg 41 site 367 at site 1260 where both sst proxy records can be determined a good match between conservative sst estimates from tex86 and 18o is observed we find that late cenomanian ssts in the equatorial atlantic ocean 33 c were substantially warmer than today 27 29 c and that the onset of oae 2 coincided with a rapid shift to an even warmer 35 36 c regime within the early stages of the oae a marked 4 c cooling to temperatures lower than pre oae conditions is observed however well before the termination of oae 2 the warm regime was reestablished and persisted into the turonian our findings corroborate the view that the c t transition represents the onset of the interval of peak cretaceous warmth more importantly they are consistent with the hypotheses that mid cretaceous warmth can be attributed to high levels of atmospheric carbon dioxide co2 and that major oaes were capable of triggering global cooling through the negative feedback effect of organic carbon burial led co2 sequestration evidently however the factors that gave rise to the observed shift to a warmer climate regime at the onset of oae 2 were sufficiently powerful that they were only briefly counterbalanced by the high rates of carbon burial attained during even the most extreme interval of organic carbon burial in the last 100 myr

pacific 187 os 188 os isotope chemistry and u pb geochronology synchroneity of global os isotope change across oae 2 studies of oae 2 sections beyond the atlantic ocean western interior seaway wis and european pelagic shelf are limited here we present initial osmium isotope stratigraphy 187os 188os osiosi from two proto pacific sites that span the cenomanian turonian boundary interval ctbi the yezo group yg section hokkaido japan and the great valley sequence gvs california usa to evaluate the 187os 188os seawater chemistry of the proto pacific additionally we combine new 206pb 238u zircon ca id tims geochronology from five volcanic tuff horizons of the yezo group section to test and facilitate inter basinal integration with the wis using radio isotopically constrained age depth models for both sections and quantitatively constrain the absolute timing and duration of events across the ctbi the yg shows an almost identical osiosi profile to that of the wis and very similar to that of other sites of the proto atlantic and european pelagic oceans turgeon and creaser 2008 and du vivier et al 2014 the characteristics of the osiosi profile are radiogenic and heterogeneous 0 55 0 85 prior to the oae 2 and synchronous with the inferred oae 2 onset the osiosi abruptly become unradiogenic and remain relatively homogeneous 0 20 0 30 before showing a gradual return to more radiogenic view the mathml sourceosi 0 70 throughout the middle to late oae 2 a206a206pb 238u zircon age of an interbedded tuff hk017 in the adjacent horizon to the first unradiogenic osiosi value constrains the age of the osiosi inflection at 94 44 0 14 ma94 44 0 14 ma this age including uncertainty agrees with the interpolated age of the same point in the osiosi profile 94 28 0 25 ma94 28 0 25 ma in the only other dated oae 2 section the wis indicating a coeval shift in seawater chemistry associated with volcanism at the oae 2 onset at the levels of temporal resolution ca 0 1 myr further prior to the onset of oae 2 an enhanced radiogenic inflection in the osiosi profile of the yg is correlative within uncertainty with a similar trend in the wis based on the u pb age depth model the interpolated ages 94 78 0 12 ma94 78 0 12 ma and 94 66 0 25 ma94 66 0 25 ma for this osiosi inflection in the yg and wis respectively indicate that palaeocirculation was sufficient to simultaneously influence transbasinal seawater chemistry in contrast the pre oae 2 osiosi profile for the gvs is disparate to that of the yg and those of the proto atlantic and european pelagic shelf locations we interpret the pre oae 2 heterogeneous osiosi values 0 30 0 95 to record a palaeobasin that was regionally influenced interchangeably by both unradiogenic hydrothermal flux and radiogenic continental flux os we conclude that the osiosi profiles from the proto pacific sections record both trends that are consistent globally oae 2 onset syn and post oae 2 but also show regional differences pre oae 2 between oae 2 sections worldwide as such the osiosi profiles coupled with u pb geochronology facilitate the correlation of oae 2 stratigraphy and demonstrate both regional and global ocean dynamics

oscillatory sr isotopic signature in plagioclase megacrysts from the damiao anorthosite complex north china implication for petrogenesis of massif type anorthosite abstract formation of proterozoic massif type anorthosites is known to be related to polybaric process involving early high pressure crystallization of plagioclase and high al orthopyroxene megacrysts at mantle crust boundary followed by emplacement of plagioclase dominated mushes to shallow level crust therefore the plagioclase megacrysts record important information about the magmatic sources and crystallization process of anorthosites the 1 74 ga damiao complex north china comprises 90 vol anorthosites and leuconorites containing abundant plagioclase megacrysts associated with minor high al orthopyroxene megacrysts haoms the plagioclase megacrysts are generally euhedral to subhedral mostly 1 to 30 cm in diameter and some of them contain very fine lamellae of orthoclase and undefined fe ti rich minerals 1 5 m the haoms occur as subhedral grains or as angular grains with an intercumulus relationship to the plagioclase megacrysts they contain abundant thin regular lamellae of exsolved plagioclase 15 20 vol indicative of originally high al features originally 6 0 7 3 wt al2o3 based on the al in orthopyroxene geobarometry the haoms and associated plagioclase megacrysts are constrained to be crystallized together at pressures of 9 4 11 2 kbar 33 36 km indicative of their crystallization at lower crust depths or crust mantle boundary in contrast orthopyroxene grains from late differentiation phases such as oxide apatite gabbronorites do not contain plagioclase lamellae and have much lower al2o3 contents 1 5 to 1 7 wt indicating final crystallization at

hydrothermal venting of greenhouse gases triggering early jurassic global warming abstract the climate change in the toarcian early jurassic was characterized by a major perturbation of the global carbon cycle the event lasted for approximately 200 000 years and was manifested by a global warming of 6 c anoxic conditions in the oceans and extinction of marine species the triggering mechanisms for the perturbation and environmental change are however strongly debated here we present evidence for a rapid formation and transport of greenhouse gases from the deep sedimentary reservoirs in the karoo basin south africa magmatic sills were emplaced during the initial stages of formation of the early jurassic karoo large igneous province and had a profound influence on the fate of light elements in the organic rich sedimentary host rocks total organic carbon contents and vitrinite reflectivity data from contact aureoles around the sills show that organic carbon was lost from the country rocks during heating we present data from a new type of geological structures termed breccia pipes rooted in the aureoles within the shale of the western karoo basin the breccia pipes are cylindrical structures up to 150 meters in diameter and are mainly comprised of brecciated and baked black shale thousands of breccia pipes were formed due to gas pressure build up during metamorphism of the shales resulting in venting of greenhouse gases to the toarcian atmosphere mass balance calculations constrained by new aureole data show that up to 1800 gt of co2 was formed from organic material in the western karoo basin about 15 times this amount of co2 27 400 gt may have formed in the entire basin during the intrusive event u pb dating of zircons from a sill related to many of the pipes demonstrates that the magma was emplaced 182 5 0 4 million years ago this supports a causal relationship between the intrusive volcanism the gas venting and the toarcian global warming

crystallization and resorption in plutonic plagioclase implications on the evolution of granodiorite magma gesiniec granodiorite strzelin crystalline massif sw poland abstract granodiorite from the gesiniec intrusion strzelin crystalline massif sw poland contains complexly zoned plagioclases five chemically and structurally distinct zones can be correlated among crystals cores 25 35 an inner mantles 40 45 an outer mantles 40 25 an resorption zones 35 50 an and rims 35 30 an good structural and chemical major and trace elements correlation of zones between crystals indicates that zonation was produced by changes in conditions of crystallization on a magma chamber scale plagioclase being the liquidus phase records a time span from the beginning of crystallization to emplacement and rapid cooling of granodiorite as thin dykes crystallization began with the formation of inner mantles the paucity and different sizes of inner mantles suggests slow crystallization in high temperature magma normally zoned inner mantles were formed under increasing undercooling compositional trends in mantles suggest closed system crystallization the major resorption zones were caused by injection of less evolved magma as indicated by the strontium increase in plagioclase the injection triggered a rapid rise of magma and plagioclase crystals facilitating mixing but also inducing fast kinetically controlled growth of complex multiple oscillatory zonation within resorption zones the ascent of magma caused decompression melting of plagioclase and produced melt inclusions within inner mantles the cores the decompression range is estimated at a minimum of 2 kbar emplacement of granodiorite as thin dykes allow rapid cooling and preservation of magmatic zonation in plagioclases melt inclusions crystallized completely during post magmatic cooling the zonation styles of plutonic plagioclase differ markedly from volcanic ones suggesting different magma evolution zones in plutonic plagioclase are well correlated indicating crystallization in quiescent magma where crystals accumulation and compositional magma stratification may occur crystals probably did not travel between different regimes resorption occurred but as single albeit complex episodes good correlation of zones in plutonic plagioclases allows a distinction between the main processes controlling zonation and superimposed kinetic effects

structural state transformation in alkali feldspar evidence for post crystallization deformation from proterozoic granite kumaun himalaya india the paleoproterozoic amritpur granite series ags constitutes a cogenetic magmatic suite of s type granites the granitic complex shows variation with respect to chemical and mineralogical properties however it shows uniformity in the structural state of alkali feldspars homogenization experiments on alkali feldspars of the ags indicate o700 8c magmatic melt temperatures the alkali feldspars are intermediate to maximum microcline dz0 604 0 833 with al concentrations ranging from 0 738 1 00 in the t1o tetrahedral site this indicates a higher degree of ordering following an ideal one step ordering path the two feldspar thermometry for granite suggests a temperature of 400g50 8c which is the inversion temperature of orthoclase into microcline due to deformation this suggests that the structural state transformation of alkali feldspar in the amritpur granite took place during a post crystallization thermal event subsequent to the crystallization of ags in the himalayas an early palaeozoic and a tertiary himalayan event associated with a low temperature event are recognized the p t conditions of the himalayan event are more conducive for the phase transformation of the alkali feldspar q 2004 elsevier ltd all rights reserved

production and preservation of organic matter the significance of iron 1 iron fertilization has been previously recognized as a potential mechanism for enhanced organic matter burial in marine sediments however the singular view of iron as a control on primary production overlooks its role in sedimentary diagenesis a factor that must be evaluated when considering organic matter accumulation this study examines the role of iron as a buffer of pore water sulfide and its implications for marine organic matter burial biogeochemical model experiments indicate that dissolved sulfide buildup in surficial marine sediments is highly sensitive to reactive iron concentration a reduction in reactive iron concentration can initiate dissolved sulfide accumulation the consequences of which include inhibition of bioturbation bioirrigation a decrease in oxygen exposure time and enhanced organic matter burial alternatively an increase in reactive iron concentration can serve to decrease organic matter burial the coupling of iron and phosphorous cycling within marine sediments provides an important positive feedback and therefore this mechanism is designated the sulfide buffer phosphorous trap hypothesis given sufficient organic carbon supply carbonate rich and opal rich sediments should be especially prone to the development of sulfidic conditions because of a deficiency in terrigenous iron widespread chalk and marl deposition during the cretaceous in association with the evolutionary expansion of calcareous plankton may have predisposed many benthic marine environments to the accumulation of toxic hydrogen sulfide and fostered the development of oceanic anoxic events comparison of model results with proxy data from oceanic anoxic event ii middle cretaceous suggests a complex role of iron as a control on both organic matter production and preservation

magma mixing in the post glacial veidivotn fissure eruption southeast iceland a microprobe study of mineral and glass variations local tephra stratigraphy and chemical analyses of lavas and tephras and their minerals provide detailed information on the eruptive history of the mixed post glacial veidivotn eruption basalts and rhyolites originated and were chemically modified in separate volcanic systems but were mobilized and mixed and erupted simultaneously in the veidivotn fissure both as tephras and lavas different extent of chemical mixing of basalt and rhyolite magmas associated with some fractionation and resorption can explain 1 significant k2o variations within the basaltic tephras stutshraun tephra 2 formation of homogeneous intermediate tephras of different compositions namshraun tephra 3 incomplete mixing with heterogeneous contamination of alkali rhyolite the mixing is proposed on the basis of the mixed appearance of different tephra compositions in the field the frequent distribution of basaltic xenocrysts in the rhyolitic and intermediate melts while intermediate mineral compositions are scarce and resorption and reversed zoning of phenocrysts in the rhyolitic lavas least squares mixing tests support the models for 1 and 2 but the present data are not sufficient to explain all the chemical variations in the alkali rhyolites

crystallization processes in the rocky hill granodiorite pluton california an interpretation based on compositional zoning of plagioclase the rocky hill pluton was chosen for study of plagioclase zoning because it has an apparently simple geometry and one stage emplacement history documented by putman and alfors 1969 the pluton is divided texturally into a hypidiomorphic granular rim fades and porphyritic core facies both comprising zoned plagioclase phenocrysts averaging 2 4 mm in diameter major features of compositional zoning profiles of plagioclase were found to be consistent within a sample showing resorbed core regions followed by a sharp drop of ca 10 an to a plateau region and ending with normal zoning the width of the plateau region is narrow in samples near the pluton rim but increases systematically toward the pluton core and the outer part of the plateau develops reverse zoning in the core facies a review of the effects of pressure water content of the melt and temperature on equilibrium and disequilibrium crystallization processes concludes that only variations of temperature and water content during disequilibrium crystallization of plagioclase phenocrysts can produce the observed zoning patterns experimental data suggest that the trend toward finer grain size toward the interior of the pluton may be due to increasing water content rather than due to increasing cooling rate the compositional zoning of plagioclase and textural variations in the pluton can be explained by a model in which the pluton crystallized by migration of a partly crystalline mush zone inward from the edge of the plutonic chamber while convection within the residual magma 1 redistributed water excluded from the mush zone and 2 slowed the cooling rate of the mush zone the reverse zoning of plagioclase growing in the convecting magma changed to normal zoning after capture in the mush zone because the cooling rate increased and water was removed comparison of the results from our study of rocky hill with published descriptions of plutons and experimental and theoretical studies of crystallization processes leads to the conclusions that 1 convection is an active process during the crystallization of many plutons causing redistribution of mainly water and heat in silicic ones but differentiating other components in intermediate ones 2 most of the crystallization of granitic rocks may occur in a mush zone or static boundary layer between the solid boundary and convecting inner magma body 3 water content may be an important factor controlling grain size 4 reverse zoning of plagioclase may be more typical of plagioclase grown under slowly cooled conditions than normal zoning and 5 variations of plagioclase zoning in plutons can provide useful information on crystallization processes

the geological history of northwestern south america from pangaea to the early collision of the caribbean large igneous province 290 75ma abstract northwestern south america preserves a record of the assembly of western pangaea its disassembly and initiation of the far western tethys wilson cycle subsequent pacific margin magmatism and ocean plateau continent interaction since the late cretaceous numerous models have been presented for various time slices although they are based on either spatially restricted datasets or dates that are inaccurate estimates of the time of crystallisation here we review a very large quantity of geochronological geochemical thermochronological sedimentological and palaeomagnetic data that collectively provide tight constraints for geological models these data have been collected over a trench pacific parallel distance of 1500 km colombia and ecuador and reveal important temporal trends in rifting and subduction the temporal framework for our model constraints are obtained from robust concordant zircon u pb ages of magmatic rocks during 290 75 ma the late cretaceous thermal history of the margin

secondary melting events in semarkona chondrules revealed by compositional zoning in low ca pyroxene abstract it is well established that many chondrules contain relict grains formed in previous generations of chondrules we here describe evidence that chondrules experienced multiple mesostasis melting events while remaining closed systems spheroidal chondrule shapes resulted from surface tension effects following a primary heating event that caused substantial melting 40 of the precursor assemblages in some high feo chondrules in ll3 00 semarkona low ca pyroxene phenocrysts show multiple overgrowth layers produced by secondary melting events we characterized these layers with the electron microprobe in terms of fe ca and cr in two semarkona chondrules the first low ca pyroxene overgrowth that forms after a minor heating melting event has low ca and fe concentrations of these incompatibles gradually increase over the next 8 4 m until falling temperatures and slowing diffusion caused growth to stop the next melting event remelts and mixes the local mesostasis cooling causes growth of a normal igneously zoned layer in the simplest cases the ca concentrations at the minima gradually increase towards the edge of the phenocryst heat deposition during heating events varied over a wide range the weakest events produced recognizable changes in slopes that we call inflections rather than minima large fractions of the individual phenocrysts were formed by the process that produced the overgrowth layers it appears that overgrowth formation stopped when the ca content of the mesostasis became high enough to make high ca pyroxene a liquidus phase both semarkona chondrules include olivine phenocrysts similar in size and modal abundance to the low ca pyroxene phenocrysts olivine compositional profiles show symmetrical apparently normal zoning except for asymmetries attributable to the presence of relict grains surface compositions of different olivine phenocrysts in the same chondrule are very similar to one another consistent with growth from mesostasis in the present chondrule hence these olivines must have experienced the same heating events as the pyroxenes with overgrowths as argued in earlier papers the fraction of chondrules heated to low temperatures sufficient to melt only mesostasis during nebular heating and melting processes is much larger than the fraction heated sufficiently to melt half or more of the mafic minerals melting is expected to result from flash heating in which heat is transported into the chondrule by radiation

monzonitic series from the variscan tormes dome central iberian zone petrogenetic evolution from monzogabbro to granite magmas abstract in the iberian massif rocks of the k rich plutonic series are not abundant but towards internal parts of the belt represented by the central iberian zone there are some sectors where shoshonitic plutonism occurs over broad areas one of these areas is the anatectic tormes dome encompassing two similar studied plutons pereruela and vitigudino a monzonitic association has been defined ranging from monzogabbros to quartz monzonites or scarce monzogranites enrichment in lree p sr and ba a high water content up to 5 5 and a high degree of oxidation ni nio buffer are the main features of magmas parental to these monzonitic rocks these petrographic and geochemical features allow these granitoids to be ascribed to the shoshonitic type sh type rather than to the i type the minimum emplacement pressure range is 410 230 mpa whereas the estimated solidus temperature range is 940 765 c i e above water saturated solidus o sr and nd isotopes point to open system processes apatite cathodoluminescence suggests that magma mixing was unlikely to have occurred for the most enriched rocks assimilation fractional crystallisation afc modelling was performed for both plutons permitting assimilation crystallization rates to be estimated between 0 16 and 0 25 different contaminants have been inferred a metapelite at upper crustal level for the vitigudino pluton and a granulitic orthogneiss for the pereruela pluton a liquid line of descent linking monzogabbroic members to quartz monzonites monzogranites can be reconstructed some loss of water and oxygen can be inferred although water remained in the system below the solidus giving rise to auto metamorphism at ca 500 c on the other hand afc processes are unlikely to have been the main factor in controlling the characteristic enrichment of the monzonitic series since the least contaminated samples are the most lile and lree enriched for both plutons thus a source controlled chemical signature can be inferred the experimental data indicate that a hybrid protholith a mixture of peridotite amphibolite and metapelite can account for the enrichment and hydrated nature of the least evolved monzogabbroic magmas late orogenic slab break off and subsequent post collisional extensional events appear to be a suitable scenario to provide the heat that triggered partial melting close to the crust mantle boundary

dinantian dolomites from east fife hydrothermal overprinting of early mixing zone stable isotopic and fe mn compositions thin marine limestones from the dinantian of the st monans syncline east fife are extensively dolomitized they occur within a deltaic sequence cut by upper carboniferous volcanic rocks the volcanic rocks have been extensively modified by co 2 enriched hydrothermal fluids the dolomite is ferroan and nonluminescent stable isotope compositions for groundmass dolomite range from 18 o 4 76 to 0 47 and 13 c 3 29 to 0 60 later void filling dolomite falls into two groups the first is 18 o depleted with 18 o as low as 10 6 while the second is 18 o enriched 18 o 2 8 to 1 2 despite almost homogeneous staining characteristics backscattered sem imaging shows the dolomites to be chemically extremely heterogeneous dolomitization was a multistage process in which an early mixed water component was variably remobilized to form the matrix dolomite biomolds and other vuggy post early dolomite porosity are filled by dolomite precipitated within a volcanically driven hydrothermal system the chemistry of the later dolomite reflects the mixing of upward moving hydrothermal fluids modified by interaction with volcanic material with downward moving seawater feeding the hydrothermal system in addition material released during normal processes of siliciclastic diagenesis added a further component to the late stage dolomitization only two of the limestones escaped complete dolomitization and appear to have undergone early post depositional diagenesis within meteoric porefluids they contain early meteoric calcite cements and later post compaction calcite cements dolomite and siderite one of the implications of this study is that the interpretation of dolomite geochemical data can be vastly enhanced by the use of back scattered electron microscopy to reveal otherwise hidden compositional heterogeneity

black shale deposition atmospheric co2 drawdown and cooling during the cenomanian turonian oceanic anoxic event 1 oceanic anoxic event 2 oae2 spanning the cenomanian turonian boundary ctb represents one of the largest perturbations in the global carbon cycle in the last 100 myr the 13ccarb 13corg and 18o chemostratigraphy of a black shale bearing ctb succession in the vocontian basin of france is described and correlated at high resolution to the european ctb reference section at eastbourne england and to successions in germany the equatorial and midlatitude proto north atlantic and the u s western interior seaway wis 13c offset between 13ccarb and 13corg is shown to be a good pco2 proxy that is consistent with pco2 records obtained using biomarker 13c data from atlantic black shales and leaf stomata data from wis sections boreal chalk 18o records show sea surface temperature sst changes that closely follow the 13c pco2 proxy and confirm tex86 results from deep ocean sites rising pco2 and sst during the late cenomanian is attributed to volcanic degassing pco2 and sst maxima occurred at the onset of black shale deposition followed by falling pco2 and cooling due to carbon sequestration by marine organic productivity and preservation and increased silicate weathering a marked pco2 minimum 25 fall occurred with a sst minimum plenus cold event showing 4 c of cooling in 40 kyr renewed increases in pco2 sst and 13c during latest cenomanian black shale deposition suggest that a continuing volcanogenic co2 flux overrode further drawdown effects maximum pco2 and sst followed the end of oae2 associated with a falling nutrient supply during the early turonian eustatic highstand

elemental abundance anomalies in the late cenomanian extinction interval a search for the source s elemental abundances have been measured by neutron activation methods across the cenomanian turonian late cretaceous extinction interval in samples collected from sixteen sites in the western interior basin of north america and from twelve widely separated locations around the globe including six odp dsdp sites in most western interior basin sites in colombia and in western europe weaker two closely spaced elemental abundance peaks occur in the upper cenomanian 92 m y spanning the ammonite zones ofsciponoceras gracile throughneocardioceras juddii elements with anomalously high concentrations include sc ti v cr mn co ni ir pt and au the lower peak coincides with the disappearance extinction of the foraminiferrotalipora cushmani in north american sectionsr greenhornensis also disappears at or just below this horizon but in europe it disappears considerably earlier thanr cushmani a series of molluscan extinction and speciation or migration events also begins near the stratigraphic level of the lower elemental abundance peak the well documented positive 13c excursion begins just before the extinctions and the elemental anomalies and continues into the lower turonian well above the upper anomaly this carbon isotope excursion has been observed in east european sections where we find little or no evidence of the elemental anomalies suggesting that the two phenomena may not be tightly coupled elemental abundance ratios in the anomalies closely resemble those of mid atlantic ridge basalt or hawaiian lava tholeiitic but not those of c1 chondrite black shale average crustal rocks or lamproite and kimberlite of roughly similar age in southeastern kansas the excess ir and other siderophiles hint at possible large body impact s for the source however we have not located microspherules other than biogenic calcispheres or shocked mineral grains in any of our samples furthermore sc ti v and mn are not enriched in differentiated solar system bodies although the weak geochemical signal from comet impact s could be masked by the strong terrestrial like overprint these anomalies more likely resulted either from intense seafloor spreading activity or merely from increased circulation of deep metal rich water associated with the large late cenomanian through early turonian eustatic rise and deep water opening of the south atlantic the flooding of continental seaways and margins also could have contributed to the anomalies by preventing much continental detritus from diluting the normal background marine geochemical component

late cretaceous magmatism in madagascar palaeomagnetic evidence for a stationary marion hotspot late cretaceous basaltic volcanics in the morondava basin sw madagascar possess high quality and pre fold palaeomagnetic data declination 353 5 inclination 54 8 95 2 4 the palaeomagnetic data are all of normal magnetic polarity and remanence acquisition is linked to the terminal stages of the cretaceous normal superchron 83 ma this is sustained by an 40ar 39ar age of 83 6 1 6 ma from one of the tested basaltic flows a precise u pb zircon baddeleyite age from northeast madagascar demonstrates magmatism at least back to 91 6 0 3 ma thus reliable isotope ages for the madagascar cretaceous igneous province span a range of 8 million years late cretaceous palaeomagnetic data obtained from volcanics and dolerites all over madagascar are directionally concordant and the combined palaeomagnetic pole latitude 68 5 n longitude 230 3 e a95 5 5 n 8 studies sampling age range ca 84 90 ma represents one of the best late cretaceous poles for the former gondwanan elements the collective palaeomagnetic data yield a palaeolatitude of 45 3 s 5 3 4 7 for the proposed focal point of the marion plume volcan de l androy southeast madagascar during the late cretaceous this is in perfect agreement with hotspot controlled reconstructions that place the marion hotspot 46 0 s beneath southeast madagascar during the late cretaceous setting true polar wander aside hotspot movements in the indian ocean do not appear to exceed ca 0 75 cm yr and the marion hotspot appears stationary within the resolution power of palaeomagnetic data

sidewall crystallization in the klokken intrusion zoned ternary feldspars and coexisting minerals the syenitic layered series in the klokken intrusion is surrounded by a zone 500 m thick of nearly structureless unlaminated syenite followed outwards by a zone of vertically banded gabbro 200 m thick at the outer rim the unlaminated syenite is intrusive into the gabbro and develops a thin 2 m transition zone of syenodiorite at the contact a traverse across the vertical transition zone and inwards towards the layered series was sampled with a portable drill mafic silicates olivine clinopyroxene biotite show inward evolution in fe fe mg across the syenodiorite unlaminated syenite zones feldspars change rapidly across the syenodiorite zone from rocks dominated by plagioclase in some cases together with two alkali feldspars one a mesoperthite or cryptomesoperthite the other a cryptoperthite to rocks in which plagioclase is seen only rarely as cores to cryptomesoperthitic alkali feldspar crystals plagioclase is absent from the layered series

midlatitude shelf seas in the cenomanian turonian greenhouse world temperature evolution and north atlantic circulation 1 an 8 million year record of subtropical and midlatitude shelf sea temperatures derived from oxygen isotopes of well preserved brachiopods from a variety of european sections demonstrates a long term cenomanian temperature rise 16 20 c midlatitudes that reached its maximum early in the late turonian 23 c midlatitudes superimposed on the long term trend shelf sea temperatures vary at shorter timescales in relation to global carbon cycle perturbations in the mid cenomanian and the late turonian two minor shelf sea cooling events 2 3 c coincide with carbon cycle perturbations and times of high amplitude sea level falls although this evidence supports the hypothesis of potential glacioeustatic effects on cretaceous sea level the occurrence of minimum shelf sea temperatures within transgressive beds argues for regional changes in shelf sea circulation as the most plausible mechanism the major carbon cycle event in the latest cenomanian oceanic anoxic event 2 is accompanied by a substantial increase in shelf sea temperatures 4 5 c that occurred 150 kyr after the commencement of the 13c excursion and is related to the spread of oceanic conditions in western european shelf sea basins our oxygen isotope record and published 18o data of pristinely preserved foraminifera allow the consideration of north atlantic surface water properties in the cenomanian along a transect from the tropics to the midlatitudes on the basis of fossil derived 18o estimated w ranges and modeled salinities temperature salinity density ranges were estimated for tropical subtropical and midlatitude surface waters accordingly the cenomanian temperate shelf seas waters have potentially the highest surface water density and could have contributed to north atlantic intermediate to deep waters in the preopening stage of the equatorial atlantic gateway

the cenomanian turonian oceanic anoxic event i stratigraphy and distribution of organic carbon rich beds and the marine δ13c excursion marine strata deposited during late cenomanian and early turonian time display lithological faunal and geochemical characteristics which indicate that significant parts of the world ocean were periodically oxygen deficient at or very close to the cenomanian turonian boundary between 90 5 and 91 5ma ago oxygen deficiencies were particularly marked over a period of 1ma this short lived episode of oceanic oxygen deficiency has been termed the cenomanian turonian oceanic anoxic event oae the widespread distribution of anoxic sediments deposited synchronously during such a short lived event indicates that such sediments are not simply the product of coincidental local climatic or basinal water mass characteristics but are the result of a global expansion and intensification of the cenomanian turonian oxygen minimum zone related to feedback between sea level rise and regional palaeoceanography the palaeoceanography of the cenomanian turonian oae is discussed in detail in a companion paper by arthur et al 1987 from authors

the phillips pluton maine usa evidence of heterogeneous crustal sources and implications for granite ascent and emplacement mechanisms in convergent orogens the phillips pluton age of 403 8 1 3 ma was assembled at a crustal level below the contemporary brittle plastic transition during regional dextral reverse transpressive deformation the pluton is composed dominantly of medium to coarse grained leucogranite sensu lato s l but within its bounds includes decametric massive outcrop of fine to medium grained granodiorite s l in places the leucogranite contains centimetric enclaves apparently of the granodiorite granodiorite is host to more biotite than muscovite and more calcic oscillatory zoned plagioclase compared to the leucogranite pegmatitic granite and composite pegmatite aplite occur as metric sheets within the pluton and as larger bodies outside the pluton to the sw magmatic fabrics defined by biotite schlieren occur locally in the leucogranite the attitude of these fabrics and layering within the leucogranite are concordant with the ne striking steeply dipping country rock foliation k2o contents rb sr ratios rb sr and ba covariations and chondrite normalized rare earth element ree patterns of leucogranite are consistent with high to moderate a h2o muscovite dehydration equilibrium eutectic melting of a predominantly pelite source similar to metasedimentary rocks of the surrounding central maine belt cmb the ree patterns and rb sr ratios of granodiorite also suggest derivation from a metasedimentary source but more likely by moderate to low a h2o muscovite biotite dehydration equilibrium eutectic to non eutectic minimum melting of a protolith dominated by greywacke in which garnet and plagioclase were residual phases both granite s l types have heterogeneous initial nd isotope compositions samples of granodiorite define a range in end 404 ma of 1 8 to 0 1 0 3 2 uncertainty and samples of leucogranite define a range in end 404 ma of 8 0 to 5 3 0 3 2 uncertainty this bimodal distribution suggests that melts were derived from a minimum of two sources the data are consistent with these sources being cmb metasedimentary rocks end 404 ma 4 for the granodiorite the range of nd isotope compositions within each granite type most likely reflects isotopic heterogeneity inherited from the source these data imply that the integrity of individual melt batches was maintained during ascent and that extensive mixing of melt batches during emplacement at this level in the pluton did not occur although centimetric enclaves have intermediate nd isotope compositions consistent with small scale interactions between magmas we infer that the phillips pluton represents the root of a larger pluton and that what remains of this larger pluton is the feeder constructed from multiple melt batches arrested during waning flow of granite magma through a crustal scale shear zone system

pin pricking the elephant evidence on the origin of the ontong java plateau from pb sr hf nd isotopic characteristics of odp leg 192 basalts age corrected pb sr and nd isotope ratios early aptian basalt from four widely separated sites on the ontong java plateau that were sampled during ocean drilling program leg 192 cluster within the small range reported for three earlier drill sites for outcrops in the solomon islands and for the nauru and east mariana basins hf isotope ratios also display only a small spread of values a vitric tuff with end t 4 5 that lies immediately above basement at site 1183 represents the only probable example from leg 192 of the singgalo magma type flows of which comprise the upper 46 750 m of sections in the solomon islands and at leg 130 site 807 on the northern flank of the plateau all of the leg 192 lavas including the high mgo 8 10 wt kroenke type basalts found at sites 1185 and 1187 have end t between 5 8 and 6 5 they are isotopically indistinguishable from the abundant kwaimbaita basalt type in the solomon islands and at previous plateau nauru basin and east mariana basin drill sites the little fractionated kroenke type flows thus indicate that the uniform isotopic signature of the more evolved kwaimbaita type basalt with 5 8 wt mgo is not simply a result of homogenization of isotopically variable magmas in extensive magma chambers but instead must reflect the signature of an inherently rather homogeneous relative to the scale of melting mantle source in the context of a plume head model the kwaimbaita type magmas previously have been inferred to represent mantle derived largely from the plume source region our isotopic modelling suggests that such mantle could correspond to originally primitive mantle that experienced a rather minor fractionation event e g a small amount of partial melting approximately 3 ga or earlier and subsequently evolved in nearly closed system fashion until being tapped by plateau magmatism in the early aptian these results are consistent with current models of a compositionally distinct lower mantle and a plume head origin for the plateau however several other key aspects of the plateau are not easily explained by the plume head model the plateau also poses significant challenges for asteroid impact icelandic type and plate separation perisphere models at present no simple model appears to account satisfactorily for all of the observed first order features of the ontong java plateau the geological society of london 2004

time scales of magmatic processes from modeling the zoning patterns of crystals the advent of polarized light microscopy in the middle of the 19th century allowed mineralogists and petrologists interested in igneous rocks to recognize the widespread occurrence of fine scale heterogeneities in the optical properties of minerals e g see young 2003 for details the interpretation of mineral zoning patterns as archives of magmatic processes has been with us for some time e g larsen et al 1938 tomkeieff 1939 the development of the electron microprobe in the 1960 s allowed mineral zoning profiles to be quantitatively analyzed and modeled e g bottinga et al 1966 moore and evans 1967 enhanced textural observations permitted recognition of many kinds of detailed structures during the growth and dissolution of magmatic minerals fig 1 e g anderson 1983 pearce and kolisnik 1990 and these processes were also explored using experimental and numerical models e g albarede and bottinga 1972 lofgren 1972 kirkpatrick et al 1976 loomis 1982 major element zoning patterns are routinely measured and with the arrival of the ion microprobe the identification of heterogeneous distribution of trace elements opened the window for more realistic and sophisticated scenarios and models fig 1 e g kohn et al 1989 blundy and shimizu 1991 singer et al 1995 we now measure abundances of naturally occurring isotopes at the scale of tens of micrometers e g davidson et al 2007a ramos and tepley 2008 and this allows in situ dating of crystals e g cooper and reid 2008 figure 1 a nomarski dic image of a plagioclase crystal from a gabbroic xenolith of volcan san pedro costa et al 2002 the crystal shows a well defined core and a rim separated by an oscillatory zoned interval ion microprobe analysis pits and the trace of the electron microprobe traverse between the pits are evident b major

mercury in the north atlantic ocean the u s geotraces zonal and meridional sections abstract mercury hg in the ocean undergoes many chemical transformations including in situ production of monomethylmercury mmhg the form that biomagnifies in marine food webs because the ocean is a primary and dynamic reservoir of hg cycling at earth s surface and the principal source of human mmhg exposures through seafood it is important to understand the distribution of hg and its chemical species in marine environments we examined total hg elemental hg hg 0 mmhg and dimethylmercury dmhg with fully resolved high resolution profiles during the u s geotraces zonal and meridional sections of the north atlantic ocean geotraces ga03 total hg in filtered water had both scavenged and nutrient type vertical distributions whereas concentrations of dmhg hg 0 and filtered mmhg were increased in the oxygen deficient zone of the permanent thermocline across the basin relative to water above and often below total hg and mmhg on suspended particles accounted for less than 10 of total concentrations the tag hydrothermal vent on the mid atlantic ridge mar was a source of total hg and mmhg to nearby waters with apparent scavenging and hg transformation occurring in the buoyant plume uniquely we observed significant horizontal segregation of filtered total hg and mmhg dmhg and hg 0 in north atlantic deep water nadw between younger water on the western and older water on the eastern side of the mar relative to eastern nadw hg concentrations in western nadw were greater on average by 1 14 for filtered total hg 1 6 for hg 0 2 5 for filtered mmhg and 2 6 for dmhg total hg enrichment in deep water of the western basin may have resulted from downwelling of anthropogenic hg during nadw formation enrichment of mmhg dmhg and hg 0 in western basin nadw may be explained by either greater hg substrate availability or greater methylation and reduction potentials in younger deep waters

trace element abundances in the rock canyon anticline pueblo colorado marine sedimentary section and their relationship to caribbean plateau construction and oxygen anoxic event 2 1 rapid eruption of submarine lava flows during formation of the caribbean plateau correlates closely with ocean anoxic event 2 oae2 which bracketed the cenomanian turonian boundary 93 5 ma these events also correspond with a positive excursion in carbon isotopic composition of seawater hydrothermal activity associated with large scale submarine volcanism may have been responsible for this abrupt change in ocean chemistry we determined the distribution of major minor and trace element abundances in the rock canyon marine sedimentary section pueblo colorado after normalizing element concentrations to zr to remove the variable contribution of terrigenous material to these sediments we detected an interval of concentrated metal abundance anomalies that coincides with the abrupt beginning of the positive 13c isotope excursion the metal abundance anomalies indicate that intermittent hydrothermal activity in the form of both water rock exchange and magmatic degassing introduced large concentrations of trace metals into the cretaceous ocean at the same time that extinctions of benthic species turnover in plankton communities and increases in isotopically light organic carbon burial occurred the stratigraphic position of this interval of trace metal anomalies matches events associated with oae2 and indicates that intermittent hydrothermal activity on a massive scale triggered abrupt changes in carbon burial and deep ocean oxygen contents

the geochemical behavior and isotopic composition of hg in a mid pleistocene western mediterranean sapropel abstract the concentrations of mercury hg and other trace metals ni cu zn mo ba re u and the hg isotopic composition were examined across a dramatic redox and productivity transition in a mid pleistocene mediterranean sea sapropel sequence characteristic trace metal enrichment in organic rich layers was observed with organic rich sapropel layers ranging in hg concentration from 314 to 488 ng g avg 385 with an average enrichment in hg by a factor of 5 9 compared to organic poor background sediments which range from 39 to 94 ng g hg avg 66 comparison of seawater concentrations and sapropel accumulations of trace metals suggests that organic matter quantitatively delivers hg to the seafloor near complete scavenging of hg from the water column renders the sapropel hg isotopic composition representative of mid pleistocene mediterranean seawater sapropels have an average 202hg value of 0 91 0 15 n 5 1 sd and 199hg value of 0 11 0 03 n 5 1 sd background sediments have an average 202hg of 0 76 0 16 n 5 1 sd and 199hg of 0 05 0 01 n 5 1 sd which is indistinguishable from the sapropel values we suggest that the sapropel isotopic composition is most representative of the mid pleistocene tyrrhenian sea

reconstruction of water column anoxia in the equatorial atlantic during the cenomanian turonian oceanic anoxic event using biomarker and trace metal proxies abstract the occurrence of the biomarker lycopane and the enrichment patterns of redox sensitive trace metals in black shales from demerara rise western tropical atlantic reveal that bottom waters were anoxic during the upper cenomanian and lower turonian at this location bottom waters were clearly oxygen depleted already before oceanic anoxic event 2 oae 2 and continued to be so afterwards furthermore the presence of fossil derivatives of isorenieratene and chlorobactene pigments derived from green sulfur bacteria demonstrates that the waters at the base of the photic zone occasionally contained sulfide i e were euxinic before and after oae 2 low concentrations of derivatives of these pigments are present while much higher concentrations occur within the oae 2 section stratification of the water column must have been strong to sustain euxinic conditions in the photic zone for prolonged periods a substantial drop in the concentrations of isorenieratene and chlorobactene derivatives demonstrates that this stratification temporarily broke down during oae 2 a simultaneous decrease in sea surface temperatures suggests that local ventilation was instrumental in this re oxygenation event a rapid decrease in seawater derived trace metal burial rates at demerara rise occurring in phase with the onset of the anoxia related to oae 2 suggests an approximately synchronous onset of oae 2 in the proto north atlantic

orbital time scale and new c isotope record for cenomanian turonian boundary stratotype previous time scales for the cenomanian turonian boundary ctb interval containing oceanic anoxic event ii oae ii vary by a factor of three in this paper we present a new orbital time scale for the ctb stratotype established independently of radiometric biostratigraphic or geochemical data sets update revisions of ctb biostratigraphic zonation and provide a new detailed carbon isotopic record for the ctb study interval the orbital time scale allows an independent assessment of basal biozone ages relative to the new ctb date of 93 55 ma gts04 the d 13 corg data document the abrupt onset of oae ii significant variability in d 13 corg values and values enriched to almost 222 these new data underscore the difficulty in defining oae ii termination using the new isotope curve and time scale estimates of oae ii duration can be determined and exported to other sites based on integration of well established chemostratigraphic and biostratigraphic datums the new data will allow more accurate calculations of biogeochemical and paleobiologic rates across the ctb

record of mega earthquakes in subduction thrusts the black fault rocks of pasagshak point kodiak island alaska on kodiak island alaska decimeterthick black fault rocks are at the core of foliated cataclasites that are tens of meters thick the cataclasites belong to melange zones that are regarded as paleodecollements active at 12 14 km depth and 230 260 c each black layer is mappable for tens of meters along strike the black fault rocks feature a complex layering made at microscale by alternation of granular and crystalline micro textures both composed of micronscale subrounded quartz and plagioclase in an ultrafi ne phyllosilicate rich matrix in the crystalline microlayers tabular zoned micro lites of plagioclase make up much of the matrix no such feldspars have been found in the cataclasite we interpret these crystalline microlayers as pseudotachylytes the granular microlayers show higher grainsize variability crushed microlites and textures typical of fl uidization and granular fl ow deformation crosscutting relationships between granular and crystalline microlayers include fl ow and intrusion structures and mutual brittle truncation this suggests that each decimeters thick composite black fault rock layer records multiple pulses of seismic slip in each pulse ultracomminuted fl uidized material and friction melt formed and deformed together in a ductile fashion brittle truncation by another pulse occurred after solidifi cation of the friction melt and the fl uidized rock x ray powder diffraction xrpd and x ray fl uorescence xrf analyses show that black fault rocks have similar mineral composition and chemical content as the cataclasites the observed systematic chemical differences cannot be explained by bulk or preferential melting of any of the cataclasite components the presence of an open fl uidinfi ltrated system with later alteration of black fault rocks is suggested the geochemical results indicate that these subductionrelated pseudotachylytes differ from those typically described in crystalline rocks and other tectonic settings

metal emissions from kilauea and a suggested revision of the estimated worldwide metal output by quiescent degassing of volcanoes abstract measurements of a large suite of metals pb cd cu zn and several others and sulfur at kilauea volcano over an extended period of time has yielded a detailed record of the atmospheric injection of ordinarily rare metals from this quiescently degassing volcano representative of an important type we have combined the kilauea data with data of recent studies by others emissions from volcanoes in the indonesian arc the large laki eruption of two centuries ago etna estimates of total volcanic emissions of sulfur to form the basis for a new working estimate of the rate of worldwide injection of metals to the atmosphere by volcanoes the new estimate is that volcanoes inject a substantially smaller mass of ordinarily rare metals into the atmosphere than was stated in a widely cited previous estimate j o nriagu a global assessment of natural sources of atmospheric trace metals nature 338 1989 47 49 our estimate which is an upper limit is an annual injection mass of about 10 000 tons of the metals considered versus the earlier estimate of about 23 000 tons also the proportions of the metals are substantially different in our new estimate