Variations In Seawater Chemistry Research Articles

Extracting Mg isotope signatures of ancient seawater from marine halite: A reconnaissance

The Mg/Ca ratio of seawater fluctuated remarkably over the Phanerozoic. The processes that controlled the temporal variation in seawater Mg/Ca ratio may also have caused the secular changes in Mg isotope ratios of seawater. Therefore, the Mg isotope composition of seawater may be useful to understand the long-term variation in seawater chemistry. Different sedimentary carbonates have been proposed as archives of ancient seawater Mg isotope signatures, but each type of carbonate has its limitations. Halite is a common mineral in evaporite deposits and their fluid inclusions may be used to infer the Mg isotope composition of contemporary seawater. In this study, we developed a method to measure the isotope composition of Mg in halite with an accuracy of better than ±0.1‰ in δ26Mg. The accuracy of the method was verified systematically, using synthetic NaCl solutions, as well as Holocene lacustrine halite samples from the Dead Sea. The δ26Mg values of marine halite samples show a large variation, ranging from −0.1‰ to −1.6‰ relative to the DSM3 international Mg isotope standard. The δ26Mg values of some ancient salt samples are lower than a published model curve for δ26Mg of seawater, and such inconsistency could be explained by 1) isotopic evolution of brines due to mineral precipitation, 2) entrapment of evaporite minerals into halite during halite precipitation or post-depositional deformation, 3) recrystallization and dissolution of pre-existing Mg minerals, and 4) limitations of the model curve of seawater δ26Mg values. Collectively, we suggest that Mg isotopes in halite are a new geochemical proxy to study the secular variations in seawater chemistry, syndepositional and post-depositional processes of evaporite deposits. Our data highlight the importance of understanding the sedimentary background and textural details of evaporites for appropriate interpretations of Mg isotope data from halite.

Sedimentology and chemostratigraphy of the terminal Ediacaran Dengying Formation at the Gaojiashan section, South China.

The late Ediacaran Dengying Formation (ca. 551.1-538.8 Ma) in South China is one of two successions where Ediacara-type macrofossils are preserved in carbonate facies along with skeletal fossils and bilaterian animal traces. Given the remarkable thickness of carbonate-bearing strata deposited in less than 12.3 million years, the Dengying Formation holds the potential for a relatively continuous chemostratigraphic profile for the terminal Ediacaran stage. In this study, a detailed sedimentological and chemostratigraphic (δ13Ccarb, δ18Ocarb, δ13Corg, δ34Spyrite, and 87Sr/86Sr) investigation was conducted on the Dengying Formation at the Gaojiashan section, Ningqiang County of the southern Shaanxi Province, South China. Sedimentological results reveal an overall shallow marine depositional environment. Carbonate breccia, void-filling botryoidal precipitates, and aragonite crystal fans are common in the Algal Dolomite Member of the Dengying Formation, suggesting that peritidal facies were repeatedly karstified. The timing of karstification was likely early, probably soon after the deposition of the dolomite sediments. The presence of authigenic aragonite cements suggests high alkalinity in the terminal Ediacaran ocean. Geochemical analysis of micro-drilled samples shows that distinct compositions are registered in different carbonate phases, which should be considered when constructing chemostratigraphic profiles representative of true temporal variations in seawater chemistry. Integrated chemostratigraphic data suggest enhanced burial of organic carbon and pyrite, and the occurrence of extensive marine anoxia (at least in the Gaojiashan Member). Rapid basinal subsidence and carbonate accumulation during a time of elevated seawater alkalinity and increased rates of pyrite burial may have facilitated the evolutionary innovation of early biomineralizing metazoans.

Uranium isotope fractionation induced by aqueous speciation: Implications for U isotopes in marine CaCO3 as a paleoredox proxy

Natural variations of 238U/235U in marine CaCO3 rocks are being explored as a novel paleoredox proxy to investigate oceanic anoxia events. Although it is generally assumed that U isotopes in CaCO3 directly record 238U/235U of seawater, recently published laboratory experiments demonstrate slight U isotope fractionation during U(VI) incorporation into abiotic calcium carbonates. This fractionation is hypothesized to depend on aqueous U(VI) speciation, which is controlled by pH, ionic strength, pCO2 and Mg2+ and Ca2+ concentrations. Secular variation in seawater chemistry could lead to changes in aqueous U(VI) speciation, and thus, may affect the extent of U isotope fractionation during U(VI) incorporation into CaCO3. In this study, we combine estimates of seawater composition over the Phanerozoic with a model of aqueous U speciation and isotope fractionation to explore variations in the expected offset between the U isotope composition of seawater and primary marine CaCO3 through time.We find that U isotope fractionation between U in primary marine CaCO3 and seawater could have varied between 0.11 and 0.23‰ over the Phanerozoic due to secular variations in seawater chemistry. Such variations would significantly impact estimates of the extent of marine anoxia derived from the U isotope record. For example, at the Permo-Triassic boundary, this effect might imply that the estimated extent of anoxia is ∼32% more extreme than previously inferred. One significant limitation of our model is that the existing experimental database covers only abiotic carbonate precipitation, and does not include a possible range of biological effects which might enhance or suppress the range of isotopic fractionation calculated here. As biotic carbonates dominate the marine carbonate record, more work is need to assess controls on U isotopic fractionation into biotic marine carbonates.

Secular variations in seawater chemistry controlling dolomitization in shallow reflux systems: insights from reactive transport modelling

AbstractDolomitization often plays a critical role in the pore network development of platform carbonates, with implications for reservoir quality distribution. Understanding both the hydrological system driving dolomitization and the chemistry of the fluids involved is fundamental to constrain predictions of the geometry and the petrophysical properties of dolomite bodies. Here, the role of secular variations in seawater Mg/Ca as a control on dolomitization and early porosity modification was evaluated using one‐dimensional reactive transport models and fluids based on modern (aragonite sea), Mississippian and Aptian (calcite sea) seawaters. The sensitivity of dolomitization to a range of extrinsic controls (brine salinity, temperature, fluid flow rate and pCO2) and to intrinsic reactivity of the sediments (effective reactive surface area) was also explored. Simulations suggest faster calcite replacement by dolomite for seawaters with higher Mg/Ca, indicating that dolomitization potential is determined more by Mg/Ca rather than saturation index. Increasing evaporative concentration enhances reaction rate independent of the effect of enhanced density‐driven fluid flux. In addition to brine composition, effective surface area of precursor sediments and temperature exert a critical control on replacement rate, while secular variations of pH and carbonate alkalinity associated with changes in pCO2 are only secondary controls. Above flow rates of 0·01 m yr−1 replacive dolomitization is reaction‐limited rather than flux limited, favouring alteration of fine‐grained carbonates and suggesting that preferential alteration of grainstone units is rare unless head gradients are low. Post‐replacement dolomite cementation is flux dependent, and thus favoured in areas of high head gradient and high permeability sediments and, contrary to replacement, supersaturation is a more important driver than Mg/Ca. While uncertainties remain regarding low‐temperature dolomitization kinetics, the capability of numerical simulations to decouple individual controls provides new insights which can be used, in conjunction with traditional comparative sedimentology, to generate more rigorous conceptual models for individual reservoir settings.

Fossil corals as an archive of secular variations in seawater chemistry since the Mesozoic

Numerous archives suggest that the major ion and isotopic composition of seawater have changed in parallel with large variations in geologic processes and Earth’s climate. However, our understanding of the mechanisms driving secular changes in seawater chemistry on geologic timescales is limited by the resolution of data in time, large uncertainties in seawater chemistry reconstructions, and ambiguities introduced by sample diagenesis. We validated the preservation of a suite of ∼60 unrecrystallized aragonitic fossil scleractinian corals, ranging in age from Triassic through Recent, for use as new archives of past seawater chemistry. Optical and secondary electron microscopy (SEM) studies reveal that fossil coral crystal fabrics are similar to those of modern coralline aragonite. X-ray diffractometry (XRD), cathodoluminescence microscopy (CL), and Raman studies confirm that these specimens contain little to no secondary calcite. In order to screen for geochemical changes indicative of alteration, we measured 87Sr/86Sr ratios, clumped isotopes, and trace element ratios sensitive to diagenesis (e.g., Mn/Ca). We retain samples when these tests either fail to identify any diagenetic modifications, or identify specific domains free of detectable alteration.Using the validated fossil coral archive we reconstruct seawater Mg/Ca and Sr/Ca ratios, measured by Secondary Ion Mass Spectrometry (SIMS), back to ∼230Ma. The effects of temperature on coral trace element incorporation cannot explain the trends observed in our fossil coral Mg/Ca and Sr/Ca data. In agreement with independent records, seawater Mg/Ca molar ratios inferred from corals are low (Mg/Ca ∼1) during the Cretaceous and Jurassic, and increase between the Early Cenozoic and present (Mg/Ca=5.2). Seawater Sr/Ca ratios from corals vary systematically between ∼8 and 13mmol/mol since 230Ma, with maximum values in the Cretaceous and Paleogene. The coral Sr/Ca record disagrees with records from hydrothermal CaCO3 veins, but is similar to those reconstructed from other biogenic carbonates, especially benthic foraminifera. The agreement between corals and other archives, for both Sr/Ca and Mg/Ca ratios, further validates our records. In return, fossil coral records improve our understanding of past variations in seawater Mg/Ca and Sr/Ca.

Opening of a trans-Pangaean marine corridor during the Early Jurassic: Insights from osmium isotopes across the Sinemurian–Pliensbachian GSSP, Robin Hood's Bay, UK

The Hispanic Corridor represents a significant phase of continental reorganisation of the Early Jurassic that eventually provided connectivity between the western Tethyan and eastern Pacific oceans along the Central Atlantic rift zone. Although the initiation of this marine corridor profoundly impacted oceanic circulation and marine faunal exchange patterns, the timing of its formation hitherto remains poorly constrained with estimates spanning both the Hettangian and Sinemurian.The Sinemurian–Pliensbachian Global Stratotype Section and Point (GSSP) at Robin Hood's Bay, UK, comprises a succession of well-exposed, immature organic-rich sediments, only previously characterised by strontium, oxygen and carbon isotope geochemistry. New Re and Os isotope profiling indicates substantial variation in seawater chemistry at this time. Initial osmium isotope data become increasing unradiogenic (0.40 to 0.20) across the boundary, providing evidence for a continual flux of unradiogenic Os into the oceans during the latest Sinemurian. The initial unradiogenic 187Os/188Os values indicate the occurrence of low-temperature hydrothermal activity associated with the formation of the Hispanic Corridor during the breakup of Pangaea. Therefore, combined with biogeography and faunal exchange patterns, the Os isotope data demonstrates that connectivity between the Eastern Pacific and Tethyan oceans initiated during the latest Sinemurian. As a result this study better constrains the timing of establishment of the Hispanic Corridor, which was previously limited to poorly defined biogeography.

Seawater acidification by CO2 in a coastal lagoon environment: Effects on life history traits of juvenile mussels Mytilus galloprovincialis

The carbonate chemistry of seawater from the Ria Formosa lagoon was experimentally manipulated, by diffusing pure CO2, to attain two reduced pH levels, by −0.3 and −0.6 pH units, relative to unmanipulated seawater. After 84days of exposure, no differences were detected in terms of growth (somatic or shell) or mortality of juvenile mussels Mytilus galloprovincialis. The naturally elevated total alkalinity of the seawater (≈3550μmolkg−1) prevented under-saturation of CaCO3, even under pCO2 values exceeding 4000μatm, attenuating the detrimental effects on the carbonate supply-side. Even so, variations in shell weight showed that net calcification was reduced under elevated CO2 and reduced pH, although the magnitude and significance of this effect varied among size-classes. Most of the loss of shell material probably occurred as post-deposition dissolution in the internal aragonitic nacre layer. Our results show that, even when reared under extreme levels of CO2-induced acidification, juvenile M. galloprovincialis can continue to calcify and grow in this coastal lagoon environment. The complex responses of bivalves to ocean acidification suggest a large degree of interspecific and intraspecific variability in their sensitivity to this type of perturbation. Further research is needed to assess the generality of these patterns and to disentangle the relative contributions of acclimation to local variations in seawater chemistry and genetic adaptation.

High-Frequency Dynamics of Ocean pH: A Multi-Ecosystem Comparison

The effect of Ocean Acidification (OA) on marine biota is quasi-predictable at best. While perturbation studies, in the form of incubations under elevated pCO2, reveal sensitivities and responses of individual species, one missing link in the OA story results from a chronic lack of pH data specific to a given species' natural habitat. Here, we present a compilation of continuous, high-resolution time series of upper ocean pH, collected using autonomous sensors, over a variety of ecosystems ranging from polar to tropical, open-ocean to coastal, kelp forest to coral reef. These observations reveal a continuum of month-long pH variability with standard deviations from 0.004 to 0.277 and ranges spanning 0.024 to 1.430 pH units. The nature of the observed variability was also highly site-dependent, with characteristic diel, semi-diurnal, and stochastic patterns of varying amplitudes. These biome-specific pH signatures disclose current levels of exposure to both high and low dissolved CO2, often demonstrating that resident organisms are already experiencing pH regimes that are not predicted until 2100. Our data provide a first step toward crystallizing the biophysical link between environmental history of pH exposure and physiological resilience of marine organisms to fluctuations in seawater CO2. Knowledge of this spatial and temporal variation in seawater chemistry allows us to improve the design of OA experiments: we can test organisms with a priori expectations of their tolerance guardrails, based on their natural range of exposure. Such hypothesis-testing will provide a deeper understanding of the effects of OA. Both intuitively simple to understand and powerfully informative, these and similar comparative time series can help guide management efforts to identify areas of marine habitat that can serve as refugia to acidification as well as areas that are particularly vulnerable to future ocean change.

Secular variations in seawater chemistry as a control on the chemistry of basinal brines: test of the hypothesis

AbstractThe hypothesis that basinal brines inherited their major ion chemistries and elevated salinities from evaporated paleoseawaters is tested by comparing the compositions of basinal brines in Silurian (Michigan basin, Illinois basin, Appalachian basin in eastern Ohio) and Jurassic/Cretaceous (Central Mississippi Salt Dome basin, Arkansas shelf, and south‐central Texas) host rocks, when the world oceans were ‘CaCl2 seas’, with those from Permian and Pennsylvanian rocks (Palo Duro basin, Central Basin Platform, and Delaware basin, Texas and New Mexico) when the world oceans were ‘MgSO4 seas’. Basinal brines examined are assumed to have originally formed from evaporation of the same seawaters that produced major evaporites. Sulfate, Mg and K levels in basinal brines are below the concentrations expected from evaporation of seawater of any type, which emphasizes the importance of diagenetic mineral–brine interactions in controlling basinal brine chemistry. There are no major differences in SO4, Mg and K concentrations between basinal brines hosted by rocks originally formed during ages when the world oceans were MgSO4 seas versus CaCl2 seas. Basinal brines in Pennsylvanian–Permian rocks are compositionally distinct (relatively high Na and low Ca) from basinal brines in Silurian, Jurassic and Cretaceous host rocks, which may reflect original differences in seawater chemistry. Basinal brines enriched in Ca and depleted in Na relative to evaporated seawater of any type have traditionally been interpreted to form by albitization of plagioclase feldspar. A new explanation for Ca enrichment and Na depletion of basinal brines is the mixing of evaporated CaCl2‐type seawater with more dilute water. Some basinal brines are similar in major ion composition to evaporated seawater of a particular age, for example basinal brines in the Cretaceous Edwards Group carbonates, Texas, where dolomitization is the only reaction required to convert evaporated Mesozoic CaCl2 seawater into Edwards Group brine.

Are secular variations in seawater chemistry reflected in the compositions of basinal brines?

It has been proposed that brines in Phanerozoic sedimentary basins inherited their chemistries and salinities from evaporated paleoseawaters during times when the world oceans were Ca-rich and SO 4-poor, such as the Silurian and Devonian. However, the compositions of typical Silurian and Devonian-hosted brines in the Illinois and Michigan basins show significant deviations from calculated Silurian seawater evaporation trends, reflecting instead, diagenetic control of compositions. In addition, brines in many basins show evidence for the dissolution of halite being an important source of salinity in addition to, or instead of, evaporated seawater. As long as there is halite present, generation of salinity could continue to occur long after the deposition of evaporites and the influx of evaporated seawater. Thus, even the concept of assigning an age to a basinal brine is problematic given the dynamics of fluid flow, mixing, and solute transport which can occur in sedimentary sequences.

Reproducibility of geochemical and climatic signals in the Atlantic coral Montastraea faveolata

Monthly resolved, 41‐year‐long stable isotopic and elemental ratio time series were generated from two separate heads of Montastraea faveolata from Looe Key, Florida, to assess the fidelity of using geochemical variations in Montastraea, the dominant reef‐building coral of the Atlantic, to reconstruct sea surface environmental conditions at this site. The stable isotope time series of the two corals replicate well; mean values of δ18O and δ13C are indistinguishable between cores (compare 0.70‰ versus 0.68‰ for δ13C and −3.90‰ versus −3.94‰ for δ18O). Mean values from the Sr/Ca time series differ by 0.037 mmol/mol, which is outside of analytical error and indicates that nonenvironmental factors are influencing the coral Sr/Ca records at Looe Key. We have generated significant δ18O–sea surface temperature (SST) (R = −0.84) and Sr/Ca‐SST (R = −0.86) calibration equations at Looe Key; however, these equations are different from previously published equations for Montastraea. Variations in growth parameters or kinetic effects are not sufficient to explain either the observed differences in the mean offset between Sr/Ca time series or the disagreement between previous calibrations and our calculated δ18O‐SST and Sr/Ca‐SST relationships. Calibration differences are most likely due to variations in seawater chemistry in the continentally influenced waters at Looe Key. Additional geochemical replication studies of Montastraea are needed and should include multiple coral heads from open ocean localities complemented whenever possible by seawater chemistry determinations.

The geochemical evolution of the Catalan potash subbasin, South Pyrenean foreland basin (Spain)

Over the last decade, our studies in ancient evaporitic basins have been based on a detailed study of a single borehole record. The detailed findings in medium- to large-sized evaporitic basins were shadowed with a relevant question: can interpretations from a representative evaporitic record in a single borehole be extended to the whole evaporitic basin? This paper addresses that question; the results obtained are compared with results from another distant point within the basin. The general methodology not only proves its reliability in interpreting the evolution of evaporitic basins from a single borehole but reveals its capability to obtain detailed palaeoenvironmental interpretations. The chemical evolution of an Upper Eocene evaporitic sequence from the South Pyrenean foreland basin (Spain) has been investigated along the Súria-19 borehole record. Detailed petrographic and mineralogical study, X-ray microanalysis of frozen primary inclusions trapped in halite (Cryo-SEM-EDS), systematic isotopic analysis ( δ 34S and δ 18O in sulphates) and computer-based evaporation models have been integrated in a multi-proxy methodology. This study revealed that a variable amount of Ca excess is required throughout different parts of the marine Lower Halite Unit (LHU) for sylvite, instead of K–Mg sulphates, to form. This Ca excess is in turn different from that required for the western sector of the same evaporitic basin (Navarrese subbasin). Quick and variable changes in Ca-rich brines or equivalent dolomitization required are explained as internal processes within the basin rather than secular variations in seawater chemistry. The general hydrological evolution of the Catalan subbasin is explained as a restricted subbasin with a first marine stage in which continental input (up to 50% of total input) had an important control on the geochemistry of the subbasin. A second stage was determined during potash precipitation, in which the subbasin was cut from any seawater input to end up in its last stage as a purely continental evaporitic basin. Coupling evaporation models and analytical results we have obtained the proportions of recycling and their sources, estimated to change from a 100% (total mass of sulphate) Eocene source to 20% Eocene and 80% Triassic (Keuper) towards the latest stage of potash precipitation. The results obtained have been compared with results from the Navarrese subbasin allowing an integrated interpretation of the hydrological evolution of the whole Upper Eocene South Pyrenean basin. Local geochemical variations within the Upper Eocene south Pyrenean basin are explained by the differences in paleogeographical setting of the Navarrese and Catalan subbasins.

Secular variation in seawater chemistry and the origin of calcium chloride basinal brines

CaCl 2 basinal brines, which are present in most Phanerozoic sedimentary basins, inherited their chemistries and salinities from evaporated paleoseawaters when the world oceans were Ca rich and SO 4 poor (CaCl 2 seas). CaCl 2 seas coincided with periods of rapid seafloor spreading, high influxes of mid-ocean-ridge brines rich in CaCl 2 , and elevated sea levels, conditions that favored accumulation of marine CaCl 2 brines in marginal and interior continental basins. Typical basinal brines in Silurian-Devonian formations of the interior Illinois basin, United States, show the same compositional trends as those of progressively evaporated CaCl 2 -rich Silurian seawater. Chemical deviations can be accounted for quantitatively by brine-rock reactions during burial (dolomitization, dolomite and K-feldspar cement). This explanation for the origin of CaCl 2 basinal brines contrasts with others that assume constancy of seawater chemistry and involve more complex brine-rock interactions.

Dolomite formation and biogeochemical cycles in the Phanerozoic

SummaryBased on present knowledge of the purely chemical controls on the kinetics of massive dolomite formation, the abundance and distribution of dolomite throughout the Phanerozoic remains an enigma, sometimes referred to as the ‘dolomite problem'. Comparing dolomite abundance to secular variation in seawater chemistry indicates that some changes in seawater chemistry are more likely to have resulted from extensive dolomitization rather than to have caused it. The recently formulated microbial dolomite model provides the opportunity to view the geological history of dolomite formation from a new perspective. A biogeochemical approach to the ‘dolomite problem' reveals a plausible connection between Phanerozoic geochemical cycles and dolomite formation. In particular, periods of more extensive dolomitization broadly correlate with diverse indicators of decreased oxygen levels in the atmosphere and oceans. Lowered oxygen levels would have fostered a more active community of anaerobic microbes, including sulphate‐reducing bacteria, which in turn could have led to more extensive dolomitization of marine carbonates.

Secular Variation in Seawater Chemistry During the Phanerozoic As Indicated By Brine Inclusions in Halite

Analysis of data on the chemical composition of primary fluid inclusions (brine inclusions) in primary‐bedded halite from many evaporite formations of northern Pangea shows that during the Phanerozoic the chemical composition of marine brines was oscillating significantly between the Na‐K‐Mg‐Ca‐Cl type and the Na‐K‐Mg‐Cl‐SO4 type. We regard those changes as corresponding to the chemical evolution of the Phanerozoic ocean. The changes correlate in time with earlier suggested secular changes in the mineralogies of marine nonskeletal limestones and potash evaporites. In addition to those secular changes of seawater chemistry, the concentrations of K, Mg, Ca, and SO4 ions in marine brines underwent important changes under the influence of local factors, including rock‐water interaction. These secondary changes did not influence the principal chemical type of the brine characteristic for a given time interval. In the past concentration of the Ca‐ion did not exceed the present concentration in marine water by a...

Diagenetic comparisons between non-tropical Cenozoic limestones of New Zealand and tropical Mississippian limestones from Indiana, USA: Is the non-tropical model better than the tropical model?

Mississippian limestones exposed in Indiana, U.S.A., were deposited in a shallow tropical ocean. However, many properties of these limestones are more like those of modern and Cenozoic non-tropical limestones such as those found in New Zealand. The dominant skeletal grains in the Indiana limestones are calcitic echinoderms, bryozoans, and brachiopods. The dominant skeletal grains in most Cenozoic limestones of New Zealand are calcitic bryozoans, echinoderms, bivalve molluscs, and foraminifera. In contrast, modern and Cenozoic tropical limestones contain an abundance of aragonitic green algae, corals, and molluscs. Early in diagenesis the metastable aragonite dissolves and reprecipitates as calcite, causing early cementation of the sediments. Originally aragonitic fossils that have dissolved can be identified as molds that are commonly filled with secondary calcite. Because they contained little aragonite, most of the Indiana and New Zealand limestones did not have an abundant source of early cement. Except for local cases in which grains were cemented in contact with carbonate supersaturated seawater, grainstones were relatively deeply buried with little cement between the grains. This resulted in mechanical and chemical compaction of skeletal grains, producing a `fitted fabric' with greatly reduced pore space, either open or filled with cement between the grains. Cement in these aragonite-poor grainstones comes largely from pressure dissolution between grains and along stylolitic seams in the rock, features that are common only after burial beyond a few hundred meters. The final product of deeply buried (up to 2000 m) Cenozoic New Zealand grainstones is similar to the Mississippian grainstones of Indiana. In the Indiana limestones we have only the final product of this extensive burial diagenesis. However, the New Zealand sediments and rocks reveal all steps of formation of the final deeply buried limestone. The reason for the scarcity of originally aragonitic fossil grains in Paleozoic rocks worldwide is unknown. Organisms with aragonitic skeletons such as some molluscan groups and calcareous green algae were present, but seldom in much abundance. The aragonitic scleractinian corals had not yet evolved. Previous researchers have noted that non-skeletal precipitates such as ooids and cements have at times during the Paleozoic been predominantly aragonite and at other times calcite. They have attributed this difference to secular variation in seawater chemistry (icehouse vs. greenhouse seas). Abundance of aragonitic and calcitic skeletal grains does not follow this pattern.

Secular variation in seawater chemistry: An explanation for the coupled secular variation in the mineralogies of marine limestones and potash evaporites over the past 600 m.y.

Secular changes in the mineralogies of marine nonskeletal limestones and potash evaporites occur in phase on a 100–200 m.y. time scale such that periods of “aragonite seas” are synchronized with MgSO4 evaporites and periods of “calcite seas” with KCl evaporites. It is proposed that these coupled changes are the result of secular variation in seawater chemistry controlled primarily by fluctuations in the mid-ocean ridge hydrothermal brine flux, which in turn have been driven by fluctuations in the rate of ocean crust production. Quantitative predictions based on this hypothesis yield secular variation in limestone and potash evaporite mineralogies that closely match the observed variation over the past 600 m.y., providing strong support for the thesis that seawater chemistry, rather than remaining constant, has oscillated significantly over geologic time.

熱水系物質循環と海水組成の進化

Geochemical data on the evolution of seawater chemistry during the past one billion years (Sr/Ca, Li/Ca, Ge/Si, 187 Os/186 Os, δ34 S, 87Sr/86 Sr) were summarized. These data indicate that the variations in seawater chemistry have been influenced by the circulation of ydrothermal solution at mid-oceanic ridges. The circulation rate of hydrothermal solution is related to ocean floor spreading rate. Thus, it is considered that tectonics is important factor in controlling the chemical evolution of seawater.Tectonics affects not only seawater chemistry, but also CO 2 content in atmosphere and consequently climate. A correlation between δ34 S and 87 Sr/86 Sr variations of seawater indicates that hydrothermal solution and seawater-rock interaction was important for causing the variations in seawater chemistry before 1 billion years ago. Geochemical data (REE etc.) on BIF (banded iron formations) and sedimentary rocks indicate that the hydrothermal solution-oceanic crust interaction controlled Archean seawater chemistry. Influence of this interaction on the seawater chemistry decreased from Archean to Proterozoic, while weathering and biogenic activity became important.

Carbon isotopes and Precambrian—Cambrian boundary geology, South Australia: ocean basin formation, seawater chemistry and organic evolution

ABSTRACTA carbon isotope stratigraphy from the lowest Cambrian strata in the Adelaide fold belt of South Australia is interpreted in terms of the geological context of the sequence: major transgression, developing circulation patterns and upwelling resulting from an adjacent opening ocean, and biomass increases stemming from the Cambrian radiation event. There is also evidence from the textures of ooids and cements in late Precambrian‐Cambrian strata for subtle variations in seawater chemistry across the boundary and these may well have been instrumental in the development of calcareous skeletons in the early metazoans.