the present day formation of apatite in mexican continental margin sediments abstract results of pore water and sediment analyses from the western mexican continental margin strongly suggest the present day formation of apatite the interstitial water phosphate and fluoride profiles indicate chemical removal at a depth which corresponds to a large maximum in the phosphorus content of the sediments apatite is identified within this maximum via x ray diffraction but is elsewhere undetectable in the core radioisotopic thorium uranium and radium data support the conclusion that this deposit is modern the present day depositional environment is consistent with those reported by other workers for phosphorite formation with the exception that pore water magnesium is not depleted below its seawater value

mobility and fractionation of rare earth elements in argillaceous sediments implications for dating diagenesis and low grade metamorphism abstract we report sm nd and rb sr data for the fine fractions of lower paleozoic argillaceous rocks from wales uk and new york usa spanning the range of low grade metamorphic conditions from the diagenetic zone zeolite facies to the epizone greenschist facies in all cases leaching of the fine fractions results in a high 147 sm 144 nd 0 09 0 29 acid soluble component and a complementary low 147 sm 144 nd 0 05 0 14 residual component the observed fractionation is an ancient feature related to diagenesis burial and metamorphism the magnitude of sm nd fractionation between leachates and residues as well as the resulting sm nd ages vary as a function of grain size and metamorphic grade uncleaved welsh mudrocks of the diagenetic zone yield sm nd leachate residue ages of 453 484 ma in agreement with their llanviian to caradocian biostratigraphic ages whereas higher grade rocks of the anchizone and epizone yield sm nd ages as young as 413 ma these ages are transitional between the time of deposition and the time of regional deformation related to the acadian orogeny at 390 ma distinct convex upward rare earth element ree patterns of the leachates suggest that the precipitation of early diagenetic apatite controls the trace element budget of the rock forcing a depletion of middle rees on the subsequently formed diagenetic phyllosilicates the amount of organic matter present and the extent of later prograde reactions are probable modifiers of this fractionation process ordovician and devonian clastic rocks associated with the trenton and onondaga limestones of new york yield single sample and multi sample sm nd isochron ages that agree well with their biostratigraphic ages of 454 ma and 390 ma respectively the ree fractionation observed in shale leachates of the ordovician utica formation is related to ca mg of the bulk rock and hence to the composition of the diagenetic carbonate cement in all cases the sm nd system remained closed subsequent to the peak of diagenesis or metamorphism including the north american rocks that show no evidence of being isotopically reset during widespread remagnetization of the subjacent limestone units in the late paleozoic

effects of experimental leaching on rbsr and kar isotopic systems and ree contents of diagenetic illite leaching with 1 n hcl 1 n nh4cl acetone humic acid extracts cation exchange resin and nh4 edta have negligible effects on the rb sr and k ar systems of different size fractions 0 4 and 0 8 2 m of a 1m diagenetic illite none of these treatments including the 1 n hcl treatment induced preferential removal of radiogenic 87sr and 40ar from mineral structures however the 1 n hcl treatment removed significant amounts of sr and ree as compared to the treatments by nh4 edta and cation exchange resin however much of these hcl derived elements resided in non clay minerals such as carbonate and fe oxide phases the k ar and rb sr ages of the samples were not affected by the hcl treatment any more than by the nh4 edta or the cation exchange resin because of potential loss of solid material during elutriation of differentially treated samples the hcl treatment is preferred over other methods allowing sufficient controls on the isotopic and mass balances between the leachate and the corresponding residue of an untreated sample for rb sr isotopic dating purposes of clay minerals from sedimentary and metasedimentary rocks leaching experiments give information about the ambient environment of crystallization analysis of both the leachate and residue under carefully controlled conditions is recommended

resetting of rb sr whole rock ages during acadian low grade metamorphism in north wales ordovician volcanic rocks and associated sub volcanic intrusions in north wales give devonian metamorphic rb sr whole rock ages isotopic resetting is not confined to acid volcanic rocks three intrusions preserve ordovician ages the closed system resetting is not directly related to metamorphic grade but appears to correlate with the extent to which the secondary metamorphic mineral assemblage is developed rocks giving devonian ages have a well developed secondary mineralogy whereas those retaining ordovician ages are less extensively altered the metamorphic ages combine to give a lower devonian mean age and weighted 2a error of 399 f 9 ma metamorphism is therefore synchronous with acadian deformation in the north wales area

authigenic potassium feldspar in cambrian carbonates evidence of alleghanian brine migration the shallow water limestones and dolostones of the conococheague limestone upper cambrian of western maryland contain large amounts of authigenic potassium feldspar the presence of halite daughter crystals in breached fluid inclusions low whole rock ratios of chlorine to bromine and thermochemical data suggest that the potassium feldspar formed at low temperature by the reaction of connate brines with intercalated siliciclastic debris analyses of argon age spectra indicate that the authigenic feldspar probably formed during late pennsylvanian to early permian time these results may indicate mobilization and migration of connate brines brought about by alleghanian folding the widespread occurrence of authigenic potassium feldspar in cambrian and ordovician carbonate rocks throughout the appalachians suggests that this may have occurred throughout the entire basin

short paper low grade metamorphism of the welsh basin lower palaeozoic succession an example of diastathermal metamorphism the lower palaeozoic succession of the welsh basin has suffered the effects of low grade metamorphism which shows features that do not accord with classical models of regional or burial metamorphism textural evidence demonstrates the development of greenschist facies metamorphism prior to deformation and cleavage development while mineralogical characters indicate a low pressure facies series in order to accommodate these features it is suggested that the area has suffered diastathermal metamorphism in which an enhanced thermal flux develops early in the tectonic cycle in response to an extensional setting temperatures remained relatively high during final closure associated with deformation of the basin sediments and consequent cleavage development such a model adequately resolves previously conflicting interpretations of burial and deformation related metamorphism

sm nd isotopic dating of proterozoic clay material an example from the francevillian sedimentary series gabon clay fractions of 0 4 m and 0 2 m and acid leachates of these clay fractions were separated from two different kerogen rich black shale samples from the francevillian sedimentary series in gabon they yielded identical sm nd isochron ages of2099 115 ma and2036 79 ma with initial nd values of 6 5 2 0 and 9 3 1 5 respectively these ages define multi episode illitization during early diagenesis as suggested by the differentsm nd ratios of the clay fractions the sm nd isotope data of the kerogen source rock up to 13 organic carbon plot between the two isochrons but close to the clay fractions suggesting that this organic matter reached nd isotopic equilibrium with respect to the clay minerals and the diagenetic fluids analyses of fracture filling bitumen showed that it had very elevated143nd 144nd and147sm 144nd ratios these values are higher than the most elevated values of the leachates but plot on the extension of the two isochrons this indicates that the bitumen reached nd isotopic equilibrium with the kerogen source rock from which it was expelled and the authigenic clay minerals secondary migration and chemical evolution of the bitumen appear to have caused the fractionation between sm and nd with an attendant increase in thesm nd ratio the results suggest that the sm nd isotope method has potential for both dating diagenetically related illitization using leachate residue pairs of small size clay fractions and reconstructing geochemical processes during diagenesis in oil producing sedimentary basins

recent developments in dating ancient crustal fluid flow several isotopic techniques have recently been developed or substantially improved allowing the accurate determination of the timing of fluid related processes these include k ar rb sr and sm nd dating of diagenetic minerals in clastic rocks u pb dating of carbonates sm nd dating of fluorite and uraninite re os and rb sr dating of sulfides 40ar 39ar and rb sr dating of fluid inclusions and u pb dating of ilmenite magnetite sphene and rutile while many of these techniques require further evaluation some have already resulted in new constraints on a variety of crustal fluid flow models

the assessment of ree patterns and 143nd 144nd ratios in fish remains abstract the ree content and isotopic composition of sr and nd have been determined in fish teeth ranging in age from the trias to the present and from various localities mostly around the atlantic these measurements have been carried out on selachian and teleost remains from the same locality in togo and show no appreciable difference which suggests with the help of a mass balance calculation of the ce anomaly that diagenetic effects are not responsible for the ree enrichment of biogenic phosphates one group of fossil teeth has about 3 times the ree abundances of shale and a shale normalized pattern with a minimum at sm it is thought to reflect deposition in the open sea environment a second group has ree concentration about 10 times higher than the first group with either a regular light ree enrichment or more frequently a maximum in the middle ree both being probably indicative of deposition in estuarine or near shore conditions the shape of the ree spectra and the size of the ce anomaly can be used semi quantitatively to determine the depth of deposition the results presented here on late cretaceous eocene fish teeth samples from morocco reflect an increasing influx of deep waters with a lowla yb ratio and strong negative ce anomaly which agrees well with the evolution of sediment chemistry and microfauna associations in contrast nd is typical of the water mass in which the fish debris decayed examples of nearly isolated basins identified with nd isotopes include the south atlantic prior to the lutetian nd 13 5 the miocene persian gulf nd 3 1 and bolivia during the late cretaceous nd 12 8 togo and guinea bissau results suggest that in the south atlantic the meridional oceanic circulation had not started before 45 ma ago combination of ree and nd data suggests that the assignment of jurassic cretaceous samples measured so far to open sea water masses is still ambiguous

south pacific dissolved nd isotope compositions and rare earth element distributions water mass mixing versus biogeochemical cycling despite its enormous extent and importance for global climate the south pacific has been poorly investigated in comparison to other regions with respect to chemical oceanography here we present the first detailed analysis of dissolved radiogenic nd isotopes end and rare earth elements rees in intermediate and deep waters of the mid latitude 40 s south pacific along a meridional transect between south america and new zealand the goal of our study is to gain better insight into the distribution and mixing of water masses in the south pacific and to evaluate the validity of nd isotopes as a water mass tracer in this remote region of the ocean the results demonstrate that biogeochemical cycling scavenging processes in the eastern equatorial pacific and release of lrees from the sediment clearly influence the distribution of the dissolved ree concentrations at certain locations nevertheless the nd isotope signatures clearly trace water masses including aaiw antarctic intermediate water average end 8 2 0 3 lcdw lower circumpolar deep water average end 8 3 0 3 npdw north pacific deep water average end 5 9 0 3 and the remnants of nadw north atlantic deep water average end 9 7 0 3 filtered water samples taken from the sediment water interface under the deep western boundary current off new zealand suggest that boundary exchange processes are limited at this location and highlight the spatial and temporal variability of this process these data will serve as a basis for the paleoceanographic application of nd isotopes in the south pacific

rb sr and k ar dating of clay diagenesis in jurassic sandstone oil reservoir north sea rb sr and k ar isotopic determinations were combined with scanning electron microscopy sem observations and x ray diffractometry xrd controls to date the diagenetic formation of clay minerals from oil bearing sandstones of the middle jurassic brent sandstone in the north sea the separated clay fractions often contain detrital components especially k feldspars which are reduced to sizes smaller than 0 4 m either by intense in situ alteration or by destructive sample preparation direct rb sr and k ar isotopic dating of diagenetic illite therefore was not possible isotopic data obtained on mixtures of detrital and newly formed components showed however that illite formed about 40 to 45 ma this value also was obtained directly on clay fractions separated by a gentle method of disaggregation illitization is related to emplacement of hydrocarbons and associated waters into the formation aqueous and hydrocarbon fluids simultaneously trapped in quartz overgrowth inclusions indicate late silicification contemporaneous with this fluid migration minimum trapping temperatures of at least 110 c for these fluid inclusions are too high for the present burial depth hot fluids are assumed to have originated in deep source rocks beneath the brent reservoirs and migrated upward during the middle eocene

structure related geochemical ree and isotopic k ar rb sr δ18o characteristics of clay minerals from rotliegend sandstone reservoirs permian northern germany abstract euhedral illite cementing the gas bearing sandstone reservoirs of the rotliegend in the niedersachsische rift system northern germany was studied along a horst to graben cross section to examine its chemical and isotopic characteristics the data show that differentiated illite particles grew during a tectono thermal event marked by distinct episodic hydrothermal activities along fault drains and in the poral space of sandstones at 210 ma and at 195 to 190 ma in horst positions at 185 to 175 ma in the nearby graben and at 170 to 165 ma in both the horst and graben varied ree distribution patterns and initial 87sr 86sr ratios from 0 7124 to 0 7142 relative to illite particle size outline a high chemical variability of the fluids during illite growth the 18o values of illite range from 20 0 to 12 4 and those of chlorite from 12 0 to 6 9 the changing 18o values of the minerals most likely relate to varied 18o values of the fluids or to different water rock ratios during crystallization differences among the ree and 87sr 86sr tracers and the 18o values of different generations of illite also suggest a changing fluid chemistry relative to time significant positive eu anomalies and negative ce anomalies in the ree distributions of illite suggest feldspar alteration by the migrating fluids in oxidizing environments

replacement of pyrite framboids by magnetite in limestone and implications for palaeomagnetism limestones are an important source of palaeomagnetic data with magnetite the dominant carrier of the magnetization because the magnetite is present in low concentrations however it has been directly observed only rarely and in trace amounts in acid treated separates such residues are composed primarily of spheres the ultimate origin of which has been enigmatic7 yet interpretation of the palaeomagnetic data depends on a knowledge of the origin of the magnetite which has been inferred to carry either a chemical or a viscous remanent magnetization here we present electron microscope data obtained from a sequence of samples of onondaga limestone from an east west traverse across northern new york which unambiguously show that magnetite spheres are derived by alteration and replacement of framboidal pyrite remagnetization is thus caused by chemical rather than viscous processes this chemical remanent magnetization is compatible with a fluid mediated event occurring on a regional scale induced by tectonic stress of alleghenian late palaeozoic age

provenance of the pre devonian sediments of england and wales sm nd isotopic evidence nd values and clast petrography of the longmyndian sediments of shropshire indicate a provenance dominated by juvenile high nd t uriconian volcanic sources but with an increasing detrital contribution from older low nd t metamorphic sources up section by contrast most lower palaeozoic strata of england and wales have low nd t values typical of sediments derived from long established continental crust the sm nd isotopic evidence suggests that avalonia received sediment from an adjacent large continent in the cambrian to lower ordovician and in the silurian ordovician and silurian volcanicity supplied juvenile detritus only during and shortly after active volcanism

thermoviscous remagnetization in some appalachian limestones experimental evidence shows that blocking temperature relaxation time theory for single domain magnetite can grossly underestimate laboratory thermal demagnetization temperatures of a present day viscous remanence in devonian limestones of new york state thermoviscous remagnetization at moderately elevated burial temperatures during the late paleozoic cannot therefore be readily excluded for the origin of the stable secondary component in these rocks more generally these results emphasize that single domain thermal activation theory cannot be assumed a priori to correctly predict temperature of thermoviscous remanence acquisition in all magnetite bearing rocks the prob leto

petrology and major element geochemistry of peru margin phosphorites and associated diagenetic minerals authigenesis in modern organic rich sediments abstract new petrographic and major element geochemical data from modern peru margin upper slope outer shelf phosphorites are presented which provide insight into their origin and paragenetic relationship with other authigenic minerals glauconite pyrite and dolomite occurring in organic rich sediments glauconites are precipitated relatively early following the partial reduction of ferric iron and following this process phosphate pyrite and then dolomite precipitation take place at progressively deeper levels in the sediment in association with microbial reduction of sulfate as in many ancient economic phosphorite deposits the phosphatic facies here consist of nodules crusts coatings and strata composed of phosphatic pelletal grains ooids structureless grains intraclasts clumps and biogenic grains in association with organic rich biosiliceous sediments all are considered to have formed within a few centimeters or within a few tens of centimeters below the sediment water interface important factors that influence which morphology will tend to develop include the amount of available pore space the presence of suitable nucleation sites the amount and size of siliciclastic detritus incorporated as inclusions and the relative solution chemistries of the precipitating solutions bacterial mediation may play an important but as yet unspecified role in the precipitation process textural data and factor analysis of chemical data suggest that structureless pellets are relatively inclusion free na f mg co3 substituted pore water precipitates whereas ooids are inclusion rich pore water precipitates poor in lattice substituted components variations in nodular cement birefringence and crystallinity are suggested to have been produced by similar lattice substitutions that directly reflect pore water carbonate ion concentrations and thus relative degrees of organic matter degradation phosphate and dolomite are intimately mixed yet mineralogically distinct phases in phosphatized dolomicrites depth stratified threshold carbonate ion concentrations may control the lower limit at which phosphatic minerals may precipitate below depths of a few centimeters excessive carbonate ion concentrations and diminished reactive iron and sulfate concentrations favor the development of dolomite while precluding further development of phosphatic minerals and pyrite periodic sediment reorganization bioturbation current winnowing and erosion mass wasting etc plays an important role in both concentrating pelletal grains and maintaining nodules and crusts at critical depth levels in the sediment as well as mixing ordered mineral parageneses into complicated sequences

low grade and very low grade regional metabasic ordovician rocks of llŷn and snowdonia gwynedd north wales metabasic assemblages belong to the prehnite pumpellyite and greenschist facies the isograds pumpellyite in pumpellyite out clinozoisite in and biotite in have been mapped and divide the area into four metamorphic zones field and petrographic evidence indicate that the metamorphic crystallization was largely syn and immediately post tectonic viz end silurian to devonian the use of published schreinemakers bundles indicates that most of the prehnite pumpellyite bearing assemblages formed at high grades within the facies and that the greenschist facies rocks crystallized in the higher pressure field as the amount of calcite increases so diagnostic ca al silicates are reduced and eventually eliminated from assemblages contrary to recent claims the evidence indicates that the gwna group and the gwyddel felsitic beds of ll n were metamorphosed prior to the arenig

diagenetic modification of sm nd model ages in tertiary sandstones and shales texas gulf coast sm nd model ages of sandstones and shales from the oligocene frio formation of south texas and the paleocene eocene wilcox group of south central texas increase with increasing depth of burial depleted mantle model ages tdm of frio shales increase from ca 800 ma at 1 km of burial to ca 1000 ma at 4km in frio sandstones tdm increases from ca 750 ma at 1 km to over 1200 ma at 4 km of burial in wilcox shales tdm increases from ca 1300 ma to ca 1500 ma over a burial depth of 1 5 to 4 5 km tdm of wilcox sandstones increases from ca 1450 ma at 2 5 km of burial to as much as ca 2000 ma at 4 0 km the sampling scheme employed minimizes but does not eliminate the possibility that these trends in tdm are due to detrital variability close correlation of these trends with diagenetic changes in the rock and evidence of rare earth element mobility preserved in the diagenetic products suggests that diagenesis has modified tdm diagenetic modification of tdm in frio sandstone and wilcox shale is due primarily to loss of radiogenic nd whereas increased 147sm 144nd produces elevated tdm in deeper wilcox sandstones the tdm of frio shales does not change appreciably with depth owing to the opposite effects on tdm of decreased 147sm 144nd and decreased nd 0 loss of radiogenic nd is due primarily to reactions involving unstable volcanic detritus which is more abundant in the frio than in the wilcox decreased 147sm 144nd in authigenic illite and consequent increased 147sm 144nd in pore fluids results in elevated tdm in wilcox and frio sandstones containing late diagenetic cement and in decreased 147sm 144nd in deeper frio shale the similar tdm trends observed in both units which have different detrital characteristics suggest that modification of sm nd model ages in siliciclastic rocks may be commonplace during burial diagenesis

late paleozoic remagnetization of the trenton limestone samples of the middle ordovician trenton limestone were collected from 8 sites in quebec ontario and new york state for paleomagnetic study stepwise thermal demagnetization reveals a very well defined characteristic magnetization that has a corresponding paleomagnetic pole at 53 0 n 126 9 e k 97 7 a 95 2 7 this pole is not at all close to other ordovician poles from cratonic north america but is near late carboniferous and early permian ones indicating that the trenton was remagnetized in the late paleozoic an earlier paleomagnetic investigation of the trenton gave a pole that did not appear to be late paleozoic in age however we demonstrate that this earlier study failed to isolate the ancient characteristic magnetization rock magnetic experiments and analyses of magnetic extracts show that the carrier of magnetization is fe3o4 that does not contain ti or other elements in solid solution that would indicate a detrital source the magnetite and its associated remanence appear to have a diagenetic origin

stratigraphic relationships and detrital composition of the medial ordovician flysch of western new england implications for the tectonic evolution of the taconic orogeny a reply to rodgers we present new stratigraphic and petrographic data on the easterly derived medial ordovician flysch sequence of western new england and eastern new york state a conformable relationship exists between the flysch and underlying early paleozoic continental rise sediments within the western taconic allochthon farther east in the allochthon we observe a possibly disconformable relationship contrary to previous interpretations these facts suggest that at any place within this paleogeographic realm the sediments were undeformed and untransported at the initiation of flysch deposition at least three sources contributed detritus to the flysch 1 taconic sequence sediments 2 deformed and metamorphosed pelitic psammitic and volcanic lithologies and 3 igneous rocks of dominantly mafic ultramafic affinities these three sources are respectively interpretable as continental rise accretionary prism and ophiolitic volcanic arc assemblages which are recognized in the regional geology of western new eng

redistribution of rare earth elements during diagenesis of turbidite hemipelagite mudrock sequences of llandovery age from central wales

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

ion probe measurement of rare earth elements in biogenic phosphates abstract the rare earth element ree distributions in individual fish teeth and conodonts have been measured by ion probe concentrations and la yb ratios show little variations except in the enamel which suggests that ree uptake from the sedimented biogenic debris takes place at the water sediment interface as an essentially quantitative process without fractionation late diagenetic disturbances remained of marginal importance hence ree in phosphatic debris might reflect the input from the overlying water column

u pb dating of a remagnetized paleozoic limestone the upper ordovician trenton group of new york state is one of a number of appalachian limestones which yields paleomagnetic poles suggesting disturbance in the late paleozoic calcite fractions dissolved from samples of the trenton limestone define a 238u 206pb age of 454 8 ma mswd 12 8 in excellent agreement with 40ar 39 ar and u pb ages for the deposition of the underlying diecke bentonite this requires that the u pb system in the calcite has been preserved since deposition and early diagenesis if late paleozoic remagnetization of this limestone was induced by fluids these fluids did not interact with significant amounts of carbonate the apparent robustness of the u pb system and the large spread in values 18 17 118 8 offers potential precision of 1 ma in determining the paleozoic time scale

effects of cation exchange treatment and acid leaching on the rb sr system of illite from fithian illinois size fractions 5 m of fithian illite were treated with 1 n hcl h from cation exchange resin and 5 nh4 edta solution and analyzed for their rb sr isotopic composition in comparison to the effects of hcl the ion exchange resin leached the same amount of sr but significantly less rb and radiogenic 87sr from poorly crystallized 1 m illite an age of 284 8 ma i r 0 7109 6 is more or less in agreement with the missourian stephanian age of deposition the agreement is fortuitous because of the presence of small amounts of detrital 2 m illite and kaolinite thus the true age of diagenesis might be somewhat less 87sr86sr ratio measurements of tithonian solnhofen limestone demonstrate that even though the silicate component constitutes less than 5 of the total the majority of the radiogenic 87sr is leached from broken bond surfaces of the nearly pure kaolinite residues during the hcl treatment ion exchange and edta treatment can be useful in this situation to obtain a precise separation of environmental sr in carbonate from radiogenic 87sr in silicates and an adequate spread of rbsr values from argillaceous fine fractions in the construction of isochrons

rb sr evidence for punctuated illite smectite diagenesis in the oligocene frio formation texas gulf coast the size fractions of a suite of upper oligocene frio formation shale samples taken from below 10 500 ft in a well on the texas gulf coast fall on a rb sr isochron corresponding to an age of 23 6 0 8 m y the isochron shows an initial 87 sr 86 sr ratio of 0 7088 0 0004 this suggests that regularly interstratified illite smectite simultaneously equilibrated soon after burial over a range of burial depths at 7 000 8 000 ft shallower than at present oxygen isotope values for these clays are also consistent with equilibration under shallower burial conditions such a pattern conflicts with the prevailing idea of a gradual illitization of smectite with progressive burial a new model of episodic or punctuated diagenesis is proposed whereby sudden diagenesis is initiated by a change in pore water chemistry clay reaction occurs over a range of temperature at this time such that the deeper clays are transformed completely to 80 illite and the shallow clays are transformed less completely subsequent pore water chemical changes inhibit further clay reaction and the mineralogic gradient and the isotopic signature formed at 23 6 m y b p are frozen in seven to eight thousand feet of additional post oligocene burial has not resulted in the creation of younger illite smectite consequently there is no evidence that illite smectite diagenesis is currently taking place in the frio formation

origin and tectonic setting of ordovician bentonites in north america isotopic and age constraints the large volume of ordovician bentonites in the eastern and central united states indicates that they originated from a major volcanic system the location and paleotectonic setting of this volcanic source is unknown nd and sr isotopic data were collected from eight samples of primary apatite phenocrysts contained in four ordovician bentonites and u pb data were collected from one bentonite to determine the origin of this extensive volcanism the range in initial isotopic ratios for the four bentonites is nd 3 5 to 5 2 87 sr 86 sr 0 71005 to 0 71200 the age of the deicke bentonite is 457 1 1 0 2 determined by a concordant u pb zircon fraction five other zircon fractions from the deicke bentonite contain an inherited lead component lines drawn through the concordant point and the extremes of the discordant points have calculated upper intercepts with concordia of 1 090 ma and 1 540 ma the nd and sr isotopic data and the u pb age data are consistent with the generation of the volcanic ash by anatexis of evolved continental crust an evolved source region with volcanics of the same age and isotopic composition as the north american bentonites has not been found this source region however may be the same as the source of ordovician bentonites in sweden because the ages of both groups of bentonites are identical the 87 sr 86 sr ratios overlap and zircon phenocrysts from both groups of bentonites contain an inherited pb component an appropriate tectonic setting for the generation of both groups of bentonites was a continental margin volcanic arc or an extensional regime associated with such an arc

the occurrence and origin of late paleozoic remagnetization in the sedimentary rocks of north america although it has been known for 25 years that some paleozoic sedimentary rock units in europe and north america were remagnetized during pennsylvanian or permian time it is only very recently that the complex and widespread nature of the late paleozoic remagnetization phenomenon has been generally acknowledged it is now recognized that many paleozoic paleomagnetic poles for north america that were once considered reliable are in fact the result of remagnetization and as a consequence the paleomagnetic data base for the paleozoic is undergoing rapid and drastic revision the causes of late paleozoic remagnetization in north america are currently the focus of much interest and active research the remagnetization can reside in either hematite or magnetite and different remagnetization mechanisms have been important in different settings chemical remagnetization processes some related to specific diagenetic events are dominant in hematite bearing sandstones and carbonates in magnetite bearing carbonates both chemical and thermoviscous remagnetization processes appear to have been important but it is difficult to determine which process is the dominant one in some settings some of the observed remagnetizations can be linked to the migration of chemically active and perhaps hot fluids during the mountain building events that affected much of the continent during the late paleozoic paleomagnetic studies promise to be important in assessing the role of orogeny in driving fluid migrations within sedimentary basins and in constraining the age of the migrations and the nature of the fluids

the absolute age of the eifelian tioga ash bed pennsylvania the tioga ash bed bed b of the zeigler pit union county pennsylvania lies in the polygnathus costatus costatus zone of the eifelian stage of the middle devonian series the 27 5 cm thick bed contains igneous zircon and monazite crystals that have been dated by precise u pb techniques zircons are characterized by inherited pb that occurs as barely perceptible interior regions enriched in inclusions the zircons are discordant and do not reveal the igneous age of the bed in contrast high quality monazite crystals lack any evidence of inheritance or loss of pb and multiple analyses have overlapping 207 pb 235 u ages of 390 0 pm 0 5 ma the monazite analyses are concordant or very slightly reversely discordant the consistency of the monazite data provides a new precise estimate of age for the lower eifelian

sm nd isochron age and provenance of the argillites of the gunflint iron formation in ontario canada abstract sm nd rb sr and k ar isotope analyses were made on argillaceous sediments from the gunflint iron formation in the lake superior region in order to provide new information on their sedimentation age and evolutionary history the investigations indicate that it might be possible to date the time of sedimentation by the sm nd method by studying specific material such as argillaceous whole rocks enriched in organic matter and clay fractions the spread in the sm nd ratios seems here to have been favoured by the incorporation of organic material in the argillites the sm nd isotope data yield an isochron age of 2 08 0 25 ga which seems to be a fair estimation of deposition age model calculations indicate that the main source supplying the animikie seawater with ree was located at the northern border of the basin the argillites and their clay minerals did not behave as closed systems with regard to the rb sr and k ar systems during further diagenetic evolution

sr and nd isotopic evidence for punctuated clay diagenesis texas gulf coast we report rb sr sm nd and mineralogical data for leached whole rock 1200 m independent of the duration of burial the exchangeable sr in the clay has remained an open system and has undergone isotopic exchange since that time minimum fluid rock ratios of 0 2 to 2 are modeled from sr isotopic data consistent with rock dominated open system diagenesis leachates and residues of the 0 1 zm fraction below the smectite illite transition appear to have achieved nd isotopic equilibrium during clay diagenesis and show no signs of subsequent exchange the clay residues have low 147sm 144nd 0 085 indicating that authigenic illite has a lower sm nd ratio than its bulk rock protolith conversely the coexisting exchangeable ree inventory has elevated sm nd as reflected by leachate 14vsm 144nd as high as 0 188 this sm nd fractionation in conjunction with the preserved isotopic equilibrium may be useful for dating diagenesis and associated fluid rock interaction in older rocks

the distinction between caledonian burial and regional metamorphism in metapelites from north wales an analysis of isocryst patterns in snowdonia and ll n three prograde stages in metapelites gwna group to wenlock are recognized stage i with white mica crystallinity values 0 43 2 stage ii 0 43 0 26 2 stage iii isocrysts at 0 03 2 intervals are drawn separately for pelites above and below the sub arenig unconformity approximately concordant isocryst patterns characterize the unconformity in the northwestern and southeastern limbs of the snowdonia syncline whereas discordant patterns are developed northwest of the aber dinlle fault and at the closure of the ynyscynhaiarn anticline the contrasting patterns are the result of a pre arenig burial metamorphism in post tremadoc pelites belts of steep metamorphic gradient coincide with belts of high strain and a broad area of higher grade caradoc pelites coincides with the core of the snowdonia syncline the later metamorphism is related to caledonian deformation rather than to burial pelite alteration adjacent to small intermediate to acid plutons suggests emplacement before the caledonian regional metamorphism a close correlation exists between metabasite zones and metapelite stages

rare earth element geochemistry of oceanic ferromanganese nodules and associated sediments abstract analyses have been made of ree contents of a well characterized suite of deep sea 4000 m principally todorokite bearing ferromanganese nodules and associated sediments from the pacific ocean ree in nodules and their sediments are closely related nodules with the largest positive ce anomalies are found on sediments with the smallest negative ce anomalies in contrast nodules with the highest contents of other rare earths 3 ree are found on sediments with the lowest 3 ree contents and vice versa 143 nd 144 nd ratios in the nodules 0 51244 point to an original seawater source but an identical ratio for sediments in combination with the ree patterns suggests that diagenetic reactions may transfer elements into the nodules analysis of biogenic phases shows that the direct contribution of plankton and carbonate and siliceous skeletal materials to ree contents of nodules and sediments is negligible inter element relationships and leaching tests suggest that ree contents are controlled by a p rich phase with a ree pattern similar to that for biogenous apatite and an fe rich phase with a pattern the mirror image of that for sea water it is proposed that 3 ree concentrations are controlled by the surface chemistry of these phases during diagenetic reactions which vary with sediment accumulation rate processes which favour the enrichment of transition metals in equatorial pacific nodules favour the depletion of 3 ree in nodules and enrichment of 3 ree in associated sediments in contrast ce appears to be added both to nodules and sediments directly from seawater and is not involved in diagenetic reactions

tem and aem constraints on the origin and significance of chlorite mica stacks in slates an example from central wales u k chlorite mica stacks grains of intergrown chlorite and white mica in a matrix of fine grained white mica and chlorite have been studied using xrd sem empa tem and aem methods the stacks occur in a weakly cleaved llandoverian mudstone central wales which has a white mica illite crystallinity index of 0 35 a20 corresponding to the lower anchizone white mica occurs as packets 100 to 8 m thick interleaved with dominant chlorite packets in stacks with both apparent coherent interfaces or cross cutting small angle boundaries with chlorite layers it is well crystallized 2m polytype with phengitic composition and low paragonite component na na k 0 0 07 chlorite in stacks is fe rich and relatively homogeneous tio2 crystals surround stacks and occur within chlorite and white mica is ti rich compared to matrix white mica fine grained white mica and chlorite in the matrix have two different orientations one parallel to bedding and one parallel to cleavage which is approximately 30 50 to bedding matrix white mica is predominantly a 2m1 polytype but some cleavage parallel white mica is 3 t and some bedding parallel white mica is 1md it is na rich na na k 0 14 0 42 and relatively heterogeneous some discrete paragonite and phengitic muscovite are observed to coexist in the cleavage orientation matrix white mica and chlorite each contain less fe than corresponding white mica and chlorite in stacks both matrix and stack chlorite are one layer polytypes the data imply that chlorite in the stacks is largely derived from the replacement of volcanogenic biotite and other ferromagnesian minerals probably via intermediate expandable trioctahedral phyllosilicates most intergrowths of chlorite and mica in stacks formed by mica replacement of chlorite and altered biotite along cleavage fissures subsequent deformation caused further modification of pre existing chlorite mica stacks whereas partial dissolution of stacks and bedding parallel matrix phyllosilicates resulted in the formation of cleavage parallel phyllosilicates