an evaluation of the single grain zircon evaporation method in highly discordant samples comparison of results from the isotope dilution and the single grain zircon evaporation methods on highly discordant samples shows that the evaporation method can yield accurate crystallization ages on some zircon populations that display complex discordant patterns three granite gneiss samples from the western gneiss region norway which crystallized at approximately 1660 ma and experienced profound lead loss in zircon during caledonian metamorphism at 400 ma were analyzed by both the isotope dilution tucker et al 1990 and evaporation methods 207ph 206pb evaporation ages on one sample agree with the isotope dilution crystallization age two other samples produced a range of anomalously young 207pb 206pb evaporation ages analyses at the highest evaporation temperatures from one of these two samples were consistent with crystallization ages determined by the isotope dilution method but it would be difficult to interpret them correctly without independent age information the anomalously young results are generally easy to recognize by the pattern of increasing 207ph 206ph ages with increasing evaporation temperature a more serious problem however is that some grains produced 207ph 206pb age plateaus over a range of increasing evaporation temperatures that cannot be correlated with any documented geologic event in the region the evaporation analyses yielding the youngest 207pb 206pb ages also display the most common lead suggesting that common lead may diffuse into the zircon grains during loss of radiogenic lead a pegmatite from massachusetts usa contains zircons with visible xenocrystic cores the 207ph 206pb evaporation ages at lower temperatures agree well with the 299 ma crystallization age determined by the isotope dilution method on the zircon rims r d tucker unpubl data at higher evaporation temperatures a range of older 207pb 206pb ages are produced by mixing pb evaporated from both the zircon rims and xenocrystic cores large changes in the 206pb 208pb ratio accompany the increase in 207pb 206pb ages and indicate mixing of two distinct zircon domains thus in addition to providing useful 207pb 206pb age information the evaporation method may help distinguish between the discordance produced by diffusional lead loss and the mixing of two domains of differing age

seasonal stratification shell flux and oxygen isotope dynamics of left coiling n pachyderma and t quinqueloba in the western subpolar north atlantic blooms this annual population overturning is marked by a 0 7 increase in d 18 o in both species the shell flux of n pachyderma peaks during the spring bloom and in late summer when stratification is close to its minimum and maximum respectively both export periods contribute about equally and account for 95 of the total annual flux shell fluxes of t quinqueloba show only a single broad pulse in summer thus following the seasonal stratification cycle the d 18 oo fn pachyderma reflects temperatures just below the base of the seasonal sml without offset from isotopic equilibrium the d 18 op attern oft quinqueloba shows a nearly identical amplitude and correlates highly with the d 18 oo fn pachyderma therefore t quinqueloba also reflects temperature near the base of the sml but with a positive offset from isotopic equilibrium these offsets contrast with observations elsewhere and suggest a variable offset from equilibrium calcification for both species in the irminger sea the species consistently show a contrast in their flux timings their flux weighted dd 18 o will thus dominantly be determined by seasonal temperature differences at the base of the sml rather than by differences in their depth habitat consequently their sedimentary dd 18 o may be used to infer the seasonal contrast in temperature at the base of the sml citation jonkers l g j a brummer f j c peeters h m van aken and m f de jong 2010 seasonal stratification shell flux and oxygen isotope dynamics of left coiling n pachyderma and t quinqueloba in the western subpolar north atlantic paleoceanography 25 pa2204 doi 10 1029 2009pa001849

burial of organic carbon and pyrite sulfur in sediments over phanerozoic time a new theory in present day marine sediments almost all of which are deposited in normal oxygenated seawater rates of burial of organic carbon c and pyrite sulfur s correlate positively and bear a constant ratio to one another c s 3 on a weight basis by contrast calculations based on the isotopic model of garrels and lerman 1981 indicate that at various times during the phanerozoic the worldwide burial ratio must have been considerably different than the present day value this ratio change is caused by the requirement that increases in the worldwide mass of organic carbon must be accompanied by equivalent decreases in the mass of sedimentary pyrite sulfur in order to maintain a roughly constant level of o2 in the atmosphere such apparently contradictory behavior can be explained if the locus of major organic carbon burial has shifted over time from normal marine environments as at present to non marine freshwater or to euxinic environments in the geologic past a shift to predominantly freshwater burial can help explain predicted high c s ratios in permo carboniferous sediments and a shift to euxinic environments can help explain predicted low c s ratios during the early paleozoic it is demonstrated that the three environments today exhibit distinguishably different average c s ratios

fluorine in formation waters alberta basin canada abstract fluorine is a common minor constituent of formation waters throughout the alberta basin and it was detected in each of the 469 samples analyzed for it contents range up to 22 mg l with an arithmetic mean of 1 83 mg l and a median value of 1 20 mg i there is a trend toward increased mean and median contents of f from the shallower cooler less saline formation waters to the deeper hotter more saline formation waters this trend parallels a trend of increasing saturation with respect to fluorite with most of the less saline formation waters being undersaturated with respect to fluorite at the same time the major portion of f occurs as f in the less saline formation waters with increasing amounts held as mgf as the ca content ionic strength and temperature increase complexes between al and f and vo and f account for only a relatively minor portion of the complexed f a significant portion of the f in high salinity formation waters from marine strata could well have originated from the initial seawater however it is speculated that water rock reactions with bentonite or bentonitic shales may have to be invoked to account for the very high contents of f in the less saline formation waters from some of the shallow cooler non marine aquifers of the upper cretaceous post colorado aquifer aquitard system finally it is possible to use knowledge of the distribution of f in formation waters from individual aquifers to check on the correctness of f determinations primarily when formation waters of similar composition show saturation with respect to fluorite and in the same case to predict the f content of formation waters in the alberta basin for which only the appropriate major ions have been determined

early diagenesis impact of organic matter on mass physical properties and processes california continental margin abstract high resolution scales of 2 5 mm to submicrometer interdisciplinary studies of california continental slope sediments 0 80 cm reveal the importance of marine organic material and mineralogy on mass physical properties in fine grained sediments during very early diagenesis the combination of organic material 2 wt with smectite 5 is associated with high depositional porosities low effective stresses low porosity reduction and dewatering and the impedance of interstitial fluid flow living microbiota and nonliving mucopolysaccharides organic matter affecting the physical properties was revealed by transmission electron microscopy and carbon isotope studies calculations using the redfield ratio show that sediments containing high organic carbon 5 wt have hydrated organic material in the pore spaces that can occupy a volume that is up to 20 of the total sediment porosity pore water chemistry and x ray diffraction show evidence of early diagenetic processes that may significantly influence sediment fabric an important geochemical process near the sediment water interface that affects sediment fabric is the rapid dissolution of biogenic opal

paleomagnetic constraints on the geodynamic history of the major blocks of china from the permian to the present paleomagnetic study of china and its environs has been the center of a major international effort for the last 10 years in this paper we critically review all available paleomagnetic poles of upper permian to tertiary age from the main blocks of china with the goal of placing constraints on models of the formation and the subsequent deformation of the region after selecting reliable poles by applying objective criteria we divide our analysis into first order motions of blocks and second order deformation within blocks for first order analysis apparent polar wander paths are constructed for the major blocks we discuss the compatibilities and contradictions between the geological and paleomagnetic records a sequence of paleogeographic configurations taking into account geological constraints but remaining within paleomagnetic uncertainties is presented in general the major blocks were probably in contact throughout the permian and triassic but the jurassic was the key age during which most of the movement toward china s present configuration took place our reconstructions include certain details which are suggested by the paleomagnetic record but whose geological signatures seem to have been hidden by subsequent events during the cretaceous chinese poles agree with poles from other continents transferred onto eurasia at the second order we observe that for almost each period with sufficient data the paleomagnetic poles are streaked along a small circle centered on the sampling region indicating that much of china has been affected by small 20 differential rotations this we interpret as deformation caused in part by the extrusion of the chinese blocks away from the indian collision the complete annotated list of poles is given as an appendix

pure siliceous ooze a diagenetic environment for early chert formation the formation of marine opal ct nodules or layers as early diagenetic deposits has been documented only in antarctic deep sea sediments in contrast porcellanites and cherts in land sections and deep sea drilling project and ocean drilling program drill sites are usually found in sediment sections of miocene age and older during r v polarstem cruises ant ix 3 and 4 young porcellanites were recovered for the first time in contact with their host sediment in two cores from the atlantic sector of the southern ocean chemical and mineralogical studies of these deposits and their surrounding sediments have increased knowledge about very early chert formation in both cores the porcellanites are embedded in sediments rich in opal a with extremely low levels of detrital minerals an environment that seems conducive to a rapid transformation of biogenic silica into porcellanites

the silicon and oxygen isotope compositions of precambrian cherts a record of oceanic paleo temperatures oxygen and silicon isotopes in cherts have been extensively used for the reconstruction of seawater temperatures during the precambrian during the past decade the advance of in situ analysis of si isotopes has enhanced the interest on cherts as a paleo environmental proxy the coupled o and si isotope composition variations show secular and correlated trends that have been interpreted as a progressive cooling of the ocean however this reconstruction has been challenged because cherts can have various origins hydrothermal sedimentary volcanic silicification and their isotopic compositions might have been reset by metamorphic fluid circulation in this case the secular oxygen and silicon isotope variation are considered as reflecting a mixing between seawater and hydrothermal sources a key point in this discussion deals with the origin of cherts sedimentary hydrothermal or chemically silicified therefore several petrographical and geochemical criteria are proposed to recognize the pristine sedimentary origin of a chert namely they are 1 the occurrence of microquartz 2 a 18o rich bulk oxygen isotopic composition 3 the occurrence of large 18o ranges at a micrometer scale 4 variation of trace element compositions coupled with 30si 5 the occurrence of large ranges of 30si in pure microquartz these criteria should be regarded as guides to the identification of pristine diagenetic cherts in order to better constrain seawater paleo temperature reconstructions by taking into account the effect of diagenesis this article will review the different interpretations about o and si isotope variation and propose a model of formation based on ancient and modern chert studies

radiolarian palaeoecology and radiolarites is the present the key to the past abstract radiolarian productivity pulses and related radiolarite deposition are phenomena difficult to understand from an exclusively actualistic viewpoint evolutionary selection pressure among silica secreting marine plankton both radiolarians and diatoms has led toward more economic usage of rapidly shrinking nutrient resources including dissolved silica of the photic zone in the late cenozoic oceans and in particular a substantial modification of oceanic cycle by the diatom explosive radiation even if there is a proved link between biomineralization and dissolved silica loading among the phytoplankton only the relative independence of modern siliceous planktic biotas from the available silica pool reflects mainly their progressive physiological specialisation during evolutionary history oceanic chemistry and productivity as well as patterns of circulation upwelling have changed radically during the phanerozoic radiolarites apparently represent an anachronistic facies as exemplified by their long lived and ocean wide distribution in palaeo pacific and hitherto highlighted actualistic models of localized intra oceanic wind driven upwelling loci are of largely questionable applicability in addition to plate drift hypersiliceous domains and intervals are explainable mostly by a large scale volcano hydrothermal activity during major plate boundary reconfigurations which in many ways favoured siliceous biotas acme and their skeletal remains accumulation and preservation factors tied to rapid voluminous submarine eruptions such as thermal buoyant megaplumes and basin overturns offer a viable alternative for traditional climatic circulation scenarios in case of hypersiliceous high productivity events irrelevant to greenhouse to icehouse climatic change the evolving carbon and silica cycles were coupled through the greenhouse effect and enhanced chemical weathering volcano hydrothermal and tectonic uplift events related mostly to extensive rifting and or accelerated oceanic spreading were the endogenous driving force that created this perturbation of the exogenous system the present biogeochemical cycle is representative only for the overall silica depleted post eocene oceanic ecosystems which broadly correlates with a major expansion of diatoms groups extremely efficient in silica removal and closely linking the silica budget with phosphorus and nitrogen cycles thus an orthodox uniformitarian approach to biosiliceous sedimentation based on a silica starved vigorous ocean is of limited significance when applied to the pre neogene settings especially in the peculiar planktic habitats of epeiric seas as well as during biotic crises marked by strong geotectonic overprint the major turnovers in marine siliceous biota composition in particular after the end permian radiolarite gap may have been coupled with discernible changes in an increasing biological control on the long term oceanic silica cycling punctuated equilibrium the evolutionary turnovers have induced a stepdown decrease of dissolved silica levels through the phanerozoic contemporaneously with the general secular trend of upward scaling of nutrient related ecological processes and increased effectiveness of resource utilization

a first look at the distribution of the stable isotopes of silicon in natural waters the first data on the distribution of the stable isotopes of silicon in marine and freshwater systems are reported both marine and riverine 30si are more positive than 30si of igneous rocks suggesting isotopic fractionation during weathering and clay formation and or biomineralization the 30si value for dissolved silicic acid from several ocean basins is 1 1 0 3 n 69 more positive values are found in surface waters due to discrimination against 30si during biogenic opal formation by diatoms the deep pacific ocean is depleted in 30si relative to the deep atlantic by roughly 0 4 30si of riverine dissolved silicon averages 0 8 0 3 n 8 the biologic fractionation of silicon isotopes coupled with effects associated with thermohaline circulation appears to play a significant role in controlling the distribution of silicon isotopes in the sea the average 30si value of inputs of silicon to the ocean most likely falls between 0 3 and 0 9 and that of the outputs falls between 0 9 to 1 9 probably in the neighborhood of 1 0

sedimentation and lithofacies paleogeography in southwestern china before and after the emeishan flood volcanism new insights into surface response to mantle plume activity abstract investigations into permian sedimentation and reconstruction of paleogeography in sw china are aimed at characterizing sedimentary responses to the emeishan mantle plume in addition to erosional features on the sediments underlying the uplifted emeishan basalts unusual depositions of permian age are also present in the emeishan large igneous province lip specifically carbonate gravity flows and submarine incised canyon fillings were developed in the western margin of the postulated uplifted area and rifting trenches were developed along the eastern margin alluvial fan deposits occur at the boundary between the inner and intermediate zones these depositions all rest on the maokou formation and are in turn covered by the emeishan basalts implying synchronism between crustal uplift and depositional events these deposits and the associated extension and normal faulting along the margin of and within the lip represent sedimentary features resulting from dynamic behavior of mantle plume com

stratigraphic changes of ge si ree y and silicon isotopes as insights into the deposition of a mesoarchaean banded iron formation in order to determine the origin of silicon si in banded iron formation bif we have undertaken a multi tracer study combining ree y data ge si ratios and si isotopes d 30 si on stratigraphically resolved layers from a 2 95 ga bif from the pongola supergroup south africa si in both si rich and fe rich layers has a common origin represented by a seawater reservoir strongly influenced by continent derived freshwaters 10 and very limited o 0 1 high t hydrothermal fluids as indicated by eu anomalies and y ho ratios the coevolution of d 30 si signatures of si and fe rich

mixed seawater and hydrothermal sources of nodular chert in middle permian limestone on the eastern paleo tethys margin south china abstract middle permian limestone and marl of the maokou formation deposited along the eastern paleo tethys margin south china host abundant chert nodules that formed in association with the global permian chert event pce an enhanced understanding of the origin of the chert may help elucidate middle permian oceanic and diagenetic conditions however the mechanisms responsible for the formation of chert especially the source of silica remain controversial maokou chert nodules which are made up of quartz and subordinate calcite hematite pyrite and fluorite and rimmed by f bearing sepiolite laminae appear to have formed mainly by the replacement of precursor nodular limestone by silica the nodular limestone may have formed by differential compaction of interbedded limestone and marl after which carbonate was replaced gradually outward from nodule centers by dissolved silica released from the dissolution of siliceous skeletal grains including spicules and radiolarians in host marl during early diagenesis the introduction of high t hydrothermal fluids into ocean water is evidenced by the presence of f bearing minerals fluorite and sepiolite a hybrid rare earth element ree y pattern and a wide range of 30si values 0 4 to 0 7 documented from the maokou nodular chert conservative estimation indicated that middle permian seawater may have had a 30si composition 0 7 to 1 8 similar to that of modern open ocean water suggesting that seawater was the dominant silica source of nodular chert mixing calculations based on ree y geochemistry suggest additional contributions of ca 0 05 0 2 high t hydrothermal fluid and ca 1 10 of continental derived freshwater to ocean water such increased influx of silica to seawater may have been related to the early rifting induced by emeishan volcanism and intensified chemical weathering during an interglacial period which played an important role in promoting the flourishing of siliceous organisms and subsequent chert enrichment during the middle permian

permian palaeogeographic evolution of the jiangnan basin south china abstract the most striking geographic feature of the permian of south china is the jiangnan basin which intimately reflects the interplay between the yangtze and cathaysia blocks geographic and sedimentological evolution suggests that the jiangnan basin superposed on a precambrian collisonial megasuture and a folded early paleozoic deep basin was an extensional intracratonic basin it opened in the longlinian and became more passive and restricted in the latest maokouan the remarkably similar geographic patterns of the jiangnan basin in the early and late palaeozoic suggest that the yangtze and cathaysia blocks were coherent during the paleozoic

permian ice volume and palaeoclimate history oxygen isotope proxies revisited abstract a high resolution oxygen isotope record based on 356 measurements of conodont apatite from several low latitudinal sections in south china usa and iran was composed in order to unravel permian palaeotemperature and ice volume history the conodont apatite 18 o record is compared to published brachiopod calcite 18 o records brachiopods and conodonts from different palaeocontinents show significantly different 18 o values suggesting differences in local climatic conditions e g evaporation precipitation ratio as a consequence secular changes in palaeotemperature and oxygen isotope composition of permian sea water cannot be reconstructed from records combined from different areas but have to be based on records from a specific area oxygen isotope analyses of different conodont taxa suggest that streptognathodus and hindeodus lived in near surface seawater and recorded surface water temperature whereas the habitat of gondolellid genera was variable depending on sea level with both near surface and deeper waters as potential life habitat the oxygen isotope record measured on conodonts from south china exhibits relative high values between 22 and 23 vsmow during the glaciated early permian translating into warm seawater temperature between 26 and 30 c assuming that the late palaeozoic ice volumes were comparable to the pleistocene glacial maxima in contrast to the earlier view that the late palaeozoic ice age lpia terminated in the late sakmarian the south china conodont apatite oxygen isotope record suggests waning of the ice sheets in the kungurian ice melting is indicated by a pronounced decrease in 18 o of 2 vsmow which is interpreted as reflecting the combined effect of climatic warming and glacial ice melting significant temperature fluctuations 4 c warming succeeded by 6 to 8 c cooling are observed during the guadalupian lopingian transition interpreted as combined climate changes induced by emeishan volcanism and changes in habitat depth of gondolellid conodonts oxygen isotope values increase to 22 vsmow in the changhsingian which suggests climate cooling and clarkina moving to deeper waters because of the changhsingian sea level rise across the permian triassic boundary 18 o values decrease from 22 to 19 vsmow parallel to the significant negative carbon isotope excursion and the eruption of the siberian traps the latter is pointing to a cause effect relationship as a consequence of the massive release of volcanic greenhouse gases derived from the siberian volcanism and related processes

paleoredox variations in ancient oceans recorded by rare earth elements in fossil apatite abstract rare earth element concentrations in biogenic apatite of conodonts fish debris and inarticulate brachiopods were determined in over 200 samples from cambrian to modern sediments tests for experimental bias caused by the chemicals used to separate fossils from the rock matrix and for interlaboratory interexperiment or interspecies related variations clearly show that no resolvable fractionation of ree occurs incorporation of ree in biogenic apatite of recent fish debris occurs near the sediment water interface soon after deposition and reflects characteristics of seawater the original ree signature apparently survives subsequent burial and diagenesis cerium variations in fish debris from modern environments are controlled by redox potential ce is fractionated by co precipitation with metallic oxides under oxidizing conditions this fractionation produces a negative ce anomaly ce anom in seawater that is reflected in the sedimented fish debris conversely no fractionation of ce occurs under reducing conditions resulting in ce concentrations that are normal to enriched in anoxic seawater and fish debris deposited under local or basinwide anoxic conditions extrapolation of observations of the redox control of ce anom in modern oceans to fossil apatite indicates that anoxic conditions were prevalent in lower paleozoic and lower triassic oceans whereas in the upper paleozoic the world ocean was generally oxidizing

age and timing of the permian mass extinctions u pb dating of closed system zircons the age and timing of the permian triassic mass extinction have been difficult to determine because zircon populations from the type sections are typically affected by pervasive lead loss and contamination by indistinguishable older xenocrysts zircons from nine ash beds within the shangsi and meishan sections china pretreated by annealing followed by partial attack with hydrofluoric acid result in suites of consistent and concordant uranium lead u pb ages eliminating the effects of lead loss the u pb age of the main pulse of the extinction is 252 6 0 2 million years synchronous with the siberian flood volcanism and it occurred within the quoted uncertainty

composition and correlation of volcanic ash beds of silurian age from the eastern baltic sanidine composition and bulk geochemistry of volcanic ash beds from the east baltic indicate the subalkaline nature of the volcanism near the margins of the baltica plate during the silurian several bentonites in the wenlock include a previously unknown sanidine with 48 to 58 mol of the na ca component in contrast to the earlier telychian volcanism sodium rich sanidine occurs in ash beds which originate from relatively moderately evolved dacitic magma the studied material from two drill cores integrated with previous research enables production of a more complete list of 49 volcanic eruption layers for the lower to middle wenlock in the east baltic this updated list of bentonites characterized by their sanidine compositions forms a good basis for future integrated bio and chemostratigraphic correlations in northern europe

interoceanic variation in the rare earth major and trace element depositional chemistry of chert perspectives gained from the dsdp and odp record rare earth element ree major and trace element abundances and relative fractionations in forty nodular cherts sampled by the deep sea drilling project dsdp and ocean drilling program odp indicate that the ree composition of chert records the interplay between terrigenous sources and scavenging from the local seawater major and non ree trace element ratios indicate that the aluminosilicate fraction within the chert is similar to nasc north american shale composite with average pacific chert including 7 nasc like particles indian chert 11 nasc atlantic chert 17 nasc and southern high latitude shl chert 53 nasc using la as a proxy for ree approximations of laex the amount of la in excess of that supplied by the detrital aluminosilicate fraction indicate that pacific chert contains the greatest laex 85 of latotal and shl chert the least 38 of latotal as shown by interelement associations this laex is most likely an adsorbed component onto aluminosilicate and phosphatic phases accordingly chert from the large pacific ocean where deposition occurs relatively removed from significant terrigenous input records a depositional ree signal dominated by adsorption of dissolved rees from seawater pacific chert cece 1 and lanybn 0 8 1 resulting from adsorption of local ce depleted seawater and preferential adsorption of lrees from seawater e g lanybn 0 4 which increases the lanybn ratio recorded in chert chert from the atlantic basin a moderately sized ocean basin lined by passive margins and with more terrigenous input than the pacific records a mix of adsorptive and terrigenous ree signals with moderately negative ce anomalies and lanybn ratios intermediate to those of the pacific and those of terrigenous input chert from the shl region is dominated by the large terrigenous input on the antarctic passive margin with inherited cece 1 and inherited lanybn values of 1 2 1 4 cece does not vary with age either throughout the entire data base or within a particular basin overall cece does not correlate with p2o5 concentrations even though phosphatic phases may be an important ree carrier this and previous studies of the large scale controlling parameters of sedimentary rees across ocean basins collectively indicate that ree indices of depositional regime e g cece lanybn laex are reproducible in a variety of sediment and rock lithologies ages and ocean basins and present a coherent tool for paleoceanographic and tectonic basin reconstructions

remarkable preservation of microbial mats in neoproterozoic siliciclastic settings implications for ediacaran taphonomic models abstract it is beyond doubt that the appearance of infaunal bioturbation and metazoan biomineralization across the ediacaran cambrian transition irreversibly affected the nature of marine sediment architecture and biogeochemistry here we review those changes in relation to their likely effect upon the processes of fossil preservation especially within siliciclastic sediments processes of soft tissue preservation in siliciclastic settings from the ediacaran period including microbes and microbial mats as well as ediacaran macrofossils are here reviewed within this context highlighted examples include the exceptional preservation of microbes found in association with wrinkle structures and ediacaran macrofossils in england and newfoundland replicated by silicate minerals and in the white sea region of russia replicated by iron sulphide these occurrences show that soft tissue preservation in siliciclastic settings went well beyond that typical for ediacaran macrofossils alone and also extended to similar modes of preservation in associated microbes using these new observations it can be argued that several existing explanations for ediacaran fossil preservation can be united within a biogeochemical model that involves evolution of the sediment mixed layer across this transition

a mid permian chert event widespread deposition of biogenic siliceous sediments in coastal island arc and oceanic basins abstract radiolarian and conodont of permian siliceous rocks from twenty three areas in teh the circum pacific and mediterranean regions reveal a widespread permian chert event during the middle leonardian to wordian radiolarian and or sponge spicule rich siliceous sediments accumulated beneath high productivity zones in coastal island arc and oceanic basins most of these deposits now crop out in fault bounded accreted terranes biogenic siliceous sediments did not accumulate in terranes lying beneath infertile waters including the marine sequences in terranes of northern and central alaska the permian chert event is coeval with major phosphorite deposition along the western margin of pangea phosphoria formation and related deposits a well known analogue for this event is middle miocene deposition of biogenic siliceous sediments beneath high productivity zones in many parts of the pacific and concurrent deposition of phosphatic as well as siliceous sediments in basins along the coast of california interrelated factors associated with both the miocene and permian depositional events include plate reorientations small sea level rises and cool polar waters

sedimentary environments of the middle permian phosphorite chert complex from the northeastern yangtze platform china the gufeng formation a continental shelf radiolarian chert abstract radiolarian chert deposited on a continental shelf occurs in the middle permian gufeng formation on the northeastern yangtze platform china the sedimentary environments of radiolarian cherts from accretionary complexes have been well studied however there are few studies about radiolarian chert deposited on continental shelves therefore we have completed a sedimentological and geochemical study of the gufeng formation the gufeng formation is subdivided into the phosphate nodule bearing mudstone member pnmm and the siliceous rock member srm in ascending order the basal pnmm consists of glauconite bearing mudstone which indicates deposition under aerobic shallow marine conditions whereas the upper pnmm is composed of mudstone including abundant phosphate nodules suggesting deposition near the outer shelf in suboxic conditions the srm consists mainly of alternating beds of black chert mudstone and siliceous mudstone with minor tuffaceous mudstone and porous chert beds the black chert contains abundant radiolarians sponge spicules and organic matter framboidal pyrite occurs in the black chert porous chert in the srm includes abundant rhombohedral cavities which are dolomite moulds surrounded by quartz suggesting dolomitization before silicification during early diagenesis the gufeng chert is characterized by high si mo ni cu and zn contents and extremely low mn content the gufeng chert has high normal paraffin concentrations with petroleum like markers these geochemical features suggest that the gufeng chert was deposited under sulfate reducing conditions and is not hydrothermal but rather biogenic in origin the sedimentological and geochemical data suggest that the gufeng formation was deposited mainly on the outer shelf in suboxic anoxic conditions caused by organic matter produced during upwelling the upwelling probably led to high radiolarian productivity abundant silica and organic matter were deposited in the gufeng basin compared with chert from other sites the gufeng chert shows many similarities with chert from platformal basins but not with chert from accretionary complexes especially with respect to age rock type stratigraphy and geochemical features the chert of the gufeng formation is similar to that of the phosphoria formation in the western u s a which is a world class phosphorite giant these similarities suggest that upwelling occurred around the eastern margins of panthalassa and the paleotethys concurrently during the middle permian in general shelf type radiolarian chert represented by the gufeng chert usually shows some of the following features dark color lack of rhythmical bedding association with phosphorite platformal limestone felsic tuff abundant organic matter and sulfides shelf type radiolarian chert is deposited in a poorly aerated restricted basin or in an oxygen minimum zone

silicon isotope compositions of dissolved silicon and suspended matter in the yangtze river china abstract silicon isotope compositions of main channel samples of the yangtze river were systematically investigated along with their chemical compositions the concentration of suspended matter in the yangtze river tends to decrease from the upper reaches to the lower reaches corresponding to settling of the sediments in the lakes and reservoirs due to reduction of the velocity of water flow the silica contents of suspended matter vary from 52 1 to 56 9 and their 30si values vary from 0 to 0 7 both similar to those of shales from the upper to lower reaches the silica contents of suspended matter tend to increase whilst their 30si values tend to decrease both trends reflect the increase of clay minerals and decrease of carbonates in suspended matter the concentrations of dissolved silicon vary from 97 to 121 mol l and their 30si values vary over a wide range from 0 7 to 3 4 from the upper to lower reaches dissolved silica concentrations tend to decrease and their 30si values tend to increase these trends mainly reflect the change of chemical and isotopic characteristics of the tributaries from the upper to lower reaches the major factors responsible for these changes may be the high meteoric precipitation and significant silicon absorption by grass in wetlands and rice in paddy fields in drainage areas of the middle and lower reaches there is no correlation between 30si of dissolved silicon and that of suspended matter the 30sidiss spm values vary over a wide range of 1 0 3 7 indicating that 1 they are out of isotopic equilibrium 2 dissolved silicon and the associated suspended matter do not belong to one physico chemical system and 3 isotopic exchange rate between them is very slow the 30si value of dissolved silicon output from the yangtze river to the east sea is estimated to be 3 0 much higher than the values reported for the amazon and congo rivers this increases the 30si range of dissolved silicon in the world s rivers from 0 4 1 2 to 0 4 3 4

determining the diagenetic conditions of concretion formation assessing temperatures and pore waters using clumped isotopes carbonate 18 o paleothermometry is used in many diagenetic studies to unravel the thermal history of basins however this approach generally requires an assumed pore water 18 o 18 o pw value a parameter that is difficult to quantify in past regimes in addition many processes can change the original isotopic composition of pore water which further complicates the assignment of an initial 18 o pw and can lead to erroneous temperature estimates here we use clumped isotope thermometry a proxy based on the 13 c 18 o bond abundance in carbonate minerals to evaluate the temperatures of concretion formation in the miocene monterey formation and the cretaceous holz shale california these temperatures are combined with established carbonate water fractionation factors to calculate the associated 18 o pw results demonstrate that diagenetic processes can modify the 18 o of ancient pore water confounding attempts to estimate diagenetic temperatures using standard approaches clumped isotope based temperature estimates for monterey formation concretions range from 17 to 35 c up to 12 c higher than traditional 18 o carbonate water paleothermometry when 18 o pw values are assumed to equal miocene seawater values calculated 18 o pw values range from 0 3 to 2 5 vsmow higher than coeval miocene seawater likely due to 18 o pw modification accompanying diagenesis of sedimentary siliceous phases clumped isotope temperatures for the holz shale concretions range from 33 to 44 c about 15 to 30 c lower than temperatures derived using the traditional method calculated 18 o pw values range from 5 0 to 2 9 and likely reflect the influx of meteoric fluids we conclude that the use of clumped isotopes both improves the accuracy of temperature reconstructions and provides insight into the evolution of 18 o pw during diagenesis addressing a longstanding conundrum in basin evolution research

chert in the pacific biogenic silica and hydrothermal circulation abstract data on sections drilled by dsdp and odp in the pacific have been compiled for 187 sites 105 of which contain chert the spatial pattern of siliceous deposits in the pacific generally follows the pattern of biologic productivity there is some evidence that enhanced vertical diffusivity in the ocean during the eocene warm climate gave rise to siliceous deposits on and near bathymetric highs and basin margins the most common occurrence of chert is in eocene and older sections however cherts do occur in sections as young as 7 ma in the sites investigated over half of the youngest chert occurrences in sedimentary sections are within 150 m of basement nearly all the chert occurrences on crust younger than 60 ma are within 150 m of basement the deficit in heat flow over ocean crust younger than 60 ma is explained as the result of heat advection by hydrothermal waters circulating in the upper part of the ocean crust these waters appear to dissolve biogenic silica and deposit it as chert in the lower parts of sedimentary sections diffusion of these waters into the lower sediment section is enhanced by small scale faulting this faulting may be associated with intra plate stresses that develop during ridge jumps and reorientations of plate motion the relatively warm bottom waters of the early cenozoic may have also enhanced the dissolution of biogenic silica during hydrothermal circulation in the upper oceanic crust and basal sediment section

sources and depositional environments of some permian and triassic cherts significance of rb sr and sm nd isotopic and ree abundance data abstract rb sr and sm nd isotopic data rare earth element ree abundances and major element compositions are reported for the triassic cherts of the mino terrane in the inner zone of southwest japan and for the permian and triassic cherts of the sambosan terrane in the outer zone of southwest japan rb sr isotopic data of the mino and sambosan cherts define separate isochron lines and the rb sr ages of ca 210 and 240 ma reflect the chert deposition and the end of the subsequent chemical diagenesis during which amorphous silica was transformed into quartz it is concluded that the rb sr isotopic system of the cherts becomes essentially homogenized among biogenic silica detrital components and hydrogeneous components during deposition and the subsequent chemical diagenesis before lithification due to high mobility of rb and sr the sr initial ratio 0 71363 of the triassic mino cherts is clearly higher than those 0 7079 and 0 7068 of the triassic and permian sambosan cherts which are close to th

the end permian regression in south china and its implication on mass extinction abstract records of more than 20 permian triassic boundary ptb sections from south china show that widespread end permian regression took place in whole south china timing of the low ebb of this regression was pinpointed to the clarkina meishanensis and hindeodus changxingensis zones biostratigraphic and paleogeographic studies at conodont zonation level reveal that the yangtze carbonate platform and isolated small carbonate platforms in the hunan guizhou guangxi hgg basin experienced sedimentary hiatus during these two zones which lasted about 50 100 kya meanwhile the basinal areas namely the northern marginal basin of yangtze platform and the hunan guizhou guangxi basin have continuous conodont zonation with silicious and ashbed deposits the basinal areas show two negative 13c shifts during the ptb interval from clarkina yini zone to isarcicella isarcica zone while on the platforms there is usually only one negative shift because the early shift at c meishanensis zone was lost during hiatus the end permian regression and successive rapid transgression taking place at the ptb casted important effects to the pattern and process of the ptb mass extinction the depositional hiatus hitherto underestimated will necessitate reassessment of some interpretations on the causes and results of that extinction

growth and demise of permian biogenic chert along northwest pangea evidence for end permian collapse of thermohaline circulation abstract the permian chert event pce was a 30 ma long episode of unusual chert accumulation along the northwest margin of pangea and possibly worldwide the onset of the pce occurred at about the sakmarian artinskian boundary in the sverdrup basin canadian arctic where it coincides with a maximum flooding event the ending of high frequency high amplitude shelf cyclicity the onset of massive biogenic chert deposition in deep water distal areas and a long term shift from warm to cool water carbonate sedimentation in shallow water proximal areas a similar and coeval shift is observed from the barents sea to the northwestern usa a landward and southward expansion of silica factories occurred during the middle and late permian at which time warm water carbonate producers disappeared completely from the northwest margin of pangea biotically impoverished and increasingly narrow cold water carbonate factories characterised by non cemented bioclasts of sponges bryozoans echinoderms and brachiopods were then progressively replaced by silica factories by late permian time little carbonate sediments accumulated in the barents sea and in the sverdrup basin where the deep to shallow water sedimentary spectrum was occupied by siliceous sponge spicules by that time biogenic silica sedimentation was common throughout the world silica factories collapsed in the late permian abruptly bringing the pce to an end in northwest pangea the end permian collapse of the pce was associated with a major transgression and with a return to much warmer oceanic and continental climatic conditions chert deposition resumed in the distal oceanic areas during the early middle triassic anisian after a 8 10 ma interruption early triassic chert gap the conditions necessary for the onset expansion and zenith of the pce were provided by the thermohaline circulation of nutrient rich cold waters along the northwestern and western margin of pangea and possibly throughout the world oceans these conditions provided an efficient transportation mechanism that constantly replenished the supply of silica in the area created a nutrient and oxygen rich environment favouring siliceous biogenic productivity established cold sea floor conditions hindering silica dissolution while increasing calcium carbonate solubility and provided conditions adverse to organic and inorganic carbonate production the northwest margin of pangea was for nearly 30 ma bathed by cold waters presumably derived from the seasonal melting of northern sea ice the assumed engine for thermohaline circulation this process started near the sakmarian artinskian boundary intensified throughout middle and late permian time and ceased suddenly in latest permian time it led to oceanic conditions much colder than normally expected from the palaeolatitudes and the influence of cold northerly derived water was felt as far south southern nevada the demise of silica factories was caused by the rapid breakdown of these conditions and the establishment of a much warmer marine environment accompanied by sluggish circulation and perhaps a reduced input of dissolved silica to the ocean complete thawing of northern sea ice would have ended thermohaline circulation and led to warm and sluggish oceanic conditions inimical to the production accumulation and preservation of biogenic silica

texture specific si isotope variations in barberton greenstone belt cherts record low temperature fractionations in early archean seawater sedimentary cherts are unusually abundant in early archean pre 3 0 ga sequences suggesting a silica cycle that was profoundly different than the modern system previously applied for the purpose of paleothermometry si isotopes in ancient cherts can offer broader insight into mass fluxes and mechanisms associated with silica concentration precipitation diagenesis and metamorphism early archean cherts contain a rich suite of sedimentological and petrographic textures that document a history of silica deposition cementation silicification and recrystallization to add a new layer of insight into the chemistry of early cherts we have used wavelength dispersive spectroscopy and then secondary ion mass spectrometry sims to produce elemental and si and o isotope ratio data from banded black and white cherts from the onverwacht group of the barberton greenstone belt south africa this geochemical data is then interpreted in the framework of depositional and diagenetic timing of silica precipitation provided by geological observations sims allows the comparison of si and o isotope ratios of distinct silica phases including black carbonaceous chert beds and bands many including well defined sedimentary grains white relatively pure chert bands including primary silica granules early cavity filling cements and later quartz filled veins including all chert types and textures analyzed the 30 si dataset spans a range from 4 78 to 3 74 with overall mean 0 20 median 0 51 and standard deviation 1 30 n 1087 most samples have broadly similar 30 si distributions but systematic texture specific 30 si differences are observed between white chert bands mean 0 60 n 750 which contain textures that represent primary and earliest diagenetic silica phases and later cavity filling cements mean 1 41 n 198 we observed variations at a 100 m scale indicating a lack of si isotope homogenization at this scale during diagenesis and metamorphism although fractionations during diagenetic phase transformations may have affected certain textures we interpret these systematic variations to reflect fractionation during silica precipitation as well as isotopically distinct fluids from which later phases originated sims 18 o values fall in a range from 16 39 to 23 39 n 381 similar to previously published data from bulk gas source mass spectrometry of onverwacht cherts we observed only limited examples of texture related variation in 18 o and did not observe correlation of 18 o with 30 si trends this is consistent with hypotheses that si isotope ratios are more resistant to alteration under conditions of rock buffered diagenesis marin carbonne et al 2011 our results indicate that low temperature processes fractionated silicon isotopes in early archean marine basins a behavior that probably precludes the application of chert 30 si as a robust paleothermometer the values we observe for facies that sedimentological and petrographic observations indicate formed as primary and earliest diagenetic silica precipitates from seawater are more 30 si rich than that expected for bulk silicate earth this is consistent with the hypothesis that the silicon isotope budget is balanced by the coeval deposition of 30 si enriched cherts and 30 si depleted iron formation lithologies precipitation of authigenic clay minerals in both terrestrial and marine settings may have also comprised a large 30 si depleted sink with the corollary of an important non carbonate alkalinity sink consuming cations released by silicate weathering

basaltic activity preserved in an upper permian radiolarian chert from the paleo tethys in the inthanon zone northern thailand basaltic sandstone composed mainly of clay to sand sized fragments of glass and basaltic rock has been discovered in a pelagic chert sequence in northern thailand the sandstone conformably underlies and is partly intercalated with the upper permian wuchiapingian early changhsingian radiolarian bearing chert geological age dating based on radiolarians petrographic examination of the bedded chert with the basaltic sandstone and geochemical studies were conducted to investigate the origin and sedimentary mode of the lithologic sequence the bedded chert overlying the basaltic sandstone yielded late permian radiolarians and was correlatable with the wuchiapingian follicucullus charveti albaillella yamakitai assemblage zone as well as the early changhsingian neoalbaillella ornithoformis assemblage zone lithofacies and microfacies of the bedded chert indicated deposition in a pelagic realm of the paleo tethys although the tectonic setting was difficult to estimate based on geochemical features because of element mobility and alteration the basaltic fragments likely originated as oceanic basalt such as oceanic island basalt microfacies and sedimentary structures of the chert and sandstone indicated that the studied sequence is composed of intermittent high sedimentation rates mainly gravity currents of basaltic fragments in a background setting of very slowly accumulating radiolarian chert the sedimentary mode of the sequence the rare terrigenous influx and the presence of fusulinoidean or other foraminiferal tests indicate that the basaltic rocks fragment were originally sourced from an oceanic topographic high such as a seamount or an oceanic plateau and that the volcanic activity occurred in the chert accumulated oceanic basin of the paleo tethys in the wuchiapingian

trace element behavior and redox facies in core shales of upper pennsylvanian kansas type cyclothems the black shale submember of core shales of pennsylvanian kansas type cyclothems is highly enriched in redox sensitive trace elements tes relative to the overlying gray shale submember as well as to many other modern and ancient organic rich deposits controls on trace element behavior in the black shale can be inferred from trace element enrichment factors efs relative to gray shale and the relationship of tes to total organic carbon toc most tes conformed to one of two patterns 1 mo u v zn and pb exhibited moderate efs and strong covariation with toc in samples having 10 wt toc and 2 cu ni cr and co exhibited low efs and moderate to strong covariation with toc in all samples these patterns are inferred to represent different responses to benthic redox conditions the first pattern is characteristic of tes of strong euxinic affinity i e those taken up in solid solution by fe sulfide or involved in other reactions catalyzed by free h2s and resident mainly in authigenic phases whereas the second pattern is characteristic of tes of weak euxinic affinity i e those not strongly influenced by the presence of free h2s and resident mainly in the organic carbon or detrital fractions of the sediment these inferences allowed development of a multiproxy technique for assessing redox facies in black shale samples euxinic conditions were considered to have existed if at least two of four redox indicator trace elements mo u v zn showed euxinic levels of enrichment and nonsulfidic anoxic conditions were inferred otherwise the validity of the procedure is indicated by 1 agreement among all four redox indicators for a large majority of samples 69 of 185 2 among samples yielding a mixed redox signal a systematic sequence of te enrichment v zn mo u and 3 for tes of weak euxinic affinity reduced variance among samples representing each redox facies sequential enrichment may be a response to differential redox thresholds for accumulation e g v or postdepositional remobilization of trace elements e g u and may provide a basis for finer assessment of redox conditions in low oxygen paleoenvironments than permitted by simple classification schemes the multiproxy procedure for redox facies analysis developed in this study is likely to be more reliable than widely used single proxy indicators based on trace elements e g mo authigenic u or v v ni or c s fe systematics e g s toc or dop d 2004 elsevier b v all rights reserved

controls of sea level fluctuations on the formation of ordovician siliceous nodules in terrigenous offshore environments abstract siliceous nodules of the ordovician period of the armorican massif and of southwest sardinia are made of a mixture of terrigenous origin material quartz and phyllosilicates and of biogenic origin components microcrystalline quartz calcium phosphate and calcite they are associated with fine grained sequences which were deposited between the distal part of the inner shelf and the outer shelf within these sequences two facies can be distinguished clayey silty facies without nodules related to episodes of high sedimentation rate and nodule bearing clayey facies linked to episodes of reduced sedimentation the genesis of the siliceous nodules can be integrated into a model taking account of the fluctuations in terrigenous flux due to eustatic variations during periods of rising sea level the terrigenous flux decreases and the sedimentation is dominated by bioclastic elements calcareous siliceous and phosphatic stability of the sediment water interface facilitates biogenic silica dissolution during early diagenesis silica precipitation leads to the formation of proto nodules the distribution of the two facies can be explained by the superposition of two eustatic signals one of very high frequency vhf and the other of high frequency hf the silty clayey facies could be accumulated during the period of falling sea level within the hf cycle and the nodule bearing clayey facies could correspond to amalgamation of several vhf cycles related to periods of low sedimentation rate in the hf cycle

rare earth element cycling in the pore waters of the bering sea slope iodp exp 323 abstract we studied the diagenetic behavior of rare earth elements rees in a highly productive passive margin setting of the bering sea slope site u1345 was drilled during the integrated ocean drilling program expedition 323 at a water depth of 1008 m currently in the center of an oxygen minimum zone pore water concentrations of fourteen rees were determined down to 140 meters below the seafloor mbsf the ree concentrations were higher in the pore water than the deep seawater indicating that there was significant liberation from the sediments during diagenesis there was a major peak at 10 mbsf that was more pronounced for the heavy ree hree this peak occurred below the sulfate methane transition zone 6 3 mbsf and coincided with high concentrations of dissolved iron and manganese at 2 mbsf there was a minor peak in ree and mn contents below 40 mbsf the ree concentration profiles remained constant the ce anomaly was insignificant and relatively constant paas normalized ce ce 1 1 0 2 throughout the depth profile showing that the ce depleted in seawater was restored in the pore water hree enrichment was observed over the entire 140 m except for the upper 1 m where a middle ree mree bulge was apparent ree release in shallow depths 2 4 mbsf is attributed to the release of light rees lrees and mrees during the organoclastic reduction of mn oxides in anoxic sediments the high hree concentrations observed at 10 mbsf can be attributed to the reduction of fe and mn minerals tied to anaerobic oxidation of methane or less significantly to ferromagnesian silicate mineral weathering the upward diffusion flux across the sediment water interface was between 3 for tm and 290 for ce pmol m 2 y 1

biological fractionation of silicon isotopes in southern ocean surface waters 1 the fractionation of silicon isotopes by diatoms during silicification i e opaline cell wall formation provides a new tool for paleoceanographic studies of the silicon cycle here we examine the natural variations of the 30si 28si ratio in silicic acid si oh 4 and biogenic silica bsio2 in surface waters of the antarctic circumpolar current acc along 170 w the results provide direct evidence of biologically mediated fractionation of silicon isotopes with an enrichment factor of between 1 1 and 1 9 depending on the model employed comparison of the mass flux of bsio2 captured in sediment traps deployed in the study area with the silicon isotopic composition of that material establishes a direct linkage between diatom dynamics in surface waters and the isotopic signature of exported particles we calculated si oh 4 no3 utilization ratios from variations in silicon and nitrogen isotopic ratios in surface waters and sediment traps that agree well with direct observations of 4 1 in this region this work supports the use of variations in silicon isotopes in sedimentary opal as a proxy for relative si oh 4 utilization in surface waters

emeishan basalts sw china and the end guadalupian crisis magnetobiostratigraphic constraints abstract a magnetostratigraphic investigation of the permian emeishan lip large igneous province was carried out on a composite section in ebian county close to the type area in sichuan sw china the main succession of twelve flows 175 m thick carries a normal polarity whilst the one reliable site from the overlying 30 m thick volcanic waning sequence is marked by a reverse polarity the data enable a correlation to be proposed with an emeishan basalt sequence in western guizhou c 400 km to the se from our knowledge of the geomagnetic field9s reversal behaviour during the permian it suggests that the main lava pile along the eastern half of the emeishan basalt outcrop belt was erupted within a half to one million years using magnetobiostratigraphic data from the adjacent south china platform the normal polarity magnetozone is correlated with the normal polarity chron associated with the upper part of the maokou limestones constrained by conodont data the main emei basalts appear to be at least two biozones older 1 1 5 ma than the mid late permian boundary it is possible however that the emei basalt waning zone sequence which represents an explosive volcanic phase might be coeval with the end guadalupian biotic crisis thus arguments implicating emei basalt volcanism as the causal mechanism behind this major global event have to accommodate the new relative age constraints

nodular chert formation in carbonate rocks mapping of carbonate dissolution in nodular chert bearing strata indicates that nodular chert formation in a diverse suite of phanerozoic limestones occurred in bulk pore waters that were at calcite saturation opal ct and quartz supersaturation was achieved in most chert bearing strata by the intraformational dissolution of amorphous silica skeletal material chertification occurred by a combination of force of crystallization controlled replacement of the host carbonate whereby non hydrostatic stresses resulting from opal ct and quartz crystal growth caused calcite dissolution and the isomineralic heterogenous nucleation of new opal ct and quartz crystal at nodule peripheries the restriction of the solution phase at silica carbonate contacts to thin films permitted the preservation of ghosts of micron sized features in the chert heterogeneities in sediment organic matter content porosity and biogenic silica concentrations promote the nucleation of chert nodules in some formations

astronomical forcing of a middle permian chert sequence in chaohu south china abstract astronomical forcing has been shown to be a fundamental driver of climate change through geological time pelagic bedded cherts deposited in mesozoic ocean basins with chert mudstone cycles have been shown to contain the imprint of milankovitch astronomical climate forcing in the chaohu region south china we studied a middle permian radiolarian chert sequence gufeng formation with chert mudstone couplets reminiscent of the mesozoic cherts but deposited on a continental shelf spectral analysis of lithologic bed thickness data from two sections of this chert sequence reveals that 13 cm to 20 cm chert mudstone cycles in the stratigraphic domain match theoretical 32 kyr middle permian obliquity cycling together with a hierarchy of other cycles with 12 cm 9 cm 7 cm 6 6 cm and 5 4 cm wavelengths tuning the 13 cm to 20 cm stratigraphic cycles to earth s obliquity cycle periodicity indicates that the cm scale cycles are precession scale variations with a strong 400 kyr amplitude modulation tuning to theoretical precession terms provides further support for the astronomical forcing of the chert sequence we propose that monsoon controlled upwelling contributed to the development of the chert mudstone cycles a seasonal monsoon controlled by astronomical forcing i e insolation influenced the intensity of upwelling stronger upwelling increased radiolarian productivity in the surface ocean increasing silica deposition glacio eustatic oscillations from ice sheet dynamics in southern gondwana modulated terrigenous mud flux to the basin the two processes jointly contributed to the astronomical rhythms of these tropical chert mudstone sequences which are characterized by comparably strong obliquity and precession responses subsequent diagenesis distorted the chert and mudstone layering but not enough to destroy the original stratigraphic patterns the resulting astronomical time scale ats assumes a roadian wordian boundary age of 268 8 ma for the onset of the first chert layer at the base of the sequence and ends at 264 1 ma for a total duration of 4 7 myr

volcanism mass extinction and carbon isotope fluctuations in the middle permian of china the 260 million year old emeishan volcanic province of southwest china overlies and is interbedded with middle permian carbonates that contain a record of the guadalupian mass extinction sections in the region thus provide an opportunity to directly monitor the relative timing of extinction and volcanism within the same locations these show that the onset of volcanism was marked by both large phreatomagmatic eruptions and extinctions amongst fusulinacean foraminifers and calcareous algae the temporal coincidence of these two phenomena supports the idea of a cause and effect relationship the crisis predates the onset of a major negative carbon isotope excursion that points to subsequent severe disturbance of the ocean atmosphere carbon cycle

silica diagenesis origin of inorganic and replacement cherts abstract silicification of originally non siliceous sediments affects a wide variety of rock types and materials and ranges from minor to pervasive partial and minor chertification occur mostly in phanerozoic carbonates carbonate bearing sandstones evaporites and fossil wood the source of the silica is predominantly biogenic in petrified wood the silicification mechanism is a permeation or void filling process not a replacement in this example the sequence of silica phase transformation is the same as that in deep sea siliceous sediments in many silicified rocks particularly in certain carbonates the transformation sequence is different from that in radiolarites or diatomites the chemical environment and conditions of early diagenetic chert formation in shallow water carbonates are delineated by the general mixing model of knauth 1979 but remain unknown for most other types an exception are the flint nodules and bands of the english chalk a detailed geochemical study of the paramoudra flint structures by clayton 1986 provided remarkable insight into the replacement process seven different recurring silica fabrics have been recognized in chert replaced carbonates including equigranular microcrystalline quartz or microquartz and megaquartz and fibrous types chalcedony quartzine or length slow chalcedony lutecite zebraic chalcedony and microflamboyant quartz among the latter quartzine and microflamboyant quartz are common in but by no means restricted to chert replaced evaporites for which milliken 1979 recognized a sequence of seven quartz fabrics as a single criterion only anhydrite inclusions in megaquartz quartzine or microflamboyant quartz provide unequivocal evidence for an evaporite precursor the relative timing between silicification and well established diagenetic carbonate reactions shows that virtually all theoretically possible sequences occur chertification of carbonate host sediment thus may take place during early intermediate or late diagenesis and even during anchimetamorphism pervasive to complete silicification has been described in lacustrine pedogenic and hydrothermal volcanogenic rocks and occurs on the scale of individual beds members or entire formations it may affect some of the aforementioned rock types too for example carbonates the source of the silica is predominantly inorganic chert formation in these environments includes direct chemical silica precipitation from solution through a gel stage magadi type cherts result from the conversion of the hydrous sodium silicate magadiite into microcrystalline quartz which has occurred in east african rift valley lakes such as lake magadi in late pleistocene time they are closely related to directly precipitated inorganic cherts which have been observed in alkaline environments of playa lakes silcretes originate from weathering and soil forming processes under climatic and environmental conditions conducive to the formation of duricrusts and laterites in more humid climates however non weathering profile silcretes occur which have been distinguished from weathering profile silcretes four to five different silcrete fabric types have been established including the 1 grain supported or quartzitic 2 floating terrazzo 3 matrix albertinia and opaline and 4 conglomeratic types in volcanic edifices silicification related to hydrothermal activity occurs 1 along the ascent routes of the fluids vents within the volcanic complexes 2 in isolated ponds and depressions on the sea floor where the fluids discharge mostly in the median rift valley of mid ocean ridges and 3 in geothermal areas on land associated with spreading lineaments volcanic islands arcs transform faults or continental hot spots attention has focussed on the associated base metal concentrations and less on the silicification and accompanying iron enrichment processes the precambrian banded iron formations may be indirectly or directly related to hydrothermal volcanic processes the origin of these cherty iron formations certainly requires more than one genetic model and at present remains a major unresolved problem despite massive efforts to tackle it

silicification of carbonate clasts in a marine environment upper miocene vera basin se spain abstract upper miocene marine sediments in the vera basin se spain contain abundant silicified marble pebbles and bivalves the silicification of these marble pebbles and bivalves represents one of the stages of their sedimentary history associated with small fluctuations in relative sea level during the late tortonian alluvial fan deposits containing the marble pebbles were invaded by the sea which caused reworking of the pebbles and the establishment of a marine biota in the environment after shallow burial numerous marble pebbles and bivalve remains were silicified both types of clasts were partially replaced by opal ct or quartz from opaline silica derived from dissolution of skeletal debris the silicified zones rinds now consist of quartzine or quartz silicification of the clasts must have taken place under shallow burial conditions during early diagenesis while pyrite formed in favourable anoxic sites iron oxides also precipitated during early diagenesis but after silicification finally part of the deposits containing the silicified clasts were transported by gravitational mass flows and redeposited in deeper areas of the basin if the hypothesis proposed for the diagenetic process is correct it indicates that the uncommon silicification of carbonate clasts does not only occur in continental environments in which it has previously been described

evaluating rare earth elements as a proxy for oil source correlation a case study from aer sag erlian basin northern china abstract the use of rare earth elements ree for oil source correlation has not yet been established in order to evaluate the potential of ree as proxies for oil source correlation we used traditional correlation approaches including biomarkers and trace elemental ratios v ni and ni co to identify the source rock of oil sands using isolated organic extracts of mudstones and oil sands and by analyzing the organic extracts and their corresponding whole rock material for ree compositions by inductively coupled plasma mass spectrometry icp ms oil source correlations using ree were not consistent with conclusions based on biomarker data and trace element ratios only one pair of oil source rock relationship was successfully established using ree ree concentrations of crude oils could possibly be controlled by the quantities of metal complexes and functional groups that provide complexing sites for v and ree as well as secondary alteration processes e g thermal alteration and biodegradation ree patterns might be linked to the organic matter types of source rocks although an accurate oil source relationship failed to be established using ree in this study ree could potentially be a novel complementary proxy for oil oil and or oil source correlations when supplemented by traditional correlation approaches including biomarkers

silicon isotope fractionation by marine sponges and the reconstruction of the silicon isotope composition of ancient deep water the silicon isotope composition d30si of biogenic opal provides a view of the silica cycle at times in the past reconstructions require the knowledge of silicon isotope fractionation during opal biomineralization the d30si of specimens of hexactinellid sponges and demosponges growing in the modern ocean ranged from 1 2 to 3 7 n 6 corresponding to the production of opal that has a d30si value 3 8 0 8 more negative than seawater silicic acid and a fractionation factor a of 0 9964 this is three times the fractionation observed during opal formation by marine diatoms and terrestrial plants and is the largest fractionation of silicon isotopes observed for any natural process on earth the d30si values of sponge spicules across the eocene oligocene boundary at ocean drilling program site 689 on maud rise range from 1 1 to 3 0 overlapping the range observed for sponges growing in modern seawater

continentally derived solutes in shallow archean seawater rare earth element and nd isotope evidence in iron formation from the 2 9 ga pongola supergroup south africa abstract the chemical composition of surface water in the photic zone of the precambrian ocean is almost exclusively known from studies of stromatolitic carbonates while banded iron formations ifs have provided information on the composition of deeper waters here we discuss the trace element and nd isotope geochemistry of very shallow water if from the pongola supergroup south africa to gain a better understanding of solute sources to mesoarchean shallow coastal seawater the pongola supergroup formed on the stable margin of the kaapvaal craton 2 9 ga ago and contains banded iron formations ifs that represent the oldest documented superior type iron formations the ifs are near shore pure chemical sediments and shale normalized rare earth and yttrium distributions reysn exhibit positive lasn gdsn and ysn anomalies which are typical features of marine waters throughout the archean and proterozoic the marine origin of these samples is further supported by super chondritic y ho ratios average y ho 42 relative to older isua ifs 3 7 ga from greenland and younger kuruman ifs 2 5 ga also from south africa the pongola ifs are depleted in heavy rare earth elements hree and appear to record variations in solute fluxes related to sea level rise and fall sm nd isotopes were used to identify potential sediment and solute sources within pongola shales and ifs the nd t for pongola shales ranges from 2 7 to 4 2 and nd t values for the coeval iron formation samples range 1 9 to 4 3 are generally indistinguishable from those of the shales although two if samples display nd t as low as 8 1 and 10 9 the similarity in nd isotope signatures between the shale and iron formation suggests that mantle derived rey were not a significant nd source within the pongola depositional environment though the presence of positive eu anomalies in the if samples indicates that high t hydrothermal input did contribute to their rey signature isotopic mass balance calculations indicate that most 72 of the nd in these seawater precipitates was derived from continental sources if previous models of fe nd distributions in archean ifs are applied then the pongola ifs suggest that continental fluxes of fe to archean seawater were significantly greater than are generally considered