seawater chemistry driven by supercontinent assembly breakup and dispersal global oceans are known to have alternated between aragonite and calcite seas these oscillations refl ect changes in the mg ca ratios of seawater that control biomineralization and the composition of marine carbonates and are thought to be caused mainly by the time dependence of crustal accretion at mid ocean ridge crests and the associated high temperature mid ocean ridge fl uid fl ux here we use global ocean basin reconstructions to demonstrate that the fl uctuations in hydrothermal ocean inputs are instead caused by the gradual growth and destruction of mid ocean ridges and their relatively cool fl anks during long term tectonic cycles thus linking ocean chemistry to off ridge low temperature hydrothermal exchange early jurassic aragonite seas were a consequence of supercontinent stability and a minimum in mid ocean ridge length and global basalt alteration the breakup of pangea resulted in a gradual doubling in ridge length and a 50 increase in the ridge fl ank area leading to an enhanced volume of basalt to be altered the associated increase in the total global hydrothermal fl uid fl ux by as much as 65 peaking at 120 ma led to lowered seawater mg ca ratios and marine hypercalcifi cation from 140 to 35 ma a return to aragonite seas with preferential aragonite and high mg calcite precipitation was driven by pronounced continental dispersal leading to progressive subduction of ridges and their fl anks along the pacifi c rim

reconstructing past seawater mg ca and sr ca from mid ocean ridge flank calcium carbonate veins proxies for past seawater chemistry such as mg ca and sr ca ratios provide a record of the dynamic exchanges of elements between the solid earth the atmosphere and the hydrosphere and the evolving influence of life we estimated past oceanic mg ca and sr ca ratios from suites of 1 6 to 170 million year old calcium carbonate veins that had precipitated from seawater derived fluids in ocean ridge flank basalts our data indicate that before the neogene oceanic mg ca and sr ca ratios were lower than in the modern ocean decreased ocean spreading since the cretaceous and the resulting slow reduction in ocean crustal hydrothermal exchange throughout the early tertiary may explain the recent rise in these ratios

an oscillating trend in phanerozoic non skeletal carbonate mineralogy textural and compositional data on ancient ooids and cements suggest the existence of an oscillating phanerozoic temporal trend in non skeletal carbonate mineralogy the trend shows good correlation with eustatic climatic oscillations proposed by others the most likely mechanism appears to be plate tectonically influenced oscillations in pco2 the vapour pressure of co2 rather than change in oceanic mg ca ratio

riverine evidence for a fractionated reservoir of ca and mg on the continents implications for the oceanic ca cycle analysis of river water rock travertine and soil from the high altitude negligible vegetation setting of the southern tibetan plateau demonstrates that ca and mg isotope ratios are fractionated during weathering dissolved ca in the two rivers studied is derived primarily by limestone dissolution 44 42ca in the rivers averages 0 43 and is statistically distinct from limestone at 0 31 the range in 44 42ca in these small rivers is 0 43 equivalent to the entire range in 44 42ca recorded in marine carbonate over the last 80 ma precipitation of isotopically light travertine with a 44 42ca of 0 21 enriches solute ca in heavy isotopes the mg isotope composition of the rivers is intermediate between limestone and silicate rock averaging 1 5 silicate soil has a 26mg of 0 03 heavier than silicate rock by 0 5 these fractionations in the soil create a companion groundwater reservoir of heavy ca and light mg seasonal variations in ca and mg isotope ratios in the dissolved load are small but define an array which can be modelled as a mixture between a fractionated groundwater reservoir and surface runoff reflecting the isotopic composition of the lithology fractionation of ca during the weathering of the continents is of importance to the global cycle of ca the riverine input of ca to the oceans dominated by carbonate weathering is controlled not only by the composition of the primary continental crust but also by the size and composition of a fractionated reservoir on the continents the impact on the oceanic cycle of ca depends on the relative residence times of dissolved ca in the ocean and the storage time of fractionated ca

episodic dolomitization of late cenozoic carbonates in the bahamas evidence from strontium isotopes abstract the minimum stratigraphic age and the timing of dolomitization have been constrained in sediments of late cenozoic age in the bahamas little bahama bank lbb andros new providence san salvador great inagua and mayaguana using the sr isotope composition 87sr 86sr of dolomites most dolomite sequences investigated are composites of several dolomitization episodes five phases of dolomitization have been recognized the most extensive of which are early late miocene and late pliocene in age two minor phases occurred later during the latest pliocene early pleistocene and late pleistocene the fifth phase late early miocene is only recognized in san salvador commonly dolomitization episodes are stacked indicating an increasing age with depth only in san salvador are younger dolomites interspersed with older ones the late pliocene episode on lbb is the best constrained lasting probably less than 0 6 ma and causing extensive dolomitization the shade of the dolomite body together with the age of diagenesis provides support for a dolomite origin from seawater in a hydrologic environment characterized by a mixing zone induced seawater circulation variable depth of burial of middle miocene dolomitized strata indicates non uniform subsidence behavior of bahamian carbonate platforms strontium isotope ratios of other late cenozoic dolomites hope gate formation jamaica seroi domi formation netherlands antilles rangiroa atoll niue atoll aharon et al 1987 also indicate early late miocene and late pliocene dolomite ages simultaneous dolomitization in the bahamas the caribbean and the pacific appears to occur during times when the marine 87sr 86sr ratio is either constant or decreasing this suggests that dolomitization of carbonate platforms and the evolution of sr isotope ratios in seawater are linked possibly via eustatic sea level fluctuations

geomorphic effectiveness sandur development and the pattern of landscape response during jokulhlaups skeiðararsandur southeastern iceland by contrast with other historical outburst floods on skeitararsandur the 1996 jokulhlaup was unprecedented in its magnitude and duration attaining a peak discharge of f53 000 m 3 s in 17 h using a combination of field sampling and remote sensing techniques landsat tm sar interferometry airphotos and laser altimetry we document the sandur wide geomorphic impacts of this event these impacts varied widely across the skeitararsandur and cannot be singularly attributed to jokulhlaup magnitude because pre jokulhlaup glacial dynamics and the extant setting largely conditioned the spatial pattern type and magnitude of these impacts topographic lowering and asymmetric retreat of the ice front during the late twentieth century has decoupled the ice sheet from the moraine sandur complex along the central and western sandur this glacial control in combination with the convex topography of the proximal sandur promoted a shift from a primarily diffuse source braided outwash system to a more point sourced channelized discharge of water and sediment deposition dominated within the proglacial depression with approximately 3 8 10 7 m 3 of sediment and along channel systems that remained connected to subglacial sediment supplies this shift to a laterally dissimilar channelized routing system creates a more varied depositional pattern that is not explicitly controlled by the concave longitudinal profile down sandur laterally contiguous units therefore may vary greatly in age and sediment character suggesting that current facies models inadequately characterize sediment transfers when the ice front is decoupled from its sandur water was routed onto the sandur in a highly organized fashion and this jokulhlaup generated major geomorphic changes including sandur incision in normally aggradational distal settings and eradication of proximal glacial landforms dating to fa d 1892 d 2002 elsevier science b v all rights reserved

equatorial convergence of india and early cenozoic climate trends india s northward flight and collision with asia was a major driver of global tectonics in the cenozoic and we argue of atmospheric co2 concentration pco2 and thus global climate subduction of tethyan oceanic crust with a carpet of carbonate rich pelagic sediments deposited during transit beneath the high productivity equatorial belt resulted in a component flux of co2 delivery to the atmosphere capable to maintain high pco2 levels and warm climate conditions until the decarbonation factory shut down with the collision of greater india with asia at the early eocene climatic optimum at 50 ma at about this time the india continent and the highly weatherable deccan traps drifted into the equatorial humid belt where uptake of co2 by efficient silicate weathering further perturbed the delicate equilibrium between co2 input to and removal from the atmosphere toward progressively lower pco2 levels thus marking the onset of a cooling trend over the middle and late eocene that some suggest triggered the rapid expansion of antarctic ice sheets at around the eocene oligocene boundary

positive correlation between li and mg isotope ratios in the river waters of the mackenzie basin challenges the interpretation of apparent isotopic fractionation during weathering during chemical weathering magnesium mg is released by the dissolution of both carbonate and silicate sources the degree to which solute concentrations and isotopic compositions of rivers reflect the relative proportions of these two inputs or cycling by a series of processes associated with weathering is poorly constrained in the river waters of the mackenzie basin canada the mg content is high and mg isotope ratios 26mg 24mg expressed as mg 26 show in excess of one per mil variability part of this variability is attributed to the 3 range in the carbonate and silicate rocks drained despite this inherent lithological control on river water mg 26 values there is also evidence for a fractionation control a linear positive covariation between lithium 7li 6li expressed as li 7 and mg isotope ratios in the river waters of the mackenzie basin is reported this covariation is not expected because previously reported fractionation related to physicochemical processes associated with clays or oxides should induce a negative covariation with mg isotope ratios

dissolved al in sediments and waters of the east china sea implications for authigenic mineral formation abstract numerous previous studies indicate that several different authigenic aluminosilicates form in the oceans in this study we show using dissolved al distributions in sediments and waters from the nearshore regions of the east china sea that the process of aluminosilicate formation probably begins rapidly upon contact of detrital clays with seawater statistical analyses of dissolved al si h relations in surface sediments indicate that the minerals forming in east china sea sediments low in dissolved fe are dioctahedral chlorites with an average composition ex 0 91 mg 0 77 al 5 0 si 2 7 o 10 oh 8 where ex exchangeable 1 cation this composition is also consistent with dissolved al and si measurements as a function of salinity in turbid overlying waters results suggest a dissolution reprecipitation mechanism for clay mineral reconstitution this mechanism can help to explain why different authigenic clays are found in different areas of the oceans in the east china sea the total amount of authigenic clays present must constitute a very minor fraction of the bottom sediments thus the formation of these minerals has a relatively small impact upon dissolved si distributions clay mineral reconstitution in nearshore regions may provide a mechanism for buffering sediments and overlying waters with respect to ph as the composition of minerals formed should be a direct function of the h activity in the surrounding environment

evolution assessment of structurally controlled differential subsidence using sbas and ps interferometry in an emblematic case in central mexico abstract the city of morelia has been affected by structurally controlled differential subsidence scds since at least 1983 modifying civil structures and infrastructure through the appearance of ground failures and differential ground subsidence the resulting damage to streets homes hydraulic lines and government facilities has caused economic losses worth millions of dollars an increase in population has led to the overexploitation of groundwater which is the main trigger for scds while the subsoil s geology and bedrock configuration are considered conditioning factors of this phenomenon this paper offers an analysis of the scds evolution over the last fourteen years and its relationship with groundwater extraction and thickness of unconsolidated sediments the former was carried out through sar interferometry techniques to detect and monitor land subsidence using small baseline subset sbas from 2003 to 2010 and persistent scatterer interferometry psi from 2014 to 2017 additionally groundwater pumping well data and lithological information from boreholes enabled a spatial analysis to evaluate the role of these factors in the development and acceleration of scds the sbas results show maximum sinking rates of 2 2 cm yr with a spatial distribution that is clearly controlled by buried geological structures in this period the maximum sinking rates were induced by high groundwater extraction rates in focused areas while intermediate rates were linked to notable depletion cones the psi results indicate a maximum sinking rate of 2 74 cm yr and an accelerated subsidence migration to the west owing to the construction of new wells and persistent high groundwater extraction rates for both periods the larger compressible sediment package reveals a good correlation with high subsidence rates mainly in the hanging wall blocks of the buried faults the identification of differential subsidence accompanied by high sinking rates in novel areas of morelia as well as the detection of the subsidence migration will provide scientific support to decision makers for the proposal of engineering solutions and urban planning capable of reducing hydrogeological hazards associated with scds

a first look at paleotemperature prospects from mg in coccolith carbonate cleaning techniques and culture measurements 1 although coccolith calcite is abundant in carbonate sediments it has not been previously utilized for mg ca paleothermometry cleaning experiments with synthetic composite samples reagent caco3 powder and organic matter from noncalcifying marine algae chlorella are used to evaluate which traditional and or novel cleaning methods permit us to recover the known carbonate mg ca ratio the most effective cleaning treatment causing the least effect on carbonate chemistry and most complete and rapid oxidation of algal organic matter was oxidation in an equal volume mixture of sodium hypochlorite 2 8 and hydrogen peroxide 30 however in some organic rich samples this method may not remove sufficient noncarbonate mg to permit precise determination of carbonate mg ca mg ca ratios in small culture samples may be determined precisely relative standard deviation of 0 65 using sector field inductively coupled plasma mass spectrometry measurements of mg ca in coccoliths from several species suggest that temperature may be an important control over mg partitioning in coccolith calcite although cleaning issues are likely to be an important limitation on paleoceanographic application

geomorphic tectonic control of sediment discharge to the ocean the importance of small mountainous rivers analysis of data from 280 rivers discharging to the ocean indicates that sediment loads yields are a log linear function of basin area and maximum elevation of the river basin other factors controlling sediment discharge e g climate runoff appear to have secondary importance a notable exception is the influence of human activity climate and geology on the rivers draining southern asia and oceania sediment fluxes from small mountainous rivers many of which discharge directly onto active margins e g western south and north america and most high standing oceanic islands have been greatly underestimated in previous global sediment budgets perhaps by as much as a factor of three in contrast sediment fluxes to the ocean from large rivers nearly all of which discharge onto passive margins or marginal seas have been overestimated as some of the sediment load is subaerially sequestered in subsiding deltas before the proliferation of dam construction in the latter half of this century rivers

mg isotopic systematics during early diagenetic aragonite calcite transition insights from the key largo limestone abstract the seawater magnesium mg isotopic composition 26mgsw can be applied to quantify marine mg cycle in earth s history however reconstruction of 26mgsw by using marine carbonate has been challenged by the large range of variation in mg isotopic composition of carbonate 26mgcarb such variation on the one hand reflects e g the mineralogy temperature and precipitation rate dependent isotopic fractionation during ca carbonate precipitation on the other hand the pristine seawater record could be modified in carbonate diagenesis during which less stable carbonate minerals would spontaneously convert to more stable mineral phases in the modern ocean with high mg ca molar ratio 5 aragonite precipitation is favored however aragonite is thermodynamically less stable than low mg calcite at ambient surface environment resulting in the spontaneous transition from aragonite to low mg calcite in the earliest stage of diagenesis i e the aragonite calcite transition as a common process in the modern ocean mg isotopic fractionation in aragonite calcite transition may provide valuable constraints on the variation of 26mgcarb in this study we measured mg isotopic compositions of pleistocene key largo limestone florida which has been experiencing the aragonite calcite transition during early diagenesis the key largo limestone samples consist of a mixture of calcite and aragonite 26mg of aragonite 26mgarag shows higher and more stable values while calcite has lower yet more variable mg isotopes 26mgcal we suggest a model conceptualizing a water film attached to the mineral surface in which the aragonite calcite transition initiates with aragonite dissolution and the mg exchange with external fluid can be variable followed by mg isotopes fractionate during low mg calcite precipitation in this model 26mgcal is controlled by 1 the chemical composition of water film which is dependent on the mineralogical composition of aragonite i e mg content and 26mgarag the composition of external fluid i e fresh water seawater or mixed fresh water and seawater and the mixing ratio between dissolved aragonite and external fluid and 2 the isotopic fractionation during calcite precipitation because the isotopic fractionation in calcite is sensitive to the rate of calcite precipitation that is dependent on the calcite saturation state of solution therefore 26mgcal could be highly heterogeneous depending on the aragonite dissolution and calcite precipitation processes further complicating the interpretation of carbonate data thus the process controlled mg isotopic fractionation should be taken into consideration when reconstructing 26mgsw by using carbonate sediments rocks

low temperature alteration of the upper oceanic crust and the alkalinity budget of seawater abstract while the input of river alkalinity into seawater is relatively well known the complementary acidity production is poorly understood using the major element budget of seafloor alteration of the upper 500 m of 120 ma old oceanic crust at dsdp odp sites 417a 417d and 418a in the central western atlantic we estimate the acidity flux associated with the low temperature weathering of the upper oceanic crust the acidity flux is calculated based on major element fluxes and charge balance considerations the relevant chemical fluxes from seawater to the upper crust are 4 1 0 1 1 4 1 4 2 2 0 6 and 12 2 1011 mol yr 1 for k mg na and silicate ca respectively the associated acidity flux is 3 5 3 1011 eq yr 1 relative to continental weathering these fluxes are significant for k and silicate ca but are minor for na mg and acidity thus riverine fluxes of alkalinity are not significantly balanced by acidity fluxes from low temperature upper ocean crust alteration

early diagenesis of biogenic silica in the amazon delta alteration authigenic clay formation and storage deltaic environments are commonly assumed to be relatively minor sites of biogenic silica burial because of the small quantities of opaline silica detected by most operational analytical techniques rapid conversion of biogenic silica into authigenic silicates is also often discounted as a significant control on oceanic silica budgets a variety of evidence for extensive early diagenetic alteration of biogenic silica in rapidly accumulating amazon delta sediments indicates that both of these general assumptions are unjustified apparent lack of significant biogenic silica storage in deltaic environments particularly in the tropics may be largely an artifact of operational definitions that do not include early diagenetic products of biogenic silica biogenic silica particles buried in suboxic amazon delta deposits can be unaltered partially dissolved covered with aluminosilicate or metal rich coatings or completely reconstituted into authigenic k fe rich aluminosilicate minerals pore water k mg f si and solid phase distributions direct observations of particles laboratory experiments and depositional context indicate that authigenic clays form rapidly 1 yr in the seasonally reworked surface layer 0 5 2 m of the delta topset and are disseminated during sediment remobilization fe al oxide rich debris derived from the tropical drainage basin is an abundant reactant and thus the supply of biogenic silica is a major control on the amount of clay formed the mild 1 na2co3 alkaline leach procedure commonly used to estimate biogenic silica was modified to include an initial mild leach step with 0 1n hcl to remove metal oxide coatings and to activate poorly crystalline authigenic phases for alkaline dissolution well crystallized clays are not significantly affected by this modification nor is bulk amazon river bed sediment the two step procedure indicates that 90 of the biogenic silica originally present in deposits is converted to clay or otherwise altered raising the effective quantity of biogenic silica stored from 33 to 296 mol si g 1 1 8 sio2 biogenic si stored in the delta increases away from the river mouth across shelf and along the dispersal system where primary production is highest the k si ratio of labile authigenic material is 0 19 mol mol 1 far higher than amazon river suspended matter 0 07 mol mol 1 diagenetic models indicate formation rates in the mobile sediment layer of 2 8 mol k g 1 yr 1 16 mol si g 1 yr 1 inclusion of authigenic alteration products of biogenic silica in estimates of reactive si burial increases the deltaic storage of riverine si to 22 of the amazon river input the rapid formation of aluminosilicates from biogenic sio2 seawater solutes and remobilized fe al oxides represents a form of reverse weathering rapid reverse weathering reactions in tropical muds and deltaic deposits the largest sediment depocenters on earth confirms the general importance of these processes in oceanic elemental cycles

the mg isotopic composition of cenozoic seawater evidence for a link between mg clays seawater mg ca and climate abstract cooling of earth s climate over the cenozoic has been accompanied by large changes in the magnesium and calcium content of seawater whose origins remain enigmatic the processes that control these changes affect the magnesium isotopic composition of seawater rendering it a useful tool for elucidating the processes that control seawater chemistry on geologic timescales here we present a cenozoic magnesium isotope record of carbonate sediments and use a numerical model of seawater chemistry and the carbon cycle to test hypotheses for the covariation between cenozoic seawater chemistry and climate records are consistent with a 2 3 increase in seawater mg ca and little change in the mg isotopic composition of seawater these observations are best explained by a change in the cycling of mg silicates we propose that mg ca changes were caused by a reduction in removal of mg from seawater in low temperature marine clays though an increase in the weathering of mg silicates cannot be excluded we attribute the reduction in the mg sink in marine clays to changes in ocean temperature directly linking the major element chemistry of seawater to global climate and providing a novel explanation for the covariation of seawater mg ca and climate over the cenozoic

densities and porosities in the oceanic crust and their variations with depth and age we have used drilling and downhole logging results from deep sea drilling project holes 395a and 418a measured properties of core samples from the seafloor and from ophiolites and seismic velocity structure models of the oceanic crust to constrain empirical statistical relationships between in situ densities porosities and seismic velocities and to estimate densities and porosities in the oceanic crust with the following principal results our review of drilling results and studies of ophiolites suggests that the velocity structure of the oceanic crust is more closely related to changes in porosity and alteration or metamorphic grade than to its igneous structure the transition from layer 2a 3 7 0 4 km s 1 to 2b 5 2 0 4 km s 1 occurs within the extrusive pile the top of layer 2c 6 2 0 2 km s 1 is associated with the top of the sheeted dike complex and with the first appearance of greenschist facies alteration products ophiolite studies have shown that the top of layer 3 occurs within the sheeted dikes where the metamorphic grade of alteration products increases from greenschist to amphibolite facies a comparison of reprocessed and corrected downhole logs from holes 395a and 418a indicates that in situ densities and fractional porosities differ by 0 2 mg m 3 and 0 07 respectively these differences are consistent with prevailing views of the progressive alteration of the upper oceanic crust statistical relationships between in situ density porosity and slowness are highly linear and indicate that the density slowness relation estimated from laboratory samples pb 3 81 0 02 6 0 0 1 s applies to in situ properties as well we obtained a similar empirical relationship for porosities from the hole 418a log data f 0 35 0 03 2 37 0 15 s r2 0 84 s e 0 015 applying these empirical models to seismic velocity structure models yields the following crustal densities and porosities layer 2 2 62 2 69 mg m 3 0 10 0 12 and layer 3 2 92 2 97 mg m 3 the estimated average density of the oceanic crust is 2 86 0 03 mg m 3 densities and porosities estimated from a seismic crustal structure model for old atlantic crust agree very well with the logging data from hole 418a suggesting that in situ densities and porosities can be estimated from seismic velocities high density and porosity gradients are characteristic of the upper oceanic crust increasing densities reflect both a progressive decrease of porosity and increasing grain density with depth based on the seismic properties of layer 2a we estimate that the layer thins at an approximate rate 20 to 45 m m y 1 while the velocity increases by 0 040 km s 1 m y 1 the corresponding rates of change of density and porosity are 0 016 0 009 mg m 3 m y 1 and 0 005 0 003 m y 1 respectively

hydrothermal alteration of a 1 km section through the upper oceanic crust deep sea drilling project hole 504b mineralogy chemistry and evolution of seawater basalt interactions deep sea drilling project hole 504b penetrates 1076 m into oceanic layer 2 and is the first hole to pass through the transition from pillow basalts altered at low temperatures into hydrothermally metamorphosed sheeted dikes alteration of the crust at site 504 occurred in four stages related to the movement of the crust away from the spreading axis 1 dikes reacted with seawater 200 300 c in the upwelling zone of an axial convection cell at the spreading axis resulting in the formation of greenschist facies parageneses in veins and host rocks mixing of the upwelling hydrothermal fluids with seawater circulating in the overlying more permeable pillow section occurred in the upper part of the lithologic transition zone causing a steep temperature gradient at the base of the pillow section secondary minerals formed in the lower pillow section from the resultant reducing mixed fluids at temperatures of around 100 c at the same time the initial effects of seafloor weathering began in the upper 320 m of the pillow section at low temperatures 50 c and under conditions of open circulation of oxidizing seawater 2 following refracturing of the dikes a second stage of axial upwelling occurred hydrothermal fluids 200 380 c were probably similar to those presently sampled from spreading ridges on the seafloor mixing of these fluids with seawater in the lithologic transition zone caused deposition of quartz epidote and sulfides in veins and formation of a sulfide rich stockworklike zone within this transition zone alteration of the pillow section proceeded under the prior conditions with the effects of seafloor weathering extending progressively downward into the crust 3 seawater recharge penetrated to depths of at least 1075 5 m subbasement and deposited anhydrite locally in veins 4 off axis alteration of the dikes was characterized by formation of zeolites calcite and prehnite in veins and host rocks from more highly evolved and lower temperature 100 250 c fluids alteration in the upper pillow section evolved from seafloor weathering conditions to more reducing and rock dominated as cracks in the basalt were sealed with secondary minerals and the basement was covered with a layer of sediment zeolites and calcite were the last phases to form throughout the pillow section sealing of the crust to convective cooling also allowed conductive reheating of the crust from below calculations of seawater crustal chemical fluxes from whole rock data are complicated by the low recovery and heterogeneity of alteration effects but indicate that basalt seawater interactions are a sink for seawater mg and k and a source for si and ca

towards a better understanding of magnesium isotope ratios from marine skeletal carbonates abstract this study presents magnesium stable isotope compositions of various biogenic carbonates of several marine calcifying organisms and an algae species seawater samples collected from the western dutch wadden sea and reference materials the aim of this study is to explore the influence of mineralogy taxonomy and environmental factors e g seawater isotopic composition temperature salinity on magnesium isotopic 26mg ratios of skeletal carbonates using high precision multi collector inductively coupled plasma mass spectrometry we observed that the magnesium isotopic composition of seawater from the semi enclosed dutch wadden sea is identical to that of open marine seawater we further found that a considerable component of the observed variability in 26mg values of marine skeletal carbonates can be attributed to differences in mineralogy furthermore magnesium isotope fractionation is species dependent with all skeletal carbonates being isotopically lighter than seawater while 26mg values of skeletal aragonite and high magnesium calcite of coralline red algae indicate the absence or negligibility of metabolic influences the 26mg values of echinoids brachiopods and bivalves likely result from a taxon specific level of control on mg isotope incorporation during biocalcification moreover no resolvable salinity and temperature effect were observed for coralline red algae and echinoids in contrast mg isotope data of bivalves yield ambiguous results which require further validation the data presented here point to a limited use of mg isotopes as temperature proxy but highlight the method s potential as tracer of seawater chemistry through earth s history

investigating the behaviour of mg isotopes during the formation of clay minerals abstract we present elemental and isotopic data detailing how the mg isotope system behaves in natural and experimentally synthesized clay minerals we show that the bulk mg isotopic composition 26 mg of a set of natural illite montmorillonite and kaolinite spans a 2 range and that their isotopic composition depends strongly on a balance between the relative proportions of structural and exchangeable mg after acid leaching these natural clays become relatively enriched in isotopically heavy mg by between 0 2 and 1 6 results of exchange experiments indicate that the mg that has adsorbed to interlayer spaces and surface charged sites is relatively enriched in isotopically light mg compared to the residual clay the isotopic composition of this exchangeable mg 1 49 to 2 03 is characteristic of the isotopic composition of mg found in many natural waters further experiments with an isotopically characterized mgcl 2 solution shows that the clay minerals adsorb this exchangeable mg with little or no isotopic fractionation although we cannot discount the possibility that the uptake of exchangeable mg does so with a slight preference for 24 mg to characterize the behaviour of mg isotopes during clay mineral formation we synthesized brucite mg oh 2 which we consider to be a good analogue for the incorporation of mg into the octahedral sheet of mg rich clay minerals or into the brucitic layer of clays such as chlorite in our experiment the brucite mineral becomes enriched in the heavy isotopes of mg while the corresponding solution is always relatively enriched in isotopically light mg the system reaches a steady state after 10 days with a final fractionation factor solid solution of 1 0005 at near neutral ph this result is consistent with the general consensus that secondary clay minerals preferentially take up isotopically heavy mg during their formation however our results also show that exchangeable mg is an important component within bulk clay minerals and can have an important influence over the bulk clay 26 mg value modeling shows that in certain soils or sediments where the percentage of exchangeable mg is 30 and the isotopic composition of the exchangeable mg is around 2 the generation of bulk 26 mg values of 26 mg values that are closer in composition to the ucc despite this results of modeling together with experimental observation suggests that the uptake of exchangeable mg into these clay rich sediments could cause a decrease in the bulk 26 mg value by up to 0 3 0 4 this should be accounted for when assessing the 26 mg value of sediments on a crustal scale

the magnesium isotope budget of the modern ocean constraints from riverine magnesium isotope ratios we have measured the magnesium mg isotope ratios in 45 rivers including 16 of the largest rivers in the world covering a range of geologic tectonic and climatic drainage basin environments the range in riverine 26mg is 2 5 half the variation in terrestrial rock although the mg isotopic composition of the source rock is important for small rivers at a global scale lithology is of limited significance for mg isotope ratios in rivers part of the variability at a global scale may be attributed to fractionation in the weathering environment the rivers analysed constitute 30 of the global mg riverine flux to the oceans and a flux weighted mg isotope composition of global runoff has been estimated at 1 09 even taking into account uncertainty this is distinct from seawater at 0 82 this difference arises either from the fractionation of mg isotope ratios in the ocean and or a mg budget which is not at steady state the difference is consistent with fractionation by carbonate precipitation in the simplest steady state scenario where the oceanic mass balance is maintained by riverine input and hydrothermal and dolomite output mg isotope ratios imply a minimum dolomite mg flux of 9 of the total output mg flux the implications of the distinct isotopic composition of the riverine flux from modern seawater is that the mg isotope ratio of seawater has probably varied outside of current analytical uncertainty mg isotope ratios may therefore provide a valuable new tracer in palaeo oceanography

the origin of dolomites in tertiary sediments from the margin of great bahama bank abstract based on an integrated geochemical and petrographic investigation of dolomites from two cores drilled on great bahama bank we have determined three different environments of formation for the dolomites that are common throughout the pliocene and miocene parts of these cores the first environment of dolomitization occurs in association with development of nondepositional surfaces dolomite typically forms below each of these surfaces the concentration and extent of which is governed by the length of the period of nondeposition these dolomites are recognized by their association with the nondepositional surfaces characteristic positive 18o values indicative of formation from cold bottom waters and 18o and sr profiles with depth that suggest formation in the presence of diffusive temperature and sr gradients the second environment of dolomitization occurs in pore fluids where the cation and anion profiles are governed by diffusive processes the dolomite forming here is termed background dolomite this is a microsucrosic dolomite and forms both by recrystallization of the existing sediment and precipitation directly into void space dolomitization by this mechanism uses a local source of mg2 and consequently the dolomite never constitutes more than between 5 and 10 of the sediment this type of dolomite is characterized by extremely high sr concentrations which reflect concentrations of sr2 in the pore fluids from which it formed the high concentrations of sr2 in the pore fluids arise through the continued recrystallization of metastable aragonite and high mg calcite to dolomite and low magnesium calcite driven by oxidation of organic material by sulfate not only does sulfate reduction provide an additional thermodynamic drive for recrystallization but because the absolute concentration of sr2 in the pore fluids is governed by the solubility of celestite srso4 removal of sulfate allows the sr2 ca2 ratio of the interstitial fluid to become much higher than normally encountered the final type of environment of dolomitization is associated with coarse grained reefal sediments the pervasive nature of the dolomitization and the relatively normal sr concentrations suggest the circulation of normal marine water in a relatively open system

continental drift and phanerozoic carbonate accumulation in shallow shelf and deep marine settings knowledge of past rates of transfer of rock forming materials among the principal geologic reservoirs is central to understanding causes and magnitudes of change in earth surface processes over phanerozoic time to determine typical rates of global sediment cycling we compiled information on area volume and lithology of shallow water sediments by epoch for both terrigenous clastics and marine carbonates data on amounts of surviving continental terrigenous rock as opposed to deep oceanic and including terrestrial marginal marine and marine deposits exhibit positive age area trends wherein greatest areas and volumes of conglomerate sandstone and shale are represented by younger sequences global volumes of terrigenous clastic sediment yield a mean cycling rate of 0 00124 m yr similar to that determined for eurasian 0 00127 north american 0 00058 a b ronov 0 00352 t d cook and a w bally african 0 0017 and south american 0 0021 clastic sequences surficial erosion results in the mean destruction of 0 124 of terrigenous rock volume per million years of reservoir age in contrast surviving epicratonic and shelf margin carbonate sequences yield negative cycling rates of about 0 164 m yr surviving areas and volumes increase with sequence age that is the amount of limestone and dolostone preserved in shallow water settings increases back in time to maximal areal extents in the middle and upper cambrian mass age data on terrigenous clastic successions indicate generally constant rates of crustal erosion over phanerozoic time decrease in size of the shallow marine carbonate reservoir forward in time therefore suggests generally invariant rates of global limestone accumulation and a shift in sites of accumulation from shallow cratonic to deep oceanic settings over much of the past 540 m yr causes of this eon scale depositional translocation of carbonate sediment from shallowto deep marine settings cannot be satisfactorily linked to either changes in global sea level or the evolution of carbonate producing plankton because neither exhibits a pattern of unidirectional change in position or abundance since the early phanerozoic however tabulation of long term variation in areas of continental shelves from paleogeographic maps reveals a generally uniform decrease in low latitude 30 platform area with decreasing age over most of the phanerozoic moreover rate of change of low latitude shelf area km 2 m yr is almost exactly

secular oscillations in the carbonate mineralogy of reef building and sediment producing organisms driven by tectonically forced shifts in seawater chemistry the primary mineralogy of oolites and early marine carbonate cements led sandberg nature 305 1983 19 22 to divide the phanerozoic eon into three intervals of aragonite seas and two intervals of calcite seas hardie geology 24 1996 279 283 has shown that these oscillations together with synchronous oscillations in the mineralogy of marine potash evaporites can be explained by secular shifts in the mg ca ratio of seawater driven by changes in spreading rates along mid ocean ridges the hardie model also predicts that high mg calcite should precipitate along with aragonite as it does in today s aragonite sea we have uncovered oscillations in the carbonate mineralogy of hypercalcifying organisms ones that have produced massive skeletons large reefs or voluminous bodies of sediment that correspond to sandberg s aragonite seas and calcite seas and that are predicted by the hardie model particular groups of corals sponges and algae appear to have been dominant reef builders only when favored by an appropriate mg ca ratio in seawater in early and middle paleozoic calcite seas calcite i reefs were dominated by calcitic tabulate heliolitid and rugose corals and calcitic stromatoporoids in contrast during the period of late paleozoic early mesozoic aragonite seas aragonite ii aragonitic groups of sponges scleractinian corals and phylloid algae as well as high mg calcitic red algae were principal reef builders during late cretaceous time at the acme of calcite ii massive rudists displaced aragonitic hermatypic corals in today s aragonite sea aragonite iii scleractinian corals are again dominant reef builders along with high mg calcitic coralline algae major sediment producing algae exhibit temporal patterns similar to those of reef builders calcitic receptaculitids flourished during calcite i whereas aragonitic dasycladaceans did not become dominant rock formers until aragonite ii during calcite ii calcitic nannoplankton formed massive coccolith chalks in warm shallow seas of the late cretaceous after the mg ca ratio of seawater had reached a very low value and calcium concentration a very high value as the mg ca ratio of seawater rose and calcium concentration fell during the cenozoic era individual coccoliths on average became less massive and encrusted cells less thickly by pliocene time during aragonite iii the prominent genus discoaster secreted only narrow rayed coccoliths that covered less than 25 of the cell surface also during aragonite iii the aragonitic green alga halimeda emerged as the dominant skeletal sediment producer in reef tracts the influence of seawater chemistry on skeletal secretion appears to have been especially strong for morphologically simple taxa that exert relatively weak control over their own calcification such groups include algae sponges corals and bryozoans morphological simplicity also permits these groups to adopt vegetative or colonial modes of growth that confer success in competition for space on reefs this linkage in addition to the basic chemical demands of hypercalcification has given the mg ca ratio of seawater strong control over the success of individual reef building taxa more generally this ratio appears to have strongly influenced evolutionary changes in the skeletal mineralogy of sponges and cheilostome bryozoans throughout their history we conclude that throughout phanerozoic time a chain of causation has extended from mid ocean ridge processes via seawater chemistry to the mineralogical and biological composition of reef communities and bioclastic carbonate deposits

precise magnesium isotope measurements in core top planktic and benthic foraminifera 1 this study presents a new methodology to obtain highly precise measurements 0 1 of magnesium isotope ratios in very small samples of foraminiferal carbonate 40 50 g here this technique is used to examine mg isotopic variation among different species of core top foraminifera over a range of different ambient conditions despite the high degree of temperature control on the abundance of elemental mg incorporated into foraminiferal tests analyses of surface dwelling globigerinoides ruber and g sacculifer from five cores with associated sea surface temperatures ranging from 20 to 31 c show no significant temperature dependent variations in their mg isotope ratios analyses of different size fractions of g sacculifer show an increase in mg ca with test size but no variation of mg isotope ratio in all nine planktic and benthic species were analyzed all show identical mg isotope ratios with a mean of 26mg 4 72 apart from small differences in three species namely o universa g sacculifer which are both 0 4 lighter than the average and p obliquiloculata which is 0 4 heavier these results highlight the constancy of foraminiferal mg isotope ratios despite changing environmental conditions which dominate mg ca variation and arguably affect ca isotope fractionation this is an important observation which needs to be included in any model of foraminiferal calcification the insusceptibility of 26mg values to external parameters makes mg isotopes ideally suited to constraining past variations in the mg isotope budget of the oceans and the information this carries about the history of oceanic dolomitization continental weathering and hydrothermal behavior

constraining magnesium cycling in marine sediments using magnesium isotopes abstract magnesium concentrations in deep sea sediment pore fluids typically decrease down core due to net precipitation of dolomite or clay minerals in the sediments or underlying crust to better characterize and differentiate these processes we have measured magnesium isotopes in pore fluids and sediment samples from ocean drilling program sites 1082 1086 1012 984 1219 and 925 that span a range of oceanographic settings at all sites magnesium concentrations decrease with depth at sites where diagenetic reactions are dominated by the respiration of organic carbon pore fluid 26mg values increase with depth by as much as 2 because carbonates preferentially incorporate 24mg low 26mg the increase in pore fluid 26mg values at these sites is consistent with the removal of magnesium in mg carbonate dolomite in contrast at sites where the respiration of organic carbon is not important and or weatherable minerals are abundant pore fluid 26mg values decrease with depth by up to 2 the decline in pore fluid 26mg at these sites is consistent with a magnesium sink that is isotopically enriched relative to the pore fluid the identity of this enriched magnesium sink is likely clay minerals using a simple 1d diffusion advection reaction model of pore fluid magnesium we estimate rates of net magnesium uptake removal and associated net magnesium isotope fractionation factors for sources and sinks at all sites independent estimates of magnesium isotope fractionation during dolomite precipitation from measured 26mg values of dolomite samples from sites 1082 and 1012 are very similar to modeled net fractionation factors at these sites suggesting that local exchange of magnesium between sediment and pore fluid at these sites can be neglected our results indicate that the magnesium incorporated in dolomite is 2 0 2 7 depleted in 26mg relative to the precipitating fluid assuming local exchange of magnesium is minor at the rest of the studied sites our results suggest that magnesium incorporated into clay minerals is enriched in 26mg by 0 to 1 25 relative to the precipitating fluid this work demonstrates the utility of magnesium isotopes as a tracer for magnesium sources sinks in low temperature aqueous systems

mg isotopic composition of carbonate insight from speleothem formation simultaneous high precision measurement of 24 mg 25 mg and 26 mg isotopic compositions were made by multiple collector inductively coupled mass spectrometry mc icp ms relative to the international standard srm980 data are presented on low mg calcite speleothems and their associated host rocks and waters from four caves one in the french alps and three in israel covering various climate conditions in addition data are presented on three dolostones and three limestones from the himalaya the overall variation is 4 13x and 2 14x in n 26 mg and n 25 mg respectively this is 35 times the uncertainty of the measurements and clearly demonstrates that the terrestrial isotopic composition of mg is not unique each speleothem shows a characteristic range of n 26 mg values that are attributed to the isotopic composition of the local water differences between the isotopic composition of mg in the water dripping from stalactites and that of the modern speleothem are interpreted as being due to mg isotopic fractionation during carbonate precipitation in the temperature range of 4 18 c the low mg calcite is enriched in light isotopes by 1 35x amu and the dependence on temperature has been found to be less than 0 02x amu c despite various geological settings the n 26 mg of the studied dolostones is 2 0 1 2x higher than the n 26 mg of the limestones all together these results suggest a strong mineralogical control and a weak temperature effect on the mg isotopic composition of carbonate a 2002 elsevier science b v all rights reserved

the effects of diagenesis and dolomitization on ca and mg isotopes in marine platform carbonates implications for the geochemical cycles of ca and mg abstract the ca mg o and c isotopic and trace elemental compositions of marine limestones and dolostones from odp site 1196a which range in depth 58 to 627 mbsf and in depositional age 5 and 23 ma are presented the objectives of the study are to explore the potential for non traditional isotope systems to fingerprint diagenesis to quantify the extent to which geochemical proxies are altered during diagenesis and to investigate the importance of diagenesis within the global ca and mg geochemical cycles the data suggest that ca which has a relatively high solid to fluid mass ratio can be isotopically altered during diagenesis in addition the alteration of ca correlates with the alteration of mg in such a way that both can serve as useful tools for deciphering diagenesis in ancient rocks bulk carbonate 44 ca values vary between 0 60 and 1 31 srm 915a scale the average limestone 44 ca is 0 97 0 24 1sd identical within error to the average dolostone 1 03 0 15 1sd magnesium isotopic compositions 26 mg dsm 3 scale range between 2 59 and 3 91 and limestones 3 60 0 25 and dolostones 2 68 0 07 are isotopically distinct carbon isotopic compositions 13 c pdb scale vary between 0 86 and 2 47 with average limestone 1 96 0 31 marginally offset relative to average dolostone 1 68 0 57 the oxygen isotopic compositions 18 o pdb scale of limestones 1 22 0 94 are substantially lower than the dolostones measured 2 72 1 07 the isotopic data from 1196a suggest distinct and coherent trends in isotopic and elemental compositions that are interpreted in terms of diagenetic trajectories numerical modeling supports the contention that such trends can be interpreted as diagenetic and suggests that the appropriate distribution coefficient k mg associated with limestone diagenesis is 1 to 5 10 3 distinctly lower than those values 0 015 reported in laboratory studies with respect to mg isotopes the modeling also suggest that diagenetic fractionation factors of 0 9955 4 5 and 0 9980 2 are appropriate for limestone diagenesis and dolomitization respectively

lithium magnesium and silicon isotope behaviour accompanying weathering in a basaltic soil and pore water profile in iceland this study presents lithium magnesium and silicon isotope ratios from pore waters and soils from a well characterised histic andosol in south west iceland the soil 7li composition ranges between values slightly lighter than basalt to those that are much heavier 1 1 to 26 8 and are possibly influenced by sea salt in contrast precipitation corrected dissolved pore water 7li values 1 8 10 0 appear to reflect preferential adsorption of 6li onto secondary minerals where allophane supersaturation results in high 7li values conversely low 7li together with high li are probably due to destabilisation of allophane at low ph and thus desorption of li when compared to icelandic river values it would appear that soil pore waters reflect an intermediate isotope composition between basalts and river waters precipitation corrected pore water mg isotope ratios 26mg range between 0 46 and 0 12 and correlate with the amount of heavy mg adsorbed onto the soil exchange complex silicon isotopes in the soils are isotopically lighter 30si 0 91 to 0 53 than basalt 0 29 whereas pore waters are heavier 0 13 to 1 03 soil 30si values show a clear evolution between unweathered basalt and a hypothetical isotopically light endmember representing secondary minerals dissolved si isotopes also respond to chemical weathering processes and show that isotopically heavy 30si corresponds to high cation fluxes and high secondary mineral formation however comparison of all these proposed isotopic weathering tracers suggests that they respond differently to the same chemical weathering conditions this indicates a differing behaviour during secondary mineral neoformation or adsorption depending on whether the incorporated element is a major or trace constituent in turn this behaviour can potentially yield important information on secondary mineral behaviour and destabilisation and thus on the chemical weathering processes

hydrothermal circulation through mid ocean ridge flanks fluxes of heat and magnesium thermally driven convection of seawater occurs through oceanic crust of all ages at the seafloor spreading axis on mid ocean ridge flanks and in the ocean basins at the ridge axis and on the flanks circulating seawater produces a major chemical exchange between the oceans and the crust based on heat budget constraints and the composition of hot springs between 10 and 40 of the river flux of mg can be taken up during high temperature alteration of the basaltic crust along the ridge axis most of the hydrothermal heat loss however occurs on the mid ocean ridge flanks where the temperatures are lower and the seawater flux correspondingly larger the estimated heat loss on the flanks is so large that upwelling must occur over a large fraction 5 30 of the seafloor less than 65 ma in age if temperatures are 20 c and seepage velocities are on the order of 10 to 100 cm y the circulating seawater needs to lose on average less than 1 2 of its mg content in order to solve the mg mass balance for the oceans chemical fluxes through mid ocean ridge flanks are poorly known because of the wide range of crustal conditions that prevail there and the paucity of study to date the most critical parameter for characterizing crustal conditions is temperature in basement which is a function of crustal age basement topography and sediment thickness and permeability basement temperature which can usually be inferred from heat flow and seismic reflection surveys largely determines the change in the composition of seawater circulating through basement this change can be inferred in turn from profiles of sediment porewater chemistry all sites studied to date with temperatures at the sediment basement interface 25 c have a large component of advective heat loss and show only a small 80 mg loss both types of sites may be important for chemical fluxes whether the cooler sites are important depends on how much the seawater changes in composition as it circulates through the crust only small changes are needed whether the warmer sites are important depends on how much heat is lost by advection in this type of setting the warmer sites could produce significant chemical fluxes even if they are scarce they could account for the entire river input of mg to the oceans even if they represent only 8 20 of the total advective heat loss on ridge flanks

calcium isotopes in the global biogeochemical ca cycle implications for development of a ca isotope proxy abstract at the earth s surface calcium ca is a critical element at a variety of scales it is soluble in natural waters a biological nutrient and a major constituent of the dominant mineral sink for carbon in the ocean caco3 there is a 4 variation in the ca isotopic composition 44ca 40ca expressed as 44ca of various ca reservoirs on earth suggesting ca isotopes as a promising tracer of ca cycling in both the present and the past fifteen years of high precision ca isotope measurements has revealed much about the behavior of ca isotopes in the earth surface environment but there remain fundamental questions concerning how ca isotopes are used to elucidate the marine and terrestrial ca cycles the current work presents a data compilation of over 70 published ca isotope studies totaling over 2600 measurements presented on a common delta scale that includes data on rivers and groundwater dust soils and soil pore fluids vegetation rainwater silicate minerals rocks and authigenic marine minerals carbonates sulfates and phosphates both modern and ancient the data compilation suggests that 1 there is a significant difference between carbonate 0 60 and silicate 44ca 0 94 2 riverine 44ca 0 88 does not simply reflect the compiled carbonate 44ca and 3 terrestrial vegetation exhibits the largest range of ca isotopic compositions 3 5 in the terrestrial setting we discuss these observations in the context of the global ca cycle exploring the extent to which seawater 44ca variability is feasible and how we can achieve accurate reconstructions of seawater 44ca over geologic time scales the current study presents simple mass balance models that quantify the leverage of inputs to change the ca isotopic composition of the ocean as this directly impacts the manner in which ca isotopes are interpreted although ca fractionates isotopically in the modern system during continental cycling the 44ca range of riverine inputs to the ocean is considerably smaller than the variability observed in putative seawater proxies such as nannofossil ooze and marine barite in the terrestrial realm plants exhibit a wide 44ca range and there is evidence that ca fluxes via biomass degradation are significant at the catchment scale we therefore assess the ability of the continental biosphere to influence riverine and consequently seawater 44ca a steady state biosphere has little leverage to alter riverine 44ca except in cases where the 44ca of the recycling flux is isotopically distinct from the 44ca of the uptake flux a non steady state biosphere can substantially impact both soil and riverine 44ca driving exchangeable ca either heavier or lighter depending on the magnitude of the recycling flux relative to the uptake flux based on estimates of the size of the global biosphere 1 5 1015 mol ca we suggest a decaying biosphere has the potential to impact riverine 44ca by tenths of a permil over time scales in the marine realm we evaluate the effect of a variable fractionation factor accompanying global removal of ca from the ocean on seawater 44ca and suggest methods by which such a mechanism can be recognized in the rock record experimental data suggest that there is considerable leverage