oxygen isotopes in titanite and apatite and their potential for crustal evolution research abstract oxygen isotope analysis of zircon often combined with geochronology and hf isotope analysis has been pivotal in understanding the evolution of continental crust in this contribution we expand the use of underexplored accessory phases titanite and apatite by demonstrating that their oxygen isotope systems can be robust and by developing geochemical indicators involving o isotopes and trace element concentrations to better constrain magma petrogenesis these minerals have the advantage over zircon of being present in less evolved magmas and being more responsive to igneous processes and crustal metamorphism we present new data on titanite apatite and zircon from carefully selected granitoids through geological time the phanerozoic high ba sr granites caledonian province scotland archean sanukitoids karelia province finland and a neoproterozoic basalt andesite dacite rhyolite suite badr guernsey channel island we demonstrate i that 18o values of the studied accessory minerals are not affected by crystal fractionation ii a strong correlation between 18o in all three accessory minerals showing that apatite and titanite can faithfully record the magmatic 18o iii that these accessory minerals can also record metamorphic and or fluid circulation events during the syn to post magmatic history of granitoids

a precise late neoproterozoic u pb zircon age for the syntectonic perelle quartz diorite guernsey channel islands uk a precise u pb zircon age of 611 4 2 0 1 1 ma has been determined for the foliated quartz diorite at perelle bay guernsey uk channel islands the age is based on the analysis of single zircons half of a single grain and groups of two and three zircons the age is nearly 100 ma younger than that suggested by other workers based on 207 pb 206 pb dates of large multi grain fractions of zircon and thus rules out this intrusion as the earliest marker of the onset of cadomian magmatism in the north armorican massif a 611 ma crystallization age for the perelle quartz diorite is consistent with previous detailed fabric development studies that suggested magmatic fabrics within the pluton are largely overprinted by similarly oriented solid state deformation fabrics resulting from syntectonic emplacement during cadomian orogenesis the u pb age is approximately 8 15 ma older than 40 ar 39 ar hornblende dates for the pluton consistent with the emplacement of the intrusion followed by slow cooling in a region of moderate to high ambient crustal temperatures these new data emphasize the fact that periods of pluton emplacement are considerably briefer than periods of deformation and thus syntectonic intrusions do not date regional deformational events but only mark events within a period of regional tectonism the ability to analyse single zircons and selected portions of single zircons using ultra low blank u pb analytical techniques documents the feasibility of determining precise emplacement ages of other neoproterozoic granitoids that contain a significant percentage of xenocrystic zircon

isotope evidence for the involvement of recycled sediments in diamond formation diamonds as chemically robust containers of material from the mantle have provided important information regarding the evolution of the earth s interior1 yet despite much effort2 9 the origins of diamonds themselves have remained controversial10 13 sulphur isotope ratios measured in most mantle or meteoritic samples exhibit minimal deviation from the meteoritic standard whereas the ratios in crustal materials deviate by as much as 70 ref 14 for this reason isotopic studies of sulphide mineral inclusions in diamonds and mantle material are an attractive means of investigating the possible role of crust mantle interaction in the formation of diamonds15 recent ion microprobe studies have found departures from mantle values in the sulphur isotope compositions of individual diamond inclusions16 and some mantle rocks17 which would be consistent with subduction of altered ocean crust into the region of diamond growth here we present new sulphur and lead isotope data from diamond sulphide inclusions which suggest that sedimentary material might also be subducted into the mantle and that the crustal recycling process has been operative for at least 1 000 million years

the composition and evolution of the continental crust rare earth element evidence from sedimentary rocks the composition of the present day upper crust inferred from the uniformity of sedimentary rock r e e rare earth element patterns is close to that of granodiorite a revised andesite model is used to obtain total crustal composition the lower crust is the composition remaining assuming that the upper crust one third of the total is derived from intracrustal partial melting the upper crustal r e e pattern has pronounced eu depletion eu eu 0 64 the lower crustal pattern has eu enrichment eu eu 1 17 and the total crust has no eu anomaly relative to chondritic abundances the eu depletion in the upper crust is attributed to retention of eu in plagioclase in the lower crust because plagioclase is not stable below 40 km 10 kbar the anomaly is intracrustal in origin the archaean upper crust has a different r e e pattern to that of the present day upper crust being lower in total r e e and la yb ratios and lacking an eu anomaly these data are used to infer the archaean upper crustal composition which resembles that of the present day total crust except that ni and cr contents are higher the archaean crustal composition can be modelled by a mixture of tholeiites and tonalite trondhjemites the latter have steep light r e e enriched heavy r e e depleted patterns consistent with equilibration with garnet and hence probable mantle derivation there is little reason to suppose that the archaean lower crust was different in composition from the upper crust except locally where partial melting episodes occurred the r e e evidence is consistent with isotopic and geological evidence for a low continental growth rate in the early archaean a massive increase to about 70 of the total crust between about 3000 and 2500 ma b p and a slow increase until the present day the change from archaean to post archaean r e e patterns in the upper crust is not isochronous but is reflected in the sedimentary rock r e e patterns at differing times in different continents on the basis of a model composition for the mantle 36 of the potassium 30 of uranium 15 of lanthanum and 3 of ytterbium are concentrated in the present continental crust this enrichment is related to ionic size and valency differences from common mantle cations e g mg fe pre 3 9 ga b p crusts were obliterated by meteorite bombardment no geochemical evidence exists for primordial anorthositic sialic or mafic crusts

uv induced mass independent sulfur isotope fractionation in stratospheric volcanic sulfate 1 sulfuric acid aerosols produced in the stratosphere following massive volcanic eruptions possess a mass independent sulfur isotopic signature acquired when volcanic so2 experiences uv photooxidation the volcanic data are consistent with laboratory so2 photooxidation experiments using uv light at 248 nm maximum absorption of ozone whereas sulfur isotopic anomalies previously observed in archean samples are consistent with photodissociation at 190 220 nm a mechanism of so2 photooxidation occurring in the early stage of a stratospheric volcanic plume in the range of 220 320 nm weak band absorption of so2 is also proposed since mass independent sulfur isotope anomalies in stratospheric volcanic sulfate appear to depend on the exposure of so2 to uv radiation their measurements might therefore offer the possibility to determine the degree of uv penetration in the ozone absorption window for the present and past atmospheres they can also be used to determine the stratospheric or tropospheric nature of volcanic eruptions preserved in glaciological records offering the possibility to reassess the climatic impact of past volcanic eruptions

relative roles of source composition fractional crystallization and crustal contamination in the petrogenesis of andean volcanic rocks there are well established differences in the chemical and isotopic characteristics of the calc alkaline basalt andesite dacite rhyolite association of the northern n v z central c v z and southern volcanic zones s v z of the south american andes volcanic rocks of the alkaline basalt trachyte association occur within and to the east of these active volcanic zones the chemical and isotopic characteristics of the n v z basaltic andesites and andesites and the s v z basalts basaltic andesites and andesites are consistent with derivation by fractional crystallization of basaltic parent magmas formed by partial melting of the asthenospheric mantle wedge containing components from subducted oceanic lithosphere conversely the alkaline lavas are derived from basaltic parent magmas formed from mantle of within plate character recent basaltic andesites from the cerro galan volcanic centre to the se of the c v z are derived from mantle containing both subduction zone and within plate components and have experienced assimilation and fractional crystallization a f c during uprise through the continental crust the c v z basaltic andesites are derived from mantle containing subduction zone components probably accompanied by a f c within the continental crust some c v z lavas and pyroclastic rocks show petrological and geochemical evidence for magma mixing the petrogenesis of the c v z lavas is therefore a complex process in which magmas derived from heterogeneous mantle experience assimilation fractional crystallization and magma mixing during uprise through the continental crust

the cadomian orogeny in the north armorican massif a brief review the north armorican massif nam of nw france is the type locality of the late precambrian cadomian orogenic belt the nam largely escaped reworking during the upper palaeozoic variscan cycle with the result that earlier geological relationships are commonly preserved intact a large part of the cadomian belt of the nam comprises variably deformed and metamorphosed supracrustal rocks of the brioverian succession barrois 1895 1896 1908 graindor 1957 cogne 1962 le corre 1977 rabu et al 1982 1983 chantraine et al 1982 the cadomian orogeny which takes its name from cadomus caen in normandy was defined by bertrand 1921 as the late precambrian orogeny which in the nam resulted in the folding and uplift of the brioverian succession prior to the deposition of lower palaeozoic red bed sequences events which have been ascribed to the cadomian orogeny span the period c 700 425 ma during which time the brioverian was heterogeneously deformed and metamorphosed and intruded by calc alkaline igneous complexes the evolution of the belt has been interpreted in terms of the gradual cratonization of calc alkaline arc complexes and syn orogenic sediments in an andean type continental margin brown et al 1990 dupret et al 1990 this contribution reviews briefly the geology of the cadomian belt of the nam fig 1 and outlines some of the more controversial debates concerning the distribution and status of precadomian basement the stratigraphy of the brioverian succession the nature of cadomian magmatism the kinematic significance of major structures and the geotectonic setting of the component parts of the belt

variations of the isotopic composition of sulfur in enstatite and ordinary chondrites abstract high precision sulfur isotopic analyses 33s 34s and 36s of bulk ordinary and enstatite chondrites demonstrate that systematic variations exist the average 34s values are 0 26 0 07 0 02 0 06 and 0 49 0 16 for enstatite and ordinary and carbonaceous chondrites respectively isotopic variations of different sample specimens of primitive meteorites e g qingzhen and abee have been observed which may be attributed to heterogeneity in the early solar nebula sulfur isotopic fractionations in both bulk samples and mineral separates are mass dependent and no nuclear isotopic anomalies have been detected the sulfur isotopic compositions of both mineral and density separates have been measured the sulfur isotopic compositions of separated chondrules from chainpur and bjurbole are reported significant isotopic difference for the chondrules from the bulk meteorite are noted for both meteorites

sources of sulphur for the proterozoic kiggavik uranium deposit nunavut canada the thelon basin is temporally and spatially related to the athabasca basin in saskatchewan canada which hosts the highest grade unconformity related uranium deposits in the world several uraniu

response of sea surface properties to hurricane dennis in the eastern gulf of mexico 1 sea surface reflectance ssr and sea surface temperature sst were assessed in the eastern gulf of mexico in early july 2005 after passage of hurricane dennis a category 4 storm using data from the modis seawifs and avhrr satellite sensors historical hydrographic and nutrient surveys and a simple vertical water column mixing model the bathymetric gradient across the shelf break the offshore deep nutricline and nearby loop current eddies led to unique ssr and sst changes after the passage of dennis in waters shallower than 50 m a strong sediment resuspension event led to higher ssr in the visible and an increase in the modis fluorescence line height flh these variables returned to pre storm conditions after about 10 days the flh change indicates increasing biomass in the short response time 50 m deep cooled down significantly but there was no apparent change in ssr presumably because the nutricline was too deep to be affected by vertical mixing due to the storm the three dimensional hydrographic and nutrient structure in waters near the west florida shelf defines what changes may be detected at the surface with remote sensing

u pb geochronology and hf nd isotope compositions of the oldest neoproterozoic crust within the cadomian orogen new evidence for a unique juvenile terrane new u pb dates combined with nd and hf isotopic data from rocks within the port morvan area of the baie de st brieuc region of brittany identify a unique portion of the neoproterozoic cadomia terrane two gneisses near port morvan yielded u pb dates of 754 6 0 8 ma and 746 0 0 9 ma ages that are more than 130 myr older than the oldest units formed during the main phase of early cadomian magmatism two trondhjemite boulders from the monogenetic facies of the cesson conglomerate yielded identical ages of 665 2 0 5 ma and 665 5 0 7 ma and a cobble from the polygenetic facies yields a 207pb 206pb date of 637 2 ma individual detrital zircons from a sandstone associated with the cesson conglomerates yield concordant u pb dates ranging from 650 3 ma to 624 1 0 6 ma initial nd values for the rocks in this region range from 5 0 to 6 6 indicative of a substantial input from depleted mantle initial hf values determined on zircons from these neoproterozoic rocks including the detrital zircons range from 6 7 to 14 5 consistent with the nd isotopic results maximum initial hf values for two 2 ga icartian gneisses considered basement to cadomia average 8 4 and 8 7 in contrast to the results of the port morvan rocks 616 608 ma syn tectonic intrusions from normandy and the british channel islands all have negative initial nd values 10 4 to 8 3 consistent with significant contamination by ancient crust such as the 2 ga gneisses the oldest arc related magmas should have interacted most extensively with cadomian basement buffering younger mantle derived magmas that were generated in subsequent magmatic episodes the rocks within the port morvan region are thus inconsistent as examples of the earliest cadomian intrusions as they show no evidence of interaction with 2 ga basement instead the older ages and mantle like isotopic composition of these rocks suggest they are part of an independent terrane that formed prior to and independently from the cadomian arc possible terrane scale structural boundaries have recently been identified including the newly recognized port morvan thrust fault and the nw dipping main cadomian thrust

igneous activity in the southern andes and northern antarctic peninsula a review the antarctic peninsula and the southern andean continental margin have been the sites of extensive and varied magmatic activity since at least late palaeozoic time the dominant activity has been of calc alkaline character and although andesite and tonalite are the main rock types there are well marked transverse variations in the major and trace element chemistry of the magmas erupted in both areas thus calc alkaline magmas erupted farthest from the ancestral trench are generally more silicic potassic and light ree enriched than magmas erupted closer to the trench in both regions the locus of calc alkaline activity has tended to move trenchwards since the palaeozoic although activity began to wane during the mid cenozoic when subduction of the pacific plate slowed down and ceased a northward cessation of calc alkaline magmatism along the antarctic peninsula can be linked in broad terms to the progressive northwards subduction of sections of the aluk ridge during the cenozoic extensional tectonics within and behind the main igneous belts caused the development of narrow back arc basins in southern chile during the mesozoic and in bransfield strait along the northern antarctic peninsula during recent times tholeiitic magmas with transitional calc alkaline characteristics were erupted in these basins in addition alkalic basalts and related undersaturated magma types were erupted onto the stable continental platform well behind the main calc alkaline and marginal basin magmatic belts during cenozoic and recent times probably in response to extensional tectonics as subduction slowed or ceased

forced stage response to a moving hurricane abstract the upper ocean s response to three hurricanes norbert 1984 josephine 1984 and gloria 1985 is examined using field observations and a numerical ocean model our goal is to describe the physical processes that determine the structure and amplitude of hurricane driven upper ocean currents all three of these northern hemisphere hurricanes produced a rightward biased response of the mixed layer current and transport this asymmetry arises because the wind stress vector rotates clockwise on the right side of the track and remains nearly parallel with the inertially rotating mixed layer current during most of the hurricane passage the maximum observed mixed layer current varied from 0 8 m s 1 in response to josephine which was a large but comparatively weak hurricane to 1 7 m s 1 in response to gloria which was very large and also intense these cases have been simulated with a three dimensional numerical model that includes a treatment of wind driven vertical mixing within the primitive

the cadomian active margin north armorican massif france a segment of the north atlantic panafrican belt abstract within the european variscan belt the armorican massif northwestern france contains an isolated fragment of the north atlantic panafrican belt the cadomian block mostly unaffected by variscan deformation this block is composed of neoproterozoic rocks ranging in age from 620 to 540 ma brioverian locally overlying a composite basement of icartian 2000 ma or pentevrian 750 ma age the cadomian tectonics the last magmatic manifestations of which are dated at around 540 ma were sealed by a cover of early cambrian rocks in normandy and early ordovician rocks in brittany five units are distinguished in this cadomian block tregor saint brieuc guingamp saint malo and fougeres although the units are bound by major faults the overall coherence of their different protolithic characteristics suggests that they can be fitted into a simple geodynamic model the tregor unit represented by the north tregor batholith of crustal affinity and its icartian host rock probably reflects an early cadomian evolution the saint brieuc unit essentially made up of magmatic rocks of juvenile affinity includes two assemblages juxtaposed by the cadomian tectonics 1 a volcanosedimentary succession formed in a typical island arc setting reflecting subduction around 610 ma and 2 a volcanic plutonic complex emplaced around 590 ma in an extensional active continental margin of pentevrian age the guingamp unit predominantly migmatitic includes a tectonic slice of deep origin the extrusion of which accompanied the exhumation of the migmatites it may represent the trace of a possible suture the saint malo unit is composed of brioverian detrital rocks the significance of which is uncertain passive continental margin or accretionary prism it is structured around a late migmatitic dome 540 ma the fougeres unit corresponds to the outer domain of the cadomian orogeny it was only weakly deformed by cadomian tectonics and is intruded by the large mancellian batholith of crustal origin dated at 540 ma together the structural units are interpreted in the framework of an evolving active margin juxtaposing continental margin marginal basin and volcanic arc before being shortened during the cadomian convergent tectonics

short paper cadomian terrane tectonics and magmatism in the armorican massif the north armorican composite terrane nw france is a collage of displaced terranes which result from the amalgamation of cadomian continental arcs and marginal basin complexes by sinistral transpression along a continental margin above a subduction zone early cadomian arc activity occurred at c 700 650 ma but terrane accretion did not occur until c 540 ma and post tectonic magmatism persisted well into the palaeozoic cadomian events thus span a considerably greater period than previously supposed

the cadomian granites of mancellia northeast armorican massif of france relationship to the st malo migmatite belt petrogenesis and tectonic setting abstract the north armorican shear zone nasz divides the cadomian belt of the armorican massif of france into two major terranes the north armorican composite terrane nact and the central armorican terrane cat the nact is a pastiche of displaced blocks and terranes st brieuc terrane st malo terrane and mancellian terrane which results from the amalgamation of cadomian continental arc and basin complexes by sinistral transpression along a continental margin above a southerly dipping subduction zone in the nact the neoproterozoic brioverian succession was deformed and metamorphosed during the cadomian orogeny and intruded by syn to post tectonic plutonic complexes the st malo migmatite belt is a syn tectonic suite of anatectic migmatites derived through partial melting of the brioverian succession using the t test on whole rock geochemical data there is no evidence to suggest that a sample of st malo diatexites comes from a population with a different mean than some samples of the brioverian succession sandstones resulting homogeneous diatexites anatectic granites of the core were emplaced syn kinematically into cadomian strike slip shear zones thus the age of anatexis of 540 ma is also the date of strike slip shearing and provides a minimum age for the sinistral transpression which amalgamated the terranes of the nact the mancellian granites to the southeast of the st malo migmatites were emplaced at 540 ma and are overlain unconformably by cambrian sediments overall geochemistry and a variety of specific geochemical parameters show that the mancellian granites are similar to the diatexites and anatectic granites of the st malo migmatite belt using the t test on whole rock geochemical data there is no evidence to suggest that the sample of mancellian granites comes from a population with a different mean than the sample of st malo diatexites additionally both suites of rocks are peraluminous they have similar distributions of rb sr and ba they have k rb ratios around 225 and they plot largely within the vag field using trace element discrimination diagrams for the interpretation of tectonic setting samples of the brioverian succession sandstones the st malo migmatites and the mancellian granites all exhibit similar primordial mantle normalized element patterns preliminary results of nd and sr isotope studies reveal a similar restricted range of values for nd between 4 0 and 7 3 and sr between 3 and 42 and depleted model ages in the range 1 7 to 1 5 ga tdmur for both mancellian granites and st malo migmatites isotopic features which set these rock types apart from other cadomian granites within the nact the st malo migmatite belt and the mancellian granites are coeval at 540 ma and both developed by anatexis at intermediate crustal depths of the brioverian succession within an inverted but only moderately overthickened behindarc basin in comparison with the st malo migmatites the mancellian granites represent farther travelled products of intracrustal melting but their geochemistry still preserves the characteristic signature of the source

caledonian plutonism in britain a summary the caledonian granites of britain are a wide ranging suite of pretectonic and posttectonic tonalite granodiorite granite intrusions which were emplaced in the time interval 650 380 ma ago the volume of magmatic products and the frequency of intrusions increased with time as closure of the iapetus ocean occurred across the caledonide belt in the british isles early pretectonic and posttectonic intrusions older than about 410 ma are distinguished from a later post 410 ma group using geophysical gravity aeromagnetic and heat production and geochemical data the evidence is interpreted in terms of a trend with time from relatively local thermal and crust dominated melting events to a final widespread melting event at deeper levels the latter event produced abundant intrusions with characteristics that resemble the calc alkaline batholiths of modern destructive margins finally we propose that crustal growth during the caledonian period took place by northward lateral accretion of the european continental foreland and by vertical accretion of continental crust on both margins by underplating and by later intrusive magmatism

geochemistry and u pb and 40ar 39ar geochronology of the man of war gneiss lizard complex sw england pre hercynian arc type crust with a sudeten iberian connection the man of war gneiss is a variably deformed meta igneous body that ranges in composition from gabbro to tonalite and comprises part of the basal structural slice of the lizard ophiolite complex sw england u pb dating of zircon demonstrates that the parental magmas crystallized in the earliest ordovician 499t s 3 ma but 40 ar 39 ar step heating analysis of amphiboles suggests that at least the northernmost zone of the gneiss was subjected to an amphibolite grade metamorphic event at c 374 ma probably associated with thrust emplacement of the ophiolite the gneiss exhibits major trace and rare earth element variations in conformity with an origin through partial melting of an amphibolitic source containing hornblende and plagioclase probably with minor garnet and zircon the elemental abundances and variations are characteristic of granitoids formed in supra subduction zone environments a granitoid sill within the adjacent old lizard head series schists previously inferred to be related to the man of war gneiss is trondhjemitic and exhibits higher sio 2 tio 2 and mgo but lower zr v ba and sr contents and therefore is probably not genetically related to the latter the sill may record local melting during ophiolite emplacement the man of war gneiss probably represents a structural inlier of pre hercynian basement incorporated in the hercynian nappes of sw england during nnw directed thrusting we emphasize the geological and geochronological similarities between variably deformed granitoid units of the lizard complex the sudeten massif of southern poland and the allochthonous complexes of northern portugal and nw spain these granitoid rocks may represent dispersed remnants of tremadoc arcs that formed oceanward from the northern margin of gondwana this is further convincing evidence that at this time eastern avalonia was separated from northern gondwana by an ocean basin that may have been connected with the tornquist sea

the rise of atmospheric oxygen when did atmospheric oxygen rise to near present concentrations and what led to this rise as kasting explains in his perspective recent results have provided stronger than ever evidence that the switch from an anoxic to an oxic atmosphere occurred around 2300 millions years ago but researchers remain divided over the mechanism catling et al resurrect a previously proposed mechanism involving hydrogen escape to space with a couple of new twists whether their mechanism is viable depends on the oxidation state of the continental and oceanic crust at this crucial time of earth9s evolution

precadomian relicts in the armorican massif their age and role in the evolution of the western and central european cadomian hercynian belt abstract well dated precambrian is mostly developed in the north of the armorican massif in which area voluminous cadomian magmatism is dated at between 650 and 550 ma much older relicts occur at cap de la hague in guernsey and in the tregor and are also found in the northern continental margin of the iberian peninsula in all these occurrences whole rock systems have been opened so that the true ages cannot be determined by the rb sr whole rock isochron method four u pb zircon ages are between 1 8 and 2 ga in guernsey icart orthogneisses in tregor port beni trebeurden morguignen orthogneisses there is no evidence from strontium isotopes that these isolated and scattered relicts have a wide extension or that such ancient continental crust played an important role in magma genesis from 650 ma to 270 ma ago on the contrary the evolution of initial 87sr 86sr ratios with time shows that the observed mid and west european continental crust is probably not older than 700 ma the increase of the initial 87sr 86sr ratios of the magmas with time suggests that after its formation in cadomian times this segment of continental crust evolved virtually as a closed system and hercynian magmatism arose principally from re melting of relatively young sialic components

formation of diatexite migmatite and granite magma during anatexis of semi pelitic metasedimentary rocks an example from st malo france petrological and geochemical variations are used to investigate the introduction formation of granite magma from diatexite migmatites derived from partial melting experiments show that protoliths of pelite metasedimentary rocks of pelitic to greywacke composition at st and greywacke composition yield up to 40 vol malo france anatexis occurred at relatively low temperatures granite melt over the temperature range 650 900 c and pressures 800 c 4 7 kbar principally through muscovite typical of anatexis of the continental crust conrad et dehydration melting biotite remained stable and serves as a tracer al 1988 vielzeuf holloway 1988 patino douce for the solid fraction during melt segregation the degree of partial johnston 1991 vielzeuf montel 1994 patino douce melting calculated from modal mineralogy and reaction stoichiometry harris 1998 therefore to make a granite magma was 40 vol there is a continuous variation in texture the melt fraction must be segregated from a solid fraction mineralogy and chemical composition in the diatexite migmatites of much greater volume and then collected together mesocratic diatexite formed when metasedimentary rocks melted the type of melt residuum separation process depends sufficiently to undergo bulk flow or magma flow but did not on the melt fraction present experience significant melt residuum separation mesocratic diatexite melt residuum separation at low degrees of partial that underwent melt segregation during flow generated 1 memelting f and consequently low melt fraction mf lanocratic diatexites at the places where the melt fraction was has been documented from metatexite migmatites in removed leaving behind a biotite and plagioclase residuum enriched these rocks melt segregation produced centimetre scale in tio2 feot mgo cao sc ni cr v zr hf th u and leucosomes distributed in a host composed of layers that ree and 2 a complementary leucocratic diatexite enriched in have melted and others that have not e g henkes sio2 k2o and rb where the melt fraction accumulated leucocratic johannes 1981 gupta johannes 1982 dougan 1983 diatexite still contained 5 15 vol residual biotite mg number sawyer 1987 tait harley 1988 barbey et al 1990 40 44 and 10 20 vol residual plagioclase an22 anatectic brown 1994 leucosomes represent small volumes of granite magma developed from the leucodiatexite first by further felsic magma formed when melt was squeezed out of the melt residuum separation then through fractional crystallization deforming matrix mclellan 1988 sawyer 1991 1994 most biotite in the anatectic granite is magmatic mg number brown 1994 brown et al 1995 and collected in low18 22 pressure sinks such as shear bands and inter boudin

petrology of a magma chamber the plutonic complex of guernsey channel islands uk the northern plutonic complex of guernsey is a calc alkaline intrusion emplaced within a metamorphic complex composed mainly of the icart gneiss and the perelle gneiss the northern plutonic complex is made up of four distinct bodies the st peter port gabbro the bordeaux diorite group the l ancresse granodiorite and the cobo granite which are roughly contemporaneous emplaced at the end of the cadomian orogeny at around 550 560 ma the st peter port gabbro and the bordeaux diorite group are relicts of a magma chamber characterized by layered rocks along the margins and heterogeneous rock associations in the core of the chamber resulting from stirring by convection oxygen isotopic data are consistent with melting of the country rock possibly the perelle gneiss in response to the intrusion of the gabbro diorite magma chamber the resulting acidic melts mixed with crystallizing gabbro diorite magma to yield the cobo granite and the l ancresse granodiorite this mechanism of acid magma genesis can probably be extended to other late cadomian magmatic events in the northern armorican massif suggesting that basic plutonism in this area may be more important than previously considered

satellite observations of asymmetrical physical and biological responses to hurricane earl 1 asymmetrical physical and biological responses to hurricane earl in 2010 are revealed with a combined data set of the moderate resolution imaging spectroradiometer modis ocean color and advanced microwave scanning radiometer eos amsr e sst observations onboard the satellite aqua hurricane earl induced broad sst drops and elevated chlorophyll a concentrations along its track the ocean s physical and biological responses are notably right biased when the hurricane passed along the u s east coast in the ranges within 100 km off the track the sst dropped 1 85 c and 1 23 c on the right and left sides respectively on the other hand the ratios of the chlorophyll a concentration before and after the passage of hurricane earl are 2 04 on the right side and 1 33 on the left in addition to the satellite observed sea surface changes temperature and salinity profiles of an argo float on earl s track show the ocean s physical response occurred mostly within the mixed layer and thermocline in the upper 70 m water column

sulphur isotopes and the early archaean sulphur cycle abstract the early archaean sulphur cycle continues to be discussed rather controversially on the basis of mass dependent and independent sulphur isotope fractionations in sedimentary sulphates and sulphides major debates are the ultimate sulphur source and the isotopic composition of seawater sulphate and the process es involved in the formation of sedimentary pyrite new results for sedimentary pyrite from the isua greenstone belt sw greenland are presented current views of the global sulphur cycle are evaluated which are based on these and additional published sulphur isotope records for southern africa western australia and india in view of the absence of unequivocal evidence for a clearly biological origin magmatic hydrothermal processes are considered to be largely responsible for the precipitation of sulphides in sedimentary environments of early archaean age sedimentary sulphides from the warrawoona group australia could represent a possible exception

evolution of the oceanic sulfur cycle at the end of the paleoproterozoic here we present new measurements of 32 s 33 s 34 s and 36 s in sedimentary sulfides and couple these measurements with modeling treatments to study the sulfur cycle of a late paleoproterozoic marine basin we target the transition in ocean chemistry from the deposition of paleoproterozoic iron formations gunflint formation biwabik formation trommald formation and mahnomen iron formations to the inferred sulfidic ocean conditions recorded by overlying shale rove formation the data suggest that certain features of the global sulfur cycle such as a control by sulfate reducing prokaryotes and low mm concentrations of oceanic sulfate were maintained across this transition this suggests that the transition was associated with changes in the structure of the basin scale sulfur cycle during deposition of these sediments sulfide data from the iron formations are interpreted to reflect sedimentary sulfides formed from microbial reduction of pore water sulfate that was supplied through steady state exchange with an overlying oceanic sulfate reservoir the sulfide data for the euxinic rove formation shales reflect the operation of a sulfur cycle that included the loss of sulfide by a rayleigh like process we suggest that the prevalence of large and variable heavy isotope enrichments observed in rove formation sulfide minerals reflect a sustained and significant net loss of sulfide from the euxinic water column either as a result of a shallow chemocline and degassing to the atmosphere or as a result of a water column pyrite sink the inclusion of 36 s measurements in addition to 32 s 33 s and 34 s illustrates the mass dependent character of these sedimentary environments ruling out contributions from the weathering of archean sulfides and pointing to at least modest levels of sustained atmospheric oxygen 10 5 present atmospheric levels of o2

multiple sulphur and iron isotope composition of detrital pyrite in archaean sedimentary rocks a new tool for provenance analysis abstract multiple s 34 s and 33 s and fe 56 fe isotope analyses of rounded pyrite grains from 3 1 to 2 6 ga conglomerates of southern africa indicate their detrital origin which supports anoxic surface conditions in the archaean rounded pyrites from meso to neoarchaean gold and uranium bearing strata of south africa are derived from both crustal and sedimentary sources the latter being characterised by non mass dependent fractionation of s isotopes 33 s as negative as 1 35 and large range of fe isotope values 56 fe between 1 1 and 1 2 most sediment sourced pyrite grains are likely derived from sulphide nodules in marine organic matter rich shales sedimentary exhalites and volcanogenic massive sulphide deposits some sedimentary pyrite grains may have been derived from in situ sulphidised fe oxides prior to their incorporation into the conglomerates as indicated by unusually high positive 56 fe values sedimentary sulphides without significant non mass dependent fractionation of s isotopes were also present in the source of some conglomerates the abundance in these rocks of detrital pyrite unstable in the oxygenated atmosphere may suggest factors other than high p o 2 as the cause for the absence of significant non mass dependent fractionation processes in the 3 2 2 7 ga atmosphere rounded pyrites from the c 2 6 ga conglomerates of the belingwe greenstone belt in zimbabwe have strongly fractionated 34 s 33 s and 56 fe values the source of which can be traced back to black shale hosted massive sulphides in the underlying strata the study demonstrates the utility of combined multiple s and fe isotope analyses for provenance reconstruction of archaean sedimentary successions

triple oxygen isotope investigation of fine grained sediments from major world s rivers insights into weathering processes and global fluxes into the hydrosphere abstract continental weathering is accompanied by formation of clays and other secondary minerals and their 18 o and 17 o values should hence reflect to some extent signatures of meteoric water 18 o mw and mean annual temperatures mat our ability to extract climate information from weathered products across the geologic history relies on analytical methods tested and calibrated against modern climate conditions we here present triple oxygen isotope analyses of clay size sediments from 45 rivers worldwide as well as 18 o analyses of corresponding silt and sand rich detrital fractions which altogether cover about 25 of the continental area that drained into the oceans extending from the tropics to polar regions the majority of studied clays closely approximate weathering products always having high 18 o signatures regardless of the bedrock type and in equilibrium with local meteoric waters silts are only 1 9 lighter on average due to greater detrital dilution overall bulk clays from across different climatic regions do not vary much isotopically an observation which we attribute to opposing effects of temperature on clay water fractionation and hydrologic relationship between temperature and 18 o mw mathematical inversion of measured clay 18 o and 17 o values corrected for detrital contribution into mat and 18 o mw compiled for each studied watershed returns satisfactory estimates globally triple o isotopes in clays appear to be water dominated being controlled almost exclusively by 18 o mw at respective temperature of weathering with minor effects related to evaporation using sand from rivers correlation of 18 o silts with detrital proportions and estimated surface outcrop of different rock types we additionally arrive at a 11 5 estimate for the exposed silicate crust undergoing weathering globally averaged sediment flux weighted clay 18 o and 17 o values are 14 80 and 0 164 respectively these values are significantly skewed toward o isotope signatures for the southeast asia and western pacific regions characterized by very high sediment fluxes to the ocean using both clay and silt size fractions the total weighted silicate weathering 18 o signature exported to the world s ocean is 2 59 almost 50 higher the previous estimate yielding an ice free world hydrosphere estimate of 0 78 overall the modern river clays represent a snapshot of modern weathering conditions on continents and associated first order climatic signatures related to mat and 18 o of the hydrosphere this implies that measured increase in 18 o and stepwise decrease in 17 o in shales in the geologic record capture evolving global hydrologic cycle upon continental emergence decrease in global mat or diagenetic conditions and decreasing ocean mass via rehydrating of the mantle by subduction of hydrated low 18 o high 17 o slabs

time span of plutonism fabric development and cooling in a neoproterozoic magmatic arc segment u pb age constraints from syn tectonic plutons sark channel islands uk abstract new u pb zircon and titanite dates from syn tectonic plutons on the british channel island of sark constrain the time span of plutonism fabric development and cooling in this part of the neoproterozoic cadomian magmatic arc the tintageu leucogneiss is a mylonitic unit that was dated previously at 615 6 4 2 2 3 ma the port du moulin quartz diorite which intruded the tintageu unit contains a high strain solid state deformation fabric that is less intense than but parallel to fabrics in the leucogneiss and yields a u pb zircon date of 613 5 2 3 1 5 ma the little sark quartz diorite also displays solid state deformation fabrics in addition to relict magmatic textures and yields a u pb zircon date of 611 4 2 1 1 3 ma the north sark granodiorite is largely penetratively undeformed exhibits mainly magmatic fabrics and textures and has a u pb zircon date of 608 7 1 1 1 0 ma two fractions of titanite from each intrusion are essentially concordant and are identical within error with mean dates of 606 5 0 4 ma port du moulin quartz diorite 606 2 0 6 ma little sark quartz diorite 606 4 0 6 ma north sark granodiorite the new u pb data in combination with previous u pb and 40 ar 39 ar data and previous field studies confirm the syn tectonic nature of the sark plutons and quantify the time span ca 7 m y required for intrusion and sufficient crystallization of each body to record incremental strain during waning deformation titanite u pb and hornblende 40 ar 39 ar dates mark final cooling about 2 m y after intrusion of the last pluton

significance of a hiatus in down temperature fabric development within syn tectonic quartz diorite complexes channel islands uk detailed fabric development histories have been deduced for neoproterozoic foliated quartz diorite complexes of the channel islands uk the plutons were emplaced during regional d2 deformation magmatic fabrics formed at low crystal contents pre rheologically critical melt percent are only locally preserved due to overprinting by solid state deformation which occurred at moderate temperatures 400 550 c this is demonstrated by brittle microcracking of plagioclase and amphibole with only local ductile bending and dynamic recrystallization marginal recrystallization and myrmekite development on alkali feldspar ductile deformation of quartz to form types 2 3 ribbons quartz recrystallization by sub grain rotation associated with a slip but not c slip biotite recrystallization within micro shears and variable amphibole recrystallization the deformation histories display a distinct division between magmatic state and moderate temperature solid state deformation features with little evidence for intervening high temperature solid state fabrics this contrasts with criteria widely considered diagnostic of syn tectonic plutons which envisage development of a continuum of magmatic through high temperature solid state deformation fabrics however we consider the plutons syn tectonic and attribute the hiatus to contrasting strain and pluton cooling rates length and nature of deformation events and host rock ambient temperatures intermediate magmas emplaced at moderate to shallow levels in the crust may be more prone to develop such apparently punctuated deformation histories than sio 2 richer granitoids

data and numerical analysis of astronomic tides wind waves and hurricane storm surge along the northern gulf of mexico the northern gulf of mexico ngom is a unique geophysical setting for complex tropical storm induced hydrodynamic processes that occur across a variety of spatial and temporal scales each hurricane includes its own distinctive characteristics and can cause unique and devastating storm surge when it strikes within the intricate geometric setting of the ngom while a number of studies have explored hurricane storm surge in the ngom few have attempted to describe storm surge and coastal inundation using observed data in conjunction with a single large domain high resolution numerical model to better understand the oceanic and nearshore response to these tropical cyclones we provide a detailed assessment based on field measurements and numerical simulation of the evolution of wind waves water levels and currents for hurricanes ivan 2004 dennis 2005 katrina 2005 and isaac 2012 with focus on mississippi alabama and the florida panhandle coasts the developed ngom3 computational model describes the hydraulic connectivity among the various inlet and bay systems gulf intracoastal waterway coastal rivers and adjacent marsh and built infrastructure along the coastal floodplain the outcome is a better understanding of the storm surge generating mechanisms and interactions among hurricane characteristics and the ngom s geophysical configuration the numerical analysis and observed data explain the 2 m s hurricane induced geostrophic currents across the continental shelf a 6 m s outflow current during ivan the hurricane induced coastal kelvin wave along the shelf and for the first time a wealth of measured data and a detailed numerical simulation was performed and was presented for isaac

archean emplacement of eclogitic components into the lithospheric mantle during formation of the kaapvaal craton re os data for selected whole rock eclogites and eclogitic sulfide inclusions in diamonds from seven kimberlites on the kaapvaal zimbabwe cratons yield ages around 3 ga the presence of such old eclogitic components in the subcontinental lithospheric mantle is more common than previously thought overlap of these ages with those of many cratonic peridotites demonstrates that incorporation of eclogitic materials accompanied or closely followed cratonic lithosphere stabilization many of these eclogitic components have fractionated c n o and s isotopic compositions which could have been created at low temperatures implying that some style of archean subduction involving emplacement of oceanic lithosphere was part of craton keel development

crustal growth and late precambrian early palaeozoic plate tectonic evolution of england and wales comparison of the basement rocks of britain reveals major contrasts to the n and s of the iapetus suture solway shannon line north of the suture polymetamorphic high grade basement schists and gneisses and igneous rocks date from about 2900 ma to c 400 ma the latter age corresponding to closure of the iapetus ocean by contrast s of the suture in england and wales the basement is dominantly low grade metamorphic rock together with intrusive and extrusive igneous and sedimentary rocks there is little geological or geochemical evidence for the presence of basement older than c 900 ma below this area and the predominant expression of crustal growth in england and wales is indicated by radiometric ages between c 700 ma and 450 ma reflecting late precambrian palaeozoic magmatism and metamorphism palaeomagnetic data from scotland demonstrate that the crust in northern britain developed as an integral part of the laurentian shield during mid proterozoic times 1600 1000 ma the palaeomagnetic record from the pre ordovician rocks of england and wales shows that this area was unrelated to the laurentian shield prior to closure of the iapetus ocean the apparent polar wander a p w path is that of a distinct microplate involved in rapid growth of iapetus during early cambrian times and emplaced in its present configuration adjacent to northern britain as a result of subduction of the ocean basin between cambrian and silurian times we conclude that whereas the basement to the north of the iapetus suture formed an essentially continental unit from 2900 to 400 ma the basement of england and wales is a result of crustal growth from about 900 ma to 400 ma and formed by accretion of island arcs associated accretionary prisms and fore arc basin sediments within the iapetus ocean

pathways for neoarchean pyrite formation constrained by mass independent sulfur isotopes it is generally thought that the sulfate reduction metabolism is ancient and would have been established well before the neoarchean it is puzzling therefore that the sulfur isotope record of the neoarchean is characterized by a signal of atmospheric mass independent chemistry rather than a strong overprint by sulfate reducers here we present a study of the four sulfur isotopes obtained using secondary ion ms that seeks to reconcile a number of features seen in the neoarchean sulfur isotope record we suggest that neoarchean ocean basins had two coexisting significantly sized sulfur pools and that the pathways forming pyrite precursors played an important role in establishing how the isotopic characteristics of each of these pools was transferred to the sedimentary rock record one of these pools is suggested to be a soluble sulfate pool and the other pool atmospherically derived elemental sulfur is suggested to be largely insoluble and unreactive until it reacts with hydrogen sulfide we suggest that the relative contributions of these pools to the formation of pyrite depend on both the accumulation of the insoluble pool and the rate of sulfide production in the pyrite forming environments we also suggest that the existence of a significant nonsulfate pool of reactive sulfur has masked isotopic evidence for the widespread activity of sulfate reducers in the rock record

contrasting evolution of calc alkalic volcanic and plutonic rocks of western chihuahua mexico two sequences of continental arc igneous rocks occur in the batopilas area of the sierra madre occidental of northwestern mexico the older includes late cretaceous to early cenozoic granitoids and the younger is a mid tertiary andesite to rhyolite series that is represented largely by voluminous ignimbrites the latter sequence contains rocks varying from 54 to 78 wt sio2 whereas the granitoids have a more restricted range in sio2 57 68 wt the major element chemistry of the two sequences is generally similar however the older granitoids have lower zr nb and higher nb y and k rb compared to volcanic rocks in addition the granitoids have generally smaller eu anomalies lower concentrations of ree and higher ce yb n 4 6 7 2 versus 3 8 4 0 than the volcanic rocks the intermediate rocks of the two sequences quartz diorites and andesites had similar petrogenetic histories and both may have originated by fractionation of mantle derived basaltic magmas in contrast the more silicic rocks granodiorites on one hand and dacites and rhyolites on the other evolved very differently the granodiorites may have originated from a crustal source leaving a residue of amphibolite or garnet granulite whereas the rhyolites were the product of protracted fractional crystallization of mantle derived melts

satellite observations of sea surface cooling by hurricanes sea surface cooling associated with 13 hurricanes in the western north atlantic between september 1981 and december 1984 is examined using satellite derived sea surface temperature fields some surface cooling is observed in all cases however because of cloud cover and the fairly weak signal in some cases we see pronounced cooling along an extensive and continuous portion of the storm path for only three strong hurricanes the persistence of cooling following the passage of a hurricane varies from a few days to at least 16 days the amplitude of cooling is moderately well correlated with hurricane strength and is as large as 3 5 c when the hurricanes move rapidly the maximum cooling occurs well to the right of the track approximately 70 km whereas for slowly moving hurricanes the maximum cooling occurs near or on the track because western north atlantic hurricanes are often found in close proximity to high pressure systems daytime satellite images must be made with some care because of diurnal warming

geochemical markers of the cretaceous tertiary boundary event at brazos river texas usa the cretaceous tertiary boundary sites around the gulf of mexico are close to the chixculub impact site and are relatively well studied yet much remains to be learned about them therefore the first integrated study of carbon soot and fullerenes in a cretaceous tertiary boundary section was undertaken at the brazos 1 site on the brazos river in texas at the most complete section of end cretaceous and basal paleocene deposits on the texas segment of the gulf coast area up to 409 ppm of native sulfur so were serendipitously discovered in a spherule bearing unit of the br 1 section and lesser amounts were found in spherule bearing units of nearby brazos riverbed sections in a section on darting minnow creek the isotopic composition 33s 12 97 34s 24 89 and 36s 46 4 implies that this so cannot have come to earth by the impactor that formed the chicxulub crater but most likely was produced by sulfate reducing bacteria during a local transient bacterial bloom for which the sulfate was provided by caso4 bearing spherules carbon and soot were determined in twelve samples representing all units of br 1 from the cretaceous corsicana kemp formation to the tertiary kincaid formation a significant increase of c and soot contents up to 2 2 104 ppm and 1 4 104 ppm respectively occurs in a sandy bed at the top of the kt complex fullerenes were determined in fifty four samples from all units of the same br 1 section less than 1 ppb was reliably detected at the same sandy bed where the strongest ir anomaly of the section is known to occur it is suggested here that the chicxulub impact 65 ma ago ignited local wildfires that produced c soot and fullerene which settled onshore or near shore whence they were transported to the brazos site by coastal flooding and associated sediment laden water plumes moving offshore

mass independent isotope effects in archean 2 5 to 3 8 ga sedimentary sulfides determined by ion microprobe analysis we report sulfur isotope anomalies with 33 s the deviation from a mass dependent fractionation line for the three isotope system 34 s 32 s vs 33 s 32 s ranging up to 2 within individual archean sedimentary sulfides from a variety of localities our measurements which are made in situ by multicollector secondary ion mass spectrometry unequivocally corroborate prior bulk measurements of mass independent fractionations mif in sulfur and provide additional evidence for an anoxic atmosphere on the earth before 2 ga this technique also offers new opportunities for exploring ancient sulfur metabolisms preserved in the rock record the presence of mif sulfur in sulfides from a 3 8 ga fe rich quartzite from akilia island west greenland is consistent with a marine sedimentary origin for this rock copyright 2003 elsevier science ltd

multiple sulfur and iron isotope composition of magmatic ni cu pge sulfide mineralization from eastern botswana we report here high precision multiple sulfur and iron isotope compositions for a series of mineralized samples from ni cu pge sulfide deposits in the archean tati greenstone belt and the phikwe complex of eastern botswana mineralized samples from the phoenix and selkirk ni cu pge deposits in the tati greenstone belt display slightly positive 34s isotope values ranging from 0 2 to 0 8 v cdt 33s values of sulfides at phoenix and selkirk are 0 01 to 0 08 v cdt suggesting either a dominantly mantle sulfur source or effective eradication of a crustal 33s anomaly through equilibration with large amounts of silicate melt in the selebi phikwe belt a granite gneiss terrane with abundant amphibolite lenses of either volcanic and or intrusive nature mineralized lower grade samples from the phikwe phokoje and dikoloti ni cu pge deposits have more variable 34s values ranging from 3 1 to 0 3 and display significant mass independent anomalies 33s values ranging from 0 89 to 0 27 suggesting that barren sulfides associated with distal or low temperature sea floor hydrothermal activity contributed sulfur to these deposits iron isotopes of sulfides from these deposits show a relatively small range of negative 56fe values 0 29 to 0 04 consistent with high temperature fractionations in magmatic systems with the exception of one sample from the dikoloti ni cu pge deposit of the selebi phikwe greenstone belt which shows a more negative 56fe value of 0 61 consistent with assimilation of sedimentary or hydrothermal sulfides rather than fractionations in high temperature magmatic systems data from this study highlight the complexity and variability that characterize ore forming processes in magmatic systems we suggest that the presence of sulfur bearing lithologic units in host rocks of mafic and ultramafic intrusions may not be essential toward the assessment of the prospectivity of a province to host orthomagmatic nickel sulfides geologic settings without any or little sulfur in the stratigraphy which have been traditionally neglected in terms of their prospectivity should thus be revisited and possibly reassessed considering the potential importance of external source of sulfur to generate ore deposits

the oxygen cycle of the terrestrial planets insights into the processing and history of oxygen in surface environments physical and chemical processes that operate at low temperature in earth s surface environments and in other planetary settings have left an indelible record of the evolution and interactions of planetary surface and near surface reservoirs this chapter reviews the chemistry of oxygen elemental and isotopic in lunar planetary and earth surface reservoirs the discussion begins with a brief review of the relative abundances of oxygen isotopes in planetary materials including lunar samples the snc martian meteorites and components that are inferred to come from martian surface pools this is followed by a brief largely historical account of the development of oxygen isotope geochemistry in earth surface materials the discussion then transitions using an earth systems perspective into an overview of developments in oxygen isotope geochemistry of atmospheric compounds this treatment includes recent studies that 1 use high precision measurements of 17 o and 18 o to characterize atmospheric oxygen 2 apply information about isotopically substituted species isotopologs for characterizing the position dependent isotopic fractionations of some oxygen bearing atmospheric species and 3 investigate non mass dependent isotopic fractionations in ozone and other atmospheric species the discussion then examines the evidence and models that point to change in the oxygen cycle and oxidation chemistry in earth surface environments over the course of geologic time we use the subdivisions of the earth systems the hydrosphere geosphere and biosphere as a basis for examining these changes this record is explored in the context of hypotheses and data that relate to the nature of the changes and transformations in the oxidation state of these different components of the earth s surface environments we conclude with a brief accounting of areas of research where scientifi c inquiry is presently very active

rapid emergence of subaerial landmasses and onset of a modern hydrologic cycle 2 5 billion years ago the history of the growth of continental crust is uncertain and several different models that involve a gradual decelerating or stepwise process have been proposed1 4 even more uncertain is the timing and the secular trend of the emergence of most landmasses above the sea subaerial landmasses with estimates ranging from about one billion to three billion years ago5 7 the area of emerged crust influences global climate feedbacks and the supply of nutrients to the oceans 8 and therefore connects earth s crustal evolution to surface environmental conditions9 11 here we use the triple oxygen isotope composition of shales from all continents spanning 3 7 billion years to provide constraints on the emergence of continents over time our measurements show a stepwise total decrease of 0 08 per mille in the average triple oxygen isotope value of shales across the archaean proterozoic boundary we suggest that our data are best explained by a shift in the nature of water rock interactions from near coastal in the archaean era to predominantly continental in the proterozoic accompanied by a decrease in average surface temperatures we propose that this shift may have coincided with the onset of a modern hydrological cycle owing to the rapid emergence of continental crust with near modern average elevation and aerial extent roughly 2 5 billion years ago the use of triple oxygen isotope data from continental shales spanning the past 3 7 billion years suggests that continental crust with near modern average elevation and extent emerged about 2 5 billion years ago

timing of cadomian deformation and magmatism within la hague nw france the la hague peninsula normandy nw france contains the most northerly components of the late neoproterozoic cadomian orogeny u pb dates for single grain and small multiple grain zircon separates from carefully selected plutons provide geochronological constraints on the timing of deformation and magmatism within the region the syntectonic jardeheu quartz diorite and omonville granodiorite were emplaced and contemporaneously deformed during the development of a greenschist facies fabric pervasive across the peninsula u pb zircon dates of 610 1 ma for the jardeheu quartz diorite and 608 2 ma for the omonville granodiorite are similar to a previously reported sensitive high resolution ion microprobe u pb date for metamorphism of the basement and indicate that a regionally significant period of metamorphism and magmatism occurred between 620 and 608 ma an emplacement age of 573 9 1 3 0 9 ma for the syntectonic thiebot granodiorite places limits on the timing of deformation along the thiebot shear zone zircons from the undeformed st martin monzonite give a precise u pb age of 581 3 1 1 ma the new dates point to reactivation of magmatism and localized greenschist facies deformation between 582 and 573 ma

evidence of local sourcing of sulfur and gold in an archaean sediment hosted gold deposit abstract determining the source of sulfur in an ore deposit is key to understanding the nature of the ore forming processes the neoarchaean paulsens sediment hosted gold deposit 1 moz 7 6 g t located in the pilbara craton of western australia exhibits many of the characteristics of phanerozoic shale hosted gold deposits e g huijiabao trend northern carlin trend and sukhoi log in that 1 black shales are the dominant host rock 2 gold is hosted in pyrite as both free gold and dissolved gold in the lattice of the pyrite and 3 multiple generations of pyrite have formed due to a variety of geological processes in this contribution we utilised secondary ion mass spectrometer sims to measure the in situ quadrupole 32 s 33 s 34 s and 36 s sulfur isotope compositions of the different generations of pyrite our results indicate that the both diagenetic and hydrothermal pyrite generations display similar and anomalous 33 s signatures up to 0 4 further the 33 s 36 s arrays in the hydrothermal pyrite generations lie on a slope which is similar to that of the diagenetic pyrite these data support the hypothesis that the sulfur in the ore zones came from the host hardey formation black shales we also performed trace element analyses of syn sedimentary and early diagenetic pyrite from the hardey formaiton using nano secondary ion mass spectrometry nanosims electron probe microanalysis epma and laser ablation inductively coupled plasma mass spectrometry la icpms all of which show that the syn sedimentary and early diagenetic pyrite contain high concentrations of many trace elements as ni co cu ag se te bi including up to 1 5 ppm au these metals contents are also abundant in the several generations of mineralised hydrothermal pyrite and form clear patterns of growth associated with couple dissolution reprecipitation reactions these findings clearly indicate that the fluid that transported the au must have also been enriched in the base and precious metals that are contained in the early syn diagenesis pyrite data from this study clearly support the hypothesis that in some sediment hosted gold systems all the sulfur and gold required to form the deposit are sourced from the local sedimentary package by using the presence of anomalous mass independent sulfur isotope signatures as chemically conservative and indelible tracers it is possible to fingerprint the source of sulfur in a wide range of mineral systems thus enhancing predictive exploration strategies at the regional to camp scales

multiple sulfur isotopes and the evolution of the atmosphere interest in multiple sulfur isotope analyses has been fueled by recent reports of mass independent sulfur isotope signatures in the geologic record a non zero multiple isotopic signature of sulfur 33s and 36s is produced primarily through photochemical reactions and it is an almost perfect tracer of the source of sulfur once the signature is passed on to a given sulfur reservoir it will be preserved unless there is addition of sulfur with a different 33s or 36s in the geological record this signature has been used to study the evolution of the earth s atmosphere and to trace movement of sulfur through geological systems early in earth s history recently small but significant mass independent signatures have been reported for some younger samples raising the possibility of additional applications of multiple isotope studies the purpose of this review is to introduce and discuss the implications of multiple isotope studies and to focus attention on these anomalous but not uncommon isotopic signatures

hurricane forced upwelling and chlorophyll a enhancement within cold core cyclones in the gulf of mexico 1 clear skies subsequent to hurricane ivan s passage across the gulf of mexico in september 2004 provided a unique opportunity to investigate upper ocean responses to a major hurricane oceanic cyclonic circulation was rapidly intensified by the hurricane s wind field 59 62 m s 1 maximizing upwelling and surface cooling 3 7 c in two large areas along ivan s track upward isothermal displacements of 50 65 m computed from wind stress and sea surface height changes caused rapid ventilation of thermoclines and nutriclines leading to phytoplankton blooms with peak concentrations 3 4 days later wind speed changes along ivan s track demonstrated that the cool waters 20 26 c provided immediate negative feedback to the hurricane s intensity although our study focused on a relatively small ocean area it revealed that mesoscale cyclones in addition to warm anticyclones may play an important role in producing along track hurricane intensity changes

the geochemical characteristics of granitoids in contrasting arcs and comments on magma sources geochemical variations in modern subduction related igneous suites with respect to arc maturity in time and space are illustrated using data for both volcanic suites basalt andesite and dacite and intrusive granitoid suites diorite tonalite granodiorite and granite from circum pacific arcs using trace element data we suggest that two groups of processes control the natural variation in the parental magmas of both suites a subduction zone enrichment of lithospheric mantle locally coupled with crustal assimilation allied with fractional crystallization afc in zones of thickened crust all of which yield magmas with enhanced concentrations of the large ion lithophile lil elements k rb th u lrees etc b with increasing distance from the active trench contributions from within plate sub continental lithosphere producing mantle derived magmas with enhanced levels of high field strength hfs elements among which nb ta hf and y are particularly distinctive thus even for the evolved granitoids of intrusive arc series ratios of hfs lil elements not significantly affected by crystal fractionation such as ta nb k rb la may throw some light on the origin of mafic intermediate precursor magmas in terms of these elements we suggest the following groupings for interpreting the tectonic associations of granitoid suites 1 primitive calcic arc granitoids with low lil and hfs element abundances 2 normal calc alkaline continental arc granitoids with enhanced lil element abundances and low hfs lil ratios 3 mature alkali calcic arc granitoids with high levels of lil and hfs elements and higher hfs lil ratios 4 back arc anorogenic alkaline granitoids with the highest levels of hfs elements

multiple sulfur isotope analyses support a magmatic model for the volcanogenic massive sulfide deposits of the teutonic bore volcanic complex yilgarn craton western australia we report sensitive high mass resolution ion microprobe stable isotopes shrimp si multiple sulfur isotope analyses 32s 33s 34s to constrain the sources of sulfur in three archean vms deposits teutonic bore bentley and jaguar from the teutonic bore volcanic complex of the yilgarn craton western australia together with sedimentary pyrites from associated black shales and interpillow pyrites the pyrites from vms mineralization are dominated by mantle sulfur but include a small amount of slightly negative mass independent fractionation mif anomalies whereas sulfur from the pyrites in the sedimentary rocks has pronounced positive mif with 33s values that lie between 0 19 and 6 20 with one outlier at 1 62 the wall rocks to the mineralization include sedimentary rocks that have contributed no detectable positive mif sulfur to the vms deposits which is difficult to reconcile with the leaching model for the formation of these deposits the sulfur isotope data are best explained by mixing between sulfur derived from a magmatic hydrothermal fluid and seawater sulfur as represented by the interpillow pyrites the massive sulfide lens pyrites have a weighted mean 33s value of 0 27 0 05 mswd 1 6 nearly identical with 0 31 0 08 mswd 2 4 for pyrites from the stringer zone which requires mixing to have occurred below the sea floor we employed a two component mixing model to estimate the contribution of seawater sulfur to the total sulfur budget of the two teutonic bore volcanic complex vms deposits the results are 15 to 18 for both teutonic bore and bentley much higher than the 3 obtained by jamieson et al 2013 for the giant kidd creek deposit similar calculations carried out for other neoarchean vms deposits give value between 2 and 30 which are similar to modern hydrothermal vms deposits we suggest that multiple sulfur isotope analyses may be used to predict the size of archean vms deposits and to provide a vector to ore deposit but further studies are needed to test these suggestions

a revised classification scheme of pyrite in the witwatersrand basin and application to placer gold deposits abstract pyrite is the most abundant ore mineral in gold bearing quartz pebble conglomerates qpcs of the witwatersrand basin and similar archaean sedimentary units much of the pyrite in archaean conglomerates is detrital in origin implying that it survived weathering transport and reworking under anoxic conditions detrital pyrite is generally found together with authigenic pyrite formed in situ as a result of syn to post depositional processes as pyrite is frequently associated with gold mineralization many authors have developed different pyrite classification schemes in order to better understand the nature and origin of the mineralization although the different classifications cannot always be easily compared as they are largely based on inferred pyrite genesis we propose a revised entirely descriptive classification scheme for detrital and authigenic pyrite in archaean qpcs the scheme was created in order to provide a consistent framework for the petrographic description of pyrite in clastic sedimentary rocks detrital pyrite is subdivided into massive inclusion bearing and coarsely crystalline types authigenic pyrite includes euhedral overgrowth infill aggregate and pseudomorphic types we evaluate the methods used in pyrite classification propose formation pathways for detrital and authigenic pyrites and apply the classification scheme to some well known occurrences of detrital pyrite bearing conglomerates

oxygen isotope perspective on crustal evolution on early earth a record of precambrian shales with emphasis on paleoproterozoic glaciations and great oxygenation event abstract we present stable isotope and chemical data for 206 precambrian bulk shale and tillite samples that were collected mostly from drillholes on all continents and span the age range from 0 5 to 3 5 ga with a dense coverage for 2 5 2 2 ga time interval when earth experienced four snowball earth glaciations and the irreversible rise in atmospheric o2 we observe significant downward shift of several and a smaller range of 18 o values 7 to 9 in shales that are associated with the paleoproterozoic and potentially neoproterozoic glaciations the paleoproterozoic samples consist of more than 50 mica minerals and have equal or higher chemical index of alteration than overlying and underlying formations and thus underwent equal or greater degrees of chemical weathering their pervasively low 18 o and d down to 85 values provide strong evidence of alteration and diagenesis in contact with ultra low 18 o glacial meltwaters in lacustrine deltaic or periglacial lake sikussak type environments associated with the paleoproterozoic glaciations the d silicate values for the rest of precambrian shales range from 75 to 50 and are comparable to those for phanerozoic and archean shales likewise these samples have similar ranges in 13 c org values 23 to 33 pdb and corg content 0 0 to 10 wt to phanerozoic shales precambrian shales have a large range of 18 o values comparable to that of the phanerozoic shales in each age group and formation suggesting similar variability in the provenance and intensity of chemical weathering except for the earliest 3 3 3 5 ga archean shales which have consistently lower 18 o values moreover paleoproterozoic shales that bracket in age the great oxidation event goe overlap in 18 o values absence of a step wise increase in 18 o and d values suggests that despite the first order change in the composition of the atmosphere weathering cycle was not dramatically affected by the goe at 2 4 2 3 ga shales do not show comparable 18 o rise in the early phanerozoic as is observed in the coeval 18 o trends for cherts and carbonates there is however a sharp increase in the average 18 o value from the early archean to the late archean followed by a progressively decelerating increase into the phanerozoic this decelerating increase with time likely reflects declining contribution of mantle extracted normal 18 o crust and lends support to crustal maturation and increasing 18o sequestration into the crust and recycling of high 18 o and 87sr 86sr sedimentary rocks this secular increase in the 18 o composition of the continental crust could have also had a mild effect on seawater 18 o composition

upper ocean response to hurricane gilbert the evolving upper ocean response excited by the passage of hurricane gilbert september 14 19 1988 was investigated using current and temperature observations acquired from the deployment of 79 airborne expendable current profilers axcps and 51 airborne expendable bathythermographs from the national oceanic and atmospheric administration wp 3d aircraft in the western gulf of mexico the sea surface temperatures ssts mixed layer depths and bulk richardson numbers were objectively analyzed to examine the spatial variability of the upper ocean response to gilbert net decreases of the ssts of 3o 4oc were observed by the profilers as well as by the airborne infrared thermometer airt along the flight tracks and advanced very high resolution radiometer avhrr imagery the axcps indicated a marked cooling from 29oc to about 25 5oc on september 17 1988 which was about 1 2 inertial periods ip following storm passage this pool of cooler water 3 5 o was located further downstream in the hurricane wake by september 19 2 7 ip following the storm as a result of the near inertial currents in the mixed layer while there was a bias of about 0 6oc and 1 7oc between the in situ and avhrr derived ssts respectively both the avhrr images and the objectively analyzed fields indicated a rightward bias in the upper ocean cooling that extended from the storm track to about 4rmax where rmax the radius of maximum winds is equal to 50 km the larger sst offset of 1 7oc was due to the difference between the time of the avhrr image and the time of the aircraft experiment on september 19 the ssts derived from the avhrr images and the airt also indicated large gradients between the cold wake and the warm eddy in the central gulf of mexico the mixed layer deepened by about 30 35 m on the right side of the track during the storm and 1 2 ip later with little evidence of continued deepening afterward the mixed layer current vectors demonstrate that a strong near inertially rotating current was excited by the passage of gilbert with maxima of about 1 1 4 m s 1 the currents observed during and subsequent to 1 2 ip the storm diverged from the storm track whereas the mixed layer current vectors 2 7 ip after storm passage converged toward the track with relative maxima of 0 8 1 m s 1 this alternating pattern of convergence and divergence of the mixed layer current was associated with the upwelling and downwelling cycles of the baroclinic response considerable current shear existed between the mixed layer and the thermocline currents in the cool wake between the storm track and the 4rmax estimates of the bulk richardson numbers ranged between 0 2 and 1 0 during gilbert and at 1 2 ip which suggests that enhanced current shears were responsible for some of the mixed layer deepening

new insights into archean sulfur cycle from mass independent sulfur isotope records from the hamersley basin australia we have measured multiple sulfur isotope ratios 34 s 33 s 32 s for sulfide sulfur in shale and carbonate lithofacies from the hamersley basin western australia the v 33 s values v 33 swn 33 s30 515un 34 s shift from 31 9 to 6 9x over a 22 m core section of the lower mount mcrae shale v2 5 ga likewise sulfide sulfur analyses of the jeerinah formation v2 7 ga yield v 33 s values of 30 1 to 8 1x over a 50 m section of core despite wide variations in v 33 s and n 34 s these two shale units yield a similar positive correlation between v 33 s and n 34 s in contrast pyrite sulfur analyses of the carawine dolomite v2 6 ga yield a broad range in n 34 s 3 2 to 16 2x but a relatively small variation and negative values in v 33 s 32 5 to 31 1x the stratigraphic distribution of n 33 s n 34 s and v 33 s in western australia allows us to speculate on the sulfur isotopic composition of archean sulfur reservoirs and to trace pathways in the archean sulfur cycle our data are explained by a combination of massindependent fractionation mif in the atmosphere and biological mass dependent fractionation in the ocean in the archean volcanic sulfur bearing gas species were photolysed by solar ultraviolet uv radiation in an oxygen free atmosphere resulting in mif of sulfur isotopes aerosols of s8 with v 33 ss 0 and sulfuric acid with v 33 s6 0 formed from the products of uv photolysis and carried mass independently fractionated sulfur into the hydrosphere the signatures of atmospheric photolysis were preserved by precipitation of pyrite in sediments pyrite precipitation was mediated by microbial enzymatic catalysis that superimposed mass dependent fractionation on mass independent atmospheric effects multiple sulfur isotope analyses provide new insights into the early evolution of the atmosphere and the evolution and distribution of early sulfur metabolizing organisms a 2003 elsevier science b v all rights reserved