Mg,Ca and O18O16 exchange in the sediment-pore water system,hole 149, DSDP

The diagenesis and geochemical evolution of deep-sea sediments are controlled by the interaction between sediments and their associated pore waters. With increasing depth, the pore water of Hole 149 (DSDP) exhibits a strong depletion in Mg and a corresponding enrichment in Ca, while the alkalinity remains relatively constant. Dissolved SiO₂ is nearly constant in the upper 100 m of sediment, but is highly enriched in the deepest pore waters. The pore waters exhibit a depletion in K with increasing depth, and $\text{O}{}^{18}\text{O}{}^{16}$ pore water ratios also decrease.The sediment section has three zones of sedimentary regimes with increasing depth in the drill hole: an upper 100 m section of detrital clays, a middle section enriched in calc-akalic volcanics which have undergone submarine weathering to a smectite phase, and a lower section of siliceous ooze which still has a diagenetic smectite phase. The quartz-feldspar ratios and $\text{O}{}^{18}\text{O}{}^{16}$ composition of the silicate phases are in agreement with these interpretations.The submarine weathering of volcanics to a smectite can account for the observed pore water gradients. Volcanics release Ca and Mg to the pore waters causing the alkalinity values to increase. Smectite is formed, depletes the pore waters in Mg and O¹⁸ and causes the alkalinity to decrease. The net reaction allows for the observed relationship between pore water Ca and Mg gradients with little net change in alkalinity. Given the abundance of volcanics in many deep-sea sediments, especially in lower sections which often form near ridge crests, the submarine formation of smectite may be an additional oceanic Mg sink which has not yet been fully considered.     

A strontium isotopic study of Smackover brines and associated solids,southern Arkansas

The isotopic composition of Sr has been measured in brine samples from the Upper Jurassic Smackover Formation in southern Arkansas; ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios range from 0.7071 to 0.7101. With one exception, the 32 Smackover brines contain Sr which is significantly more radiogenic than the Sr in Late Jurassic sea water, indicating sizable Sr contributions from detrital sources. Isotopic analyses of core samples from rock units associated with the brines and regional stratigraphic relationships suggest that the radiogenic Sr was released from detrital minerals in Bossier shale to interstitial fluids expelled from the underlying Louann Salt in the North Louisiana salt basin. These fluids migrated through the Bossier Formation updip to the South Arkansas shelf, where they entered the upper Smackover carbonate grainstone. The radiogenic fluids mixed with Sr-rich interstitial marine waters that had the isotopic composition of Late Jurassic sea water; mixing in variable proportions resulted in the random distribution pattern of variable ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios that is observed in Smackover brines within the 5000 km² study area. Isotopic analyses of nonskeletal carbonate grains and coexisting coarse calcspar cement from the upper Smackover grainstone imply that the grains were diagenetically stabilized in the presence of interstitial marine waters, whereas the calcspar cement is a relatively late diagenetic phase precipitated after the arrival of radiogenic fluids.     

A study of strontium in core 119K,Discovery deep,Red Sea

The isotopic composition of strontium of pore water and of authigenic minerals leached from the sediment of core 119K with hot aqua regia is similar to that of the brine in the Discovery deep and differs from that of normal seawater. The average ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratio of strontium removed by acid leaching is 0.7077 ± 0.0007 (1σ) compared to a value of 0.70904 for the Red Sea. The detrital silicate fraction exhibits an approximate inverse correlation between ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios and strontium concentrations which provides tentative support for a model in which the detrital silicate fraction of deep-sea sediment is considered to be a mixture of terrigenous dust of sialic composition enriched in radiogenic ⁸⁷Sr and of volcanogenic material of basaltic composition and low ⁸⁷Sr abundance. The ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios of the shells of foraminifers and pteropods, expressed as δ ⁸⁷Sr‰ relative to 0.70904 for seawater, decrease from $\text{?0.23 ± 0.17‰}$ at 90 cm to $\text{?0.82 ± 0.17‰}$ at 273 cm and remain constant at this value to a depth of 450 cm. The lowering of the δ ⁸⁷Sr values is attributed both to the presence of aragonite overgrowths on pteropod shells and to possible isotope exchange with strontium in the connate fluid.     

Strontium isotope geochemistry of Icelandic geothermal systems and implications for sea water chemistry

Chemical and Sr isotopic analyses have been made of waters from 16 geothermal sites in Iceland with particular reference to the systems at Reykjanes and Svartsengi for which compositions of geothermal sea water and fresh and hydrothermally-altered rocks have been compared. The alkalies display mixing relationships indicating a hydrothermal input of Rb and K to local meteoric and sea waters as do results for Sr and Ca involving high-temperature fluids. ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios of the geothermal waters of meteoric origin parallel those of associated rocks but are higher. Ratios for geothermal sea waters are 0.7042 (Reykjanes) and 0.7040 (Svartsengi), lower than for normal sea water (0.7092) because of leaching of Sr from rocks followed by partial removal into alteration minerals, of which epidote and chlorite may be most important. Consequently, associated hydrothermally-altered rocks have been subject to significant Sr isotopic contamination by sea water Sr raising ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios from 0.7032 for fresh rock to 0.7038–0.7042 (Reykjanes) and to 0.7039–0.7041 (Svartsengi). Altered basalt is only ~50% equilibrated isotopically with geothermal sea water, at a water/rock ratio of ~2, but is internally equilibrated whereas palagonitized rocks (water/rock ratio of 3 to 4) are close to Sr isotopic equilibrium with associated sea water but show significant internal Sr disequilibrium. Hydrothermal input is unlikely to be important in the oceanic mass balance of Sr but is likely to be highly significant in controlling the strontium isotopic composition of sea water.     

Micromanganese nodules in deep-sea sediments: Uranium-isotopic evidence for post-depositional origin

Micromanganese nodules from three deep-sea cores are found to contain less U than average nodules dredged from the sea floor. The ${}^{234}\text{U}{}^{238}\text{U}$ ratio in these micronodules is higher than any previously reported in deep-sea sediments. We interpret these data to mean that at least some micronodules form well after deposition of the enclosing sediments, in particular where conditions are less oxidizing than average.     

Oxygen isotopic exchangeability of diatom valve silica; interpretation and consequences for paleoclimatic studies

Problems of analytical reproducibility have impeded the application of ${}^{18}\text{O}{}^{16}\text{O}$ ratio measurements of biogenic opal to paleoclimatology. Lack of reproducibility has been attributed to the labile nature of part of the oxygen of the silica. This has been studied using oxygen isotopic exchange between diatom silica and water vapor. This reaction involves the reversible hydrolysis of weak Si-O bonds. Using controlled exchange with waters of different oxygen isotopic composition, the isotopic ratio of both the exchanged and the unexchanged silica-bound oxygen were estimated. Optimum conditions for reproducible measurement of the oxygen isotopic composition of diatom silica are defined.     

The RbSr isotope system as an index of origin and diagenetic evolution of southern Pacific red clays

Morphological, mineralogical, chemical and RbSr isotopic studies have been made on Fesmectites (nontronites) from southern Pacific red clays cored near the Marquisas Islands. These minerals have at the top of the core, an ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratio of 0.70917 ± 0.00007, which indicates an authigenic origin in isotopic equilibrium with seawater. Weak leaching experiments with 1N HCl show that the nontronites also contain a volcanic component with a lower ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratio which, combined with the morphology of the particles, suggests a transportation by bottom currents of clay formed elsewhere.During burial, the nontronites experience diagenetic modifications resulting in an increase in Fe, K and Rb contents, a concomitant decrease of Mg, Ca, Ti, Na and Sr, and a preferential migration of radiogenic ⁸⁷Sr from the clays into the surrounding pore waters.The ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratio of the Sr adsorbed on the outermost surfaces of the nontronites does not change with depth in the core, and is, therefore, independent of diagenetic influence, which is rather characterized by the ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios of the interstitial waters. The isotopic composition of both the adsorbed Sr and that of the pore fluids may yield useful information on the crystallization environment and subsequent history of deep sea red clays.     

Annual periodicity of the 18O16O and 13C12C ratios in the coral Montastrea annularis

The isotopic ratios ${}^{18}\text{O}{}^{16}\text{O}$ and ${}^{13}\text{C}{}^{12}\text{C}$ show an annual periodicity in the coral Montastrea annularis from Bermuda, Jamaica and Barbados. The abundances of ¹⁸O and ¹³C are positively correlated in the Jamaica and Barbados samples, but inversely related in the Bermuda sample. Annual high density growth bands are formed during the season of warmest water temperature at all 3 sites and are enriched in ¹⁶O. M. Annularis has a constant displacement from oxygen isotopic equilibrium and accurately records seasonal temperature variations via the temperature-dependent aragonite-water fractionation factor. Light intensity, through the activity of the coral's endosymbiotic algae, regulates the depth-dependent and seasonal variations in the skeletal carbon isotopic composition.     

Untersuchung von isotopenfeinvariationen des calciums in der natur an rezenten carbonaten und sulfaten

Investigations of isotopic variations of calcium were carried out. For that purpose natural calcium carbonate and calcium sulfate samples were analysed. The isotopic ratios ${}^{44}\text{Ca}{}^{40}\text{Ca}$ and ${}^{48}\text{Ca}{}^{40}\text{Ca}$ were measured with a mass spectrometer by thermal ionization. The precision of the isotopic abundance measurements was better than 1%. per mass unit. One can conclude from the results that in general chemical exchange reactions of calcium ions which imply isotopic fractionation do not take place in nature. Only in the case of one sample (‘Gipsrose’) an isotopic variation of calcium was found. This fractionation can be explained by ion exchange or different diffusion rates of the calcium isotopes.     

Hydrogen isotope exchange between clay minerals and sea water

The D/H ratios of separated size fractions of clay minerals in two deep sea sediments taken from depths of 30 and 1100cm in a North Pacific Ocean core were measured to investigate the extent of hydrogen isotope exchange between detrital clay minerals and sea water. The D/H ratio of each size fraction of the shallower sample was compared with that of the corresponding size fraction of the deeper sample. No differences were detected between D/H ratios of corresponding size fractions from the two levels in the core except for the <0.1μm size fraction, which makes up only 5% of the sample. Even in this size fraction only about 8–28% D/H exchange is apparent. This is interpreted as indicating that no significant hydrogen isotope exchange between clay minerals and sea water has occurred during the past 2–3 Myr. Therefore information concerning the provenance and mode of formation of detrital clay minerals can be obtained from the D/H ratios of deep sea sediments younger than 2–3 Myr.     

Isotope and trace element geochemistry of sediments from the Barbados Ridge-Demerara Plain region,Atlantic Ocean

Twenty-four piston core sediment samples and 13 sediments and 3 basalts from DSDP Leg 78 Site 543 were analyzed for Sr, Nd and Pb isotopic compositions. The results show sediment with highly radiogenic Pb${}^{206}\text{Pb}{}^{204}\text{Pb}$ up to 19.8) and rather radiogenic Sr and unradiogenic Nd has been deposited in the region since the Cretaceous. The source of this sediment is probably the Archean Guiana Highland, which is drained by the Orinoco River. Pb and Sr isotopic compositions and sediment thickness decrease and${}^{143}\text{Nd}{}^{144}\text{Nd}$ increases northward due to a decrease in turbiditic component. This decrease is partly due to the damming action of basement ridges. Rare earth concentrations in the sediments are somewhat low, due to the abundance of detrital and biogenic components in the sediment and rapid sedimentation rates. Both positive and negative Ce anomalies occur in the surface sediments, but only positive Ce anomalies occur in the Site 543 sediments. It is unlikely that sediment subducted to the source region of Lesser Antilles arc magmas could be the cause of negative Ce anomalies in those magmas.Isotopic compositions of Site 543 basalts show some effect of contamination by seawater-basalt reaction products and sediments. Beyond this, however, they are typical of “normal” depleted MORB.     

Thorium and radium isotopic relationships in manganese nodules and sediments at MANOP Site S

Relationships among Th and Ra isotopes in nodule, sediment and water phases at MANOP Site S establish the most likely source for Th in the nodules, the frequency of nodule turning, and the similarity of micro and macro nodules. Manganese nodules and bottom waters have ${}^{230}\text{Th}{}^{232}\text{Th}$ activity ratios considerably higher than other phases at this site suggesting that sea water is the likely source of Th for the nodules. Similar ${}^{230}\text{Th}{}^{232}\text{Th}$ activity ratios in nodule tops and bottoms and in certain cases departure from expected ${}^{226}\text{Ra}{}^{230}\text{Th}$ activity ratios in nodule tops and bottoms indicate that the nodules rotate every one to ten thousand years. The micro nodules have diffusion coefficients of Ra similar to macro nodule bottoms. I suggest that they may act as a carrier phase for transporting metals through oxic sediments to nodules.     

Aragonite from deep sea ultramafic rocks

Aragonite mineralization was observed in serpentinized peridotites from the Romanche and Vema Fracture Zones in the Atlantic and the Owen Fracture Zone in the Indian Ocean, either in veins or as radial aggregates in cavities within the serpentinites. Evidence of incipient dissolution of the aragonite crystals was observed in one case. The aragonites tend to have lower Mg content (< 0.03%) and higher Sr content (> 0.95%) relative to other marine aragonites. Their ${}^{18}\text{O}{}^{16}\text{O}$, ${}^{13}\text{C}{}^{12}\text{C}$ and ${}^{87}\text{Sr}{}^{86}\text{Sr}$ isotopic ratios suggest the aragonite was deposited at ocean floor temperatures from solutions derived from sea water circulating in fissures and fractures within the ultramafic rocks. The ${}^{18}\text{O}{}^{16}\text{O}$ ratios of the serpentines indicate serpentinization occurred at higher temperatures, probably deeper in the crust. Low-T reactions between circulating seawater and Mg-silicates (primarily serpentine and pyroxenes) caused high pH and enrichment of Mg and Ca in the solution, conditions favoring carbonate precipitation. Aragonite was formed rather than calcite presumably because the high Mg²⁺ concentration in the solution inhibited calcite precipitation. The high Sr content of the aragonites is probably related, at least in part, to their low temperature of formation. Opaque mineral grains containing over 8% NiO and over 40% MnO were observed concentrated along the margins of some of the aragonite veins, suggesting that Ni is one of the elements mobilized during reactions between ultramafic rocks and circulating seawater.     

Experimental hydrogen isotope studies—I. Systematics of hydrogen isotope fractionation in the systems epidote-H2O,zoisite-H2O and AlO(OH)-H2O

$\text{H}\text{D}$ Fractionation factors between epidote minerals and water, and between the AlO(OH) dimorphs boehmite and diaspore and water, have been determined between 150 and 650°C. Small water mineral ratios were used to minimise the effect of incongruent dissolution of epidote minerals. Waters were extracted and analysed directly by puncturing capsules under vacuum. Hydrogen diffusion effects were eliminated by using thick-walled capsules.$\text{H}\text{D}$ Exchange rates are very fast between epidote and water (and between boehmite and water), complete exchange taking only minutes above 450°C but several months at 250°C. Exchange between zoisite and water (and between diaspore and water) is very much slower, and an interpolation method was necessary to determine fractionation factors at 450 and below.For the temperature range 300–650°C, the $\text{H}\text{D}$ equilibrium fractionation factor (α^e) between epidote and water is independent of temperature and Fe content of the epidote, and is given by 1000 In α_epidote-H2O^e = ?35.9 ± 2.5, while below 300°C 1000 In , with a ‘cross-over’ estimated to occur at around 185°C. By contrast, zoisite-water fractionations fit the relationship 1000 In .All studied minerals have hydrogen bonding. Fractionations are consistent with the general relationship: the shorter the O-H -- O bridge, the more depleted is the mineral in D.On account of rapid exchange rates, natural epidotes probably acquired their H-isotope compositions at or below 200°C, where fractionations are near or above 0%.; this is in accord with the observation that natural epidotes tend to concentrate D relative to other coexisting hydrous minerals.     

Strontium isotopic contamination and oxidation during ocean floor hydrothermal metamorphism of the ophiolitic rocks of the Troodos Massif,Cyprus

Twenty-six new high precision ${}^{87}\text{Sr}{}^{86}\text{Sr}$ratio determinations and existing analyses are used to discuss the strontium isotopic composition of the Upper Cretaceous ophiolitic rocks of the Troodos Massif, Cyprus. Relative to initial magmatic ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios (0.70338 ± 0.00010 to 0.70365 ± 0.00005), the hydrothermally metamorphosed pillow lavas and dyke complex have been contaminated by isotopically heavier strontium.This observation confirms the hypothesis that hydrothermal metamorphism was a consequence of sea water-rock interaction, since sea water was the only readily accessible reservoir of isotopically heavier strontium. The fact that metagabbros and altered trondhjemites were also Sr isotopically contaminated shows that sea water penetrated approximately 2 km into the oceanic crust represented by the ophiolitic sequence.The amount of Sr isotopic contamination requires that the bulk sea water: rock ratio was at least ~15:1 and shows that water-rock interaction occurred in a flow system. The degree of oxidation decreases with increasing depth. This shows that the vertical component of fluid flow was downward. The absolute bulk water/rock ratio (for water at S.T.P.), as estimated from the oxidation profile, may have been as large as ~3 × 10³:1 —a large figure which independently confirms that rocks showing strong δ¹⁸O shifts have interacted with large volumes of water.The sites of discharge of the hot fluid, which must have come out of the system, are identified as the cupriferous pyrite ore deposits. This process of mass transfer corresponds to hydrothermal convection in a permeable medium with an open upper boundary surface.     

Composition isotopique du strontium d'eaux interstitielles extraites de sédiments récents: un argument en faveur de l'homogénéisation isotopique des minéraux argileux

The ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratio of interstitial waters squeezed from recent sediments of the Pacific Ocean increases from 0.70920 ± 0.00017 (2σ) to 0.70960 ± 0.0023 and 0.70984 ± 0.00040 at 1.50 and 1.60 m depth—reference value for sea water: 0.70910 ± 0.00035. This variation underlines the likely existence of exchanges between the clays and the interstitial environment. The isotopic homogenization of strontium between the clays and their environment, result of these changes, becomes thus a credible phenomenon. This is a new argument for the dating of clays by the $\text{Rb}\text{Sr}$ method.     

Diffusion of ions in sea water and in deep-sea sediments

The tracer-diffusion coefficient of ions in water, D_j⁰, and in sea water, $\text{D}{}_{\mathrm{j}}{}^1$, differ by no more than zero to 8 per cent. When sea water diffuses into a dilute solution of water, in order to maintain the electro-neutrality, the average diffusion coefficients of major cations become greater but of major anions smaller than their respective $\text{D}{}_{\mathrm{j}}{}^1$ or D_j⁰ values. The tracer diffusion coefficients of ions in deep-sea sediments, D_j,sed., can be related to $\text{D}{}_{\mathrm{j}}{}^1$ by $\text{D}{}_{\mathrm{j,sed.}}\text{= D}{}_{\mathrm{j}}{}^1\text{·}\text{α}\text{θ}{}^2$, where θ is the tortuosity of the bulk sediment and a a constant close to one.     

Strontium isotopic composition of some brines from the Precambrian Shield of Canada

Twenty-four groundwater samples from seven operating mines at Sudbury, Yellow-knife and Thompson (Ontario, North West Territories and Manitoba, resp.), all from depths greater than 1 km and ranging in total dissolved solids (TDS) from 1900 to 250,000 mg l^?1, were measured for their ${}^{87}\text{Sr}{}^{86}\text{Ar}$ values. Each geographic location gives a limited range in values and each location is distinct from the others. This is interpreted as the result of extensive water-rock interaction on a local scale. For most of the time, these brines were isolated and only recently have been exposed to surface water as a result of the mining operations. The extent of the isolation is shown by the contrasting isotopic values of two “pockets” of water (0.711 vs. 0.716) located on opposite sides of the same fault system on the North Range at Sudbury. The exchange at all sites probably has continued until the present, as indicated by the close agreement between water and present-day${}^{87}\text{Sr}{}^{86}\text{Sr}$ whole-rock values. If so, it suggests that there is no single age for such brines, but it may be possible to date stages in the water's evolution by determining the age of secondary minerals that equilibrated with the water.     

Strontium isotopic studies of the volcanic rocks of the Saunda arc,Indonesia, and their petrogenetic implications

Pleistocene and Recent lavas from the Sunda arc range from those showing affinities with the island arc tholeiitic series, through a spectrum of calc-alkaline to high-K alkaline rocks. The tholeiitic rocks have relatively low ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios averaging 0–7043; the calc-alkaline rocks show a wide range (from 0.7038 to 0.7059, averaging 0.7048); the high-K alkaline rocks average 0.7045. A rhyolitic ignimbrite from Sumatra has an ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratio of 0.7139.The relationship between ${}^{87}\text{Sr}{}^{86}\text{Sr}$ and major and trace element geochemistry is variable and complex. Lavas from the same volcano sometimes show significant differences in ${}^{87}\text{Sr}{}^{86}\text{Sr}$ despite close geochemical relationships. Rocks of the calc-alkaline suite show a regular decrease in ${}^{87}\text{Sr}{}^{86}\text{Sr}$ from West Java to Bali and there is some evidence for increasing ${}^{87}\text{Sr}{}^{86}\text{Sr}$ with increasing depth to the Benioff zone. Calc-alkaline and tholeiitic rocks from the Sunda arc have significantly higher ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios than those from other island arcs, except from those arcs where continental crustal involvement has been inferred (e.g. New Zealand).A model of ⁸⁷Sr enrichment due to isotopic equilibration of oceanic crust with sea water and disequilibrium melting in the slab and/or mantle is favoured to explain the Sr isotopic composition of the tholeiitic and normal calc-alkaline lavas. Calc-alkaline lavas with high ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios are best explained by either sialic contamination, or the presence of alkali basalt as a component of the downgoing slab. The Sr isotopic data for the high-K alkaline lavas suggest a mantle origin. The high ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratio in the Lake Toba rhyolite implies a crustal origin.