259 resultados para STABLE CONTINENTAL REGIONS


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We determined the stable oxygen and carbon isotopic composition of live (Rose Bengal stained) tests belonging to different size classes of two benthic foraminiferal species from the Pakistan continental margin. Samples were taken at 2 sites, with water depth of about 135 and 275 m, corresponding to the upper boundary and upper part of the core region of the oxygen minimum zone (OMZ). For Uvigerina ex gr. U. semiornata and Bolivina aff. B. dilatata, delta13C and delta18O values increased significantly with increasing test size. In the case of U. ex gr. U. semiornata, delta13C increased linearly by about 0.105 per mil for each 100-µm increment in test size, whereas delta18O increased by 0.02 to 0.06 per mil per 100 µm increment. For B. aff. B. dilatata the relationship between test size and stable isotopic composition is better described by logarithmic equations. A strong positive linear correlation is observed between delta18O and delta13C values of both taxa, with a constant ratio of delta18O and delta13C values close to 2:1. This suggests that the strong ontogenetic effect is mainly caused by kinetic isotope fractionation during CO2 uptake. Our data underline the necessity to base longer delta18O and delta13C isotope records derived from benthic foraminifera on size windows of 100 µm or less. This is already common practice in down-core isotopic studies of planktonic foraminifera.

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Causes of change in deep water delta13C can be either global or local in extent. Global causes include (1) climatically-induced changes in the amount of terrestrial biomass which alter the average carbon isotopic composition of the oceanic reservoir (Shackleton, 1977), and (2) erosion and deposition of organic-rich, continental shelf sediments during sea level fluctuations which change the mean oceanic carbon: phosphorus ratio (Broecker, 1982 doi:10.1016/0079-6611(82)90007-6). Regional gradients of delta13C are created by remineralization of organic detritus within the deep ocean itself thus reflecting the distribution of water masses and modern thermohaline flow. Changes in a single geological record of benthic foraminiferal delta13C can result from any combination of these global and abyssal circulation effects. By sampling a large number of cores collected over a wide bathymetric range yet confined to a small geographical region we have minimized the ambiguity. We can assume that each delta13C record was equally affected by global causes of delta13C variation. The differences seen between the delta13C records must, therefore, reflect changes in the distribution of delta13C in the deep ocean. We interpret these differences in distribution in terms of changes in the ocean's abyssal circulation. Benthic foraminiferal carbon isotopic evidence from a suite of Sierra Leone Rise cores indicates that the deeper parts of the eastern Atlantic basins underwent a reduction in [O2] during the maximum of the last glaciation. Reduced advection of O2-rich deep water through low-latitude fracture zones, associated with increased delivery of organic matter to the deep ocean, lowered the delta13C of deep water SumCO2 at all depths below the sill separating the eastern and western Atlantic basins (Metcalf et al., 1964 doi:10.1016/0011-7471(64)91078-2). This decreased advection into the eastern Atlantic Ocean coincides with the overall decrease in deep water production in the North Atlantic during the last glacial maximum (Curry and Lohmann, 1982 doi:10.1016/0033-5894(82)90071-0; Boyle and Keigwin, 1982 doi:10.1126/science.218.4574.784; Schnitker, 1979 doi:10.1016/0377-8398(79)90020-3; Streeter and Shackleton, 1979 doi:10.1126/science.203.4376.168).

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Celebes Basin sediments from Ocean Drilling Program Site 767 (Leg 124) containing both marine and terrestrial organic matter have been investigated through palynofacies and geochemical analyses. The main degradation processes affecting or having affected organic matter are recorded in the sedimentary column as shown by ammonium, phosphate and sulfate pore-water profiles, and by petrographic and geochemical analyses of sediments. In the upper part of the sedimentary section (down to 200 mbsf), the decrease of the ratio of total organic carbon to sulfur (TOC/S) with depth, generally related to the sulfate reduction process, is accompanied by an increase of framboidal pyrite content in the marine organic matter, and by an increasing amount of amorphous marine organic matter relative to the total organic matter. However, as the terrestrial organic input also varies with depth, dilution effects are superimposed on diagenesis. This continental supply affects the TOC/S ratio by increasing total organic carbon and decreasing the ability of the bulk organic matter to be metabolized through sulfate reduction. A positive relationship between the TOC/P ratio and the amount of degraded organic matter of marine origin clearly displays the effect of an organic source on the composition of the sediment. Each lithostratigraphic unit possesses its own characteristics in terms of composition and preservation of organic matter. The effects of diagenesis can only be appreciated within a single lithostratigraphic unit and mainly affect the less-resistant marine organic matter.

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In order to investigate a possible connection between tropical northeast (NE) Atlantic primary productivity, Atlantic meridional overturning circulation (AMOC), and drought in the Sahel region during Heinrich Stadial 1 (HS1), we used dinoflagellate cyst (dinocyst) assemblages, Mg/Ca based reconstructed temperatures, stable carbon isotopes (d13C) and geochemical parameters of a marine sediment core (GeoB 9508-5) from the continental slope offshore Senegal. Our results show a two-phase productivity pattern within HS1 that progressed from an interval of low marine productivity between ~ 19 and 16 kyr BP to a phase with an abrupt and large productivity increase from ~ 16 to 15 kyr BP. The second phase is characterized by distinct heavy planktonic d13C values and high concentrations of heterotrophic dinocysts in addition to a significant cooling signal based on reconstructions of past sea surface temperatures (SST). We conclude that productivity variations within HS1 can be attributed to a substantial shift of West African atmospheric processes. Taken together our results indicate a significant intensification of the North East (NE) trade winds over West Africa leading to more intense upwelling during the last millennium of HS1 between ~ 16 and 15 kyr BP, thus leaving a strong imprint on the dinocyst assemblages and sea surface conditions. Therefore, the two-phase productivity pattern indicates a complex hydrographic setting suggesting that HS1 cannot be regarded as uniform as previously thought.

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We examine the link between organic matter degradation, anaerobic methane oxidation (AMO), and sulfate depletion and explore how these processes potentially influence dolomitization. We determined rates and depths of AMO and dolomite formation for a variety of organic-rich sites along the west African Margin using data from Ocean Drilling Program (ODP) Leg 175. Rates of AMO are calculated from the diffusive fluxes of CH4 and SO4, and rates of dolomite formation are calculated from the diffusive flux of Mg. We find that the rates of dolomite formation are relatively constant regardless of the depth at which it is forming, indicating that the diffusive fluxes of Mg and Ca are not limiting. Based upon the calculated log IAP values, log K(sp) values for dolomite were found to narrowly range between -16.1 and -16.4. Dolomite formation is controlled in part by competition between AMO and methanogenesis, which controls the speciation of dissolved CO2. AMO increases the concentration of CO3[2-] through sulfate reduction, favoring dolomite formation, while methanogenesis increases the pCO2 of the pore waters, inhibiting dolomite formation. By regulating the pCO2 and alkalinity, methanogenesis and AMO can regulate the formation of dolomite in organic-rich marine sediments. In addition to providing a mechanistic link between AMO and dolomite formation, our findings provide a method by which the stability constant of dolomite can be calculated in modern sediments and allow prediction of regions and depth domains in which dolomite may be forming.

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The upper 38 m of Hole 722B sediments (Owen Ridge, northwest Arabian Sea) was sampled at 20 cm intervals and used to develop records of lithogenic percent, mass accumulation rate, and grain size spanning the past 1 m.y. Over this interval, the lithogenic component of Owen Ridge sediments can be used to infer variability in the strength of Arabian Sea summer monsoon winds (median grain size) and the aridity of surrounding dust source-areas (mass accumulation rate; MAR in g/cm**2/k.y). The lithogenic MAR has strong 100, 41, and 23 k.y. cyclicities and is forced primarily by changes in source-area aridity associated with glacial-interglacial cycles. The lithogenic grain size, on the other hand, exhibits higher frequency variability (23 k.y.) and is forced by the strength of summer monsoon winds which, in turn, are forced by the effective sensible heating of the Indian-Asian landmass and by the availability of latent heat from the Southern Hemisphere Indian Ocean. These forcing mechanisms combine to produce a wind-strength record which has no strong relationship to glacial-interglacial cycles. Discussion of the mechanisms responsible for production of primary Milankovitch cyclicities in lithogenic records from the Owen Ridge is presented elsewhere (Clemens and Prell, 1990, doi:10.1029/PA005i002p00109). Here we examine the 1 m.y. record from Hole 722B focusing on different aspects of the lithogenic components including an abrupt change in the monsoon wind-strength record at 500 k.y., core-to-core reproducibility, comparison with magnetic susceptibility, coherency with a wind-strength record from the Pacific Ocean, and combination frequencies in the wind-strength record. The Hole 722B lithogenic grain-size record shows an abrupt change at 500 k.y. possibly indicating decreased monsoon wind-strength over the interval from 500 k.y. to present. The grain-size decrease appears to be coincident with a loss of spectral power near the 41 k.y. periodicity. However, the grain-size decrease is not paralleled in the Globigerina bulloides upwelling record, an independent record of summer monsoon wind-strength (Prell, this volume). These observations leave us with competing hypotheses possibly involving: (1) a decrease in the sensitivity of monsoon windstrength to obliquity forcing, (2) decoupling of the grain size and G. bulloides records via a decoupling of the nutrient supply from wind-driven upwelling, and/or (3) a change in dust source-area or the patterns of dust transporting winds. Comparison of the lithogenic grain size and weight percent records from Hole 722B with those from a nearby core shows that the major and most minor events are well replicated. These close matches establish our confidence in the lithogenic extraction techniques and measurements. Further, reproducibility on a core-to-core scale indicates that the eolian depositional signal is regionally strong, coherent, and well preserved. The lithogenic weight percent and magnetic susceptibility are extremely well correlated in both the time and frequency domains. From this we infer that the magnetically susceptible component of Owen Ridge sediments is of terrestrial origin and transported to the Owen Ridge via summer monsoon winds. Because of the high correlation with the lithogenic percent record, the magnetic susceptibility record can be cast in terms of lithogenic MAR and used as a high resolution proxy for continental aridity. In addition to primary Milankovitch periodicities, the Hole 722B grain-size record exhibits periodicity at 52 k.y. and at 29 k.y. Both periodicities are also found in the grain-size record from piston core RC11-210 in the equatorial Pacific Ocean. Comparison of the two grain-size records shows significant coherence and zero phase relationships over both the 52 and 29 k.y. periodicities suggesting that the strengths of the Indian Ocean monsoon and the Pacific southeasterly trade winds share common forcing mechanisms. Two possible origins for the 52 and 29 k.y. periodicities in the Hole 722B wind-strength record are (1) direct Milankovitch forcing (54 and 29 k.y. components of obliquity) and (2) combination periodicities resulting from nonlinear interactions within the climate system. We find that the 52 and 29 k.y. periodicities show stronger coherency with crossproducts of eccentricity and obliquity (29 k.y.) and precession and obliquity (52 k.y.) than with direct obliquity forcing. Our working hypothesis attributes these periodicities to nonlinear interaction between external insolation forcing and internal climatic feedback mechanisms involving an interdependence of continental snow/ice-mass (albedo) and the hydrological cycle (latent heat availability).

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A variety of evidence suggests that average sea surface temperatures (SSTs) during the last glacial maximum in the California Borderlands region were significantly colder than during the Holocene. Planktonic foraminiferal delta18O evidence and average SST estimates derived by the modern analog technique indicate that temperatures were 6°-10°C cooler during the last glacial relative to the present. The glacial plankton assemblage is dominated by the planktonic foraminifer Neogloboquadrina pachyderma (sinistral coiling) and the coccolith Coccolithus pelagicus, both of which are currently restricted to subpolar regions of the North Pacific. The glacial-interglacial average SST change determined in this study is considerably larger than the 2°C change estimated by Climate: Long-Range Investigation, Mapping, and Prediction (CLIMAP) [1981]. We propose that a strengthened California Current flow was associated with the advance of subpolar surface waters into the Borderlands region during the last glacial.

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Lower ocean crust is primarily gabbroic, although 1-2% felsic igneous rocks that are referred to collectively as plagiogranites occur locally. Recent experimental evidence suggests that plagiogranite magmas can form by hydrous partial melting of gabbro triggered by seawater-derived fluids, and thus they may indicate early, high-temperature hydrothermal fluid circulation. To explore seawater-rock interaction prior to and during the genesis of plagiogranite and other late-stage magmas, oxygen-isotope ratios preserved in igneous zircon have been measured by ion microprobe. A total of 197 zircons from 43 plagiogranite, evolved gabbro, and hydrothermally altered fault rock samples have been analyzed. Samples originate primarily from drill core acquired during Ocean Drilling Program and Integrated Ocean Drilling Program operations near the Mid-Atlantic and Southwest Indian Ridges. With the exception of rare, distinctively luminescent rims, all zircons from ocean crust record remarkably uniform d18O with an average value of 5.2 ± 0.5 per mil (2SD). The average d18O(Zrc) would be in magmatic equilibrium with unaltered MORB [d18O(WR) ~5.6-5.7 per mil], and is consistent with the previously determined value for equilibrium with the mantle. The narrow range of measured d18O values is predicted for zircon crystallization from variable parent melt compositions and temperatures in a closed system, and provides no indication of any interactions between altered rocks or seawater and the evolved parent melts. If plagiogranite forms by hydrous partial melting, the uniform mantle-like d18O(Zrc) requires melting and zircon crystallization prior to significant amounts of water-rock interactions that alter the protolith d18O. Zircons from ocean crust have been proposed as a tectonic analog for >3.9 Ga detrital zircons from the earliest (Hadean) Earth by multiple workers. However, zircons from ocean crust are readily distinguished geochemically from zircons formed in continental crustal environments. Many of the >3.9 Ga zircons have mildly elevated d18O (6.0-7.5 per mil), but such values have not been identified in any zircons from the large sample suite examined here. The difference in d18O, in combination with newly acquired lithium concentrations and published trace element data, clearly shows that the >3.9 Ga detrital zircons did not originate by processes analogous to those in modern mid-ocean ridge settings.

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Carbon cycling is an important but poorly understood process on passive continental margins. In this study, we use the ionic and stable isotopic composition of interstitial waters and the petrology, mineralogy, and stable isotopic composition of authigenic carbonates collected from Ocean Drilling Program (ODP) Leg 174A (Sites 1071 and 1072) to constrain the origin of the carbonates and the evolution of methane on the outer New Jersey shelf. The pore fluids of the New Jersey continental shelf are characterized by (1) a fresh-brackish water plume, and (2) organic matter degradation reactions, which proceed through sulfate reduction. However, only minor methanogenesis occurs. The oxygen isotopic composition of the pore fluids supports a meteoric origin of the low salinity fluids. Authigenic carbonates are found in nodules, thin (~1-cm) layers, and carbonate cemented pavements. Siderite is the most common authigenic carbonate, followed by dolomite and calcite. The oxygen isotopic composition of the authigenic carbonates, i.e. 1.3-6.5 per mil PeeDee Belemnite (PDB), indicates an origin in marine pore fluids. The carbon isotopic composition of dolomite cements range from -16.4 to -8.8 per mil PDB, consistent with formation within the zone of sulfate reduction. Siderite d13C values show a greater range (-17.67-16.4 per mil), but are largely positive (mean=2.8 per mil) and are interpreted to have formed throughout the zone of methanogenesis. In contrast, calcite d13C values are highly negative (as low as -41.7 per mil)and must have formed from waters with a large component of dissolved inorganic carbon derived from methane oxidation. Pore water data show that despite complete sulfate reduction, methanogenesis appears not to be an important process presently occurring in the upper 400 m of the outer New Jersey shelf. In contrast, the carbon isotopic composition of the siderites and calcites document an active methanogenic zone during their formation. The methane may have been either oxidized or vented from shelf sediments, perhaps during sea-level fluctuations. If this unaccounted and variable methane flux is an areally important process during Neogene sea-level fluctuations, then it likely plays an important role in long-term carbon cycling on passive continental margins

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The middle Miocene delta18O increase represents a fundamental change in the ocean-atmosphere system which, like late Pleistocene climates, may be related to deepwater circulation patterns. There has been some debate concerning the early to early middle Miocene deepwater circulation patterns. Specifically, recent discussions have focused on the relative roles of Northern Component Water (NCW) production and warm, saline deep water originating in the eastern Tethys. Our time series and time slice reconstructions indicate that NCW and Tethyan outflow water, two relatively warm deepwater masses, were produced from ~20 to 16 Ma. NCW was produced again from 12.5 to 10.5 Ma. Another feature of the early and middle Miocene oceans was the presence of a high delta13C intermediate water mass in the southern hemisphere, which apparently originated in the Southern Ocean. Miocene climates appear to be related directly to deepwater circulation changes. Deep-waters warmed in the early Miocene by ~3°C (?20 to 16 Ma) and cooled by a similar amount during the middle Miocene delta18O increase (14.8 to 12.6 Ma), corresponding to the increase (?20 Ma) and subsequent decrease (~16 Ma) in the production of NCW and Tethyan outflow water. Large (>0.6 per mil), relatively rapid (~0.5 m.y.) delta18O increases in both benthic and planktonic foraminifera (i.e., the Mi zones of Miller et al. (1991a) and Wright and Miller (1992a)) were superimposed in the long-term deepwater temperature changes; they are interpreted as reflecting continental ice growth events. Seven of these m.y. glacial/interglacial cycles have been recognized in the early to middle Miocene. Two of these glacial/interglacial cycles (Mi3 and Mi4) combined with a 2° to 3°C decrease in deepwater temperatures to produce the middle Miocene delta18O shift.

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A major change in Cenozoic deep-sea benthic foraminifera occurred in the Atlantic, Indian, and Pacific oceans near the Paleocene/Eocene boundary. Benthic foraminiferal abundance changes began at about 61.5 Ma at Pacific Deep Sea Drilling Project (DSDP) Site 577. A major extinction event followed at 58-57 Ma (between Zones P6a and P6b), and a series of first appearances continued until circa 55.5 Ma (Zone P6c). These faunal changes occurred during a 6°C warming of Pacific bottom water and may indicate that the primary cause was changing temperature. Other potential causes of the faunal turnover include global changes in surface ocean productivity and changing bottom water source regions. Comparison of benthic and planktonic delta13C records requires no change in the ratio of oceanic phosphorous to carbon during the late Paleocene to early Eocene, which weakens the case for (but does not disprove) a change in surface ocean productivity at this time. Interbasinal comparisons of benthic foraminiferal delta13C records document that water with high delta13C values filled the Cape Basin during the late Paleocene and possibly the early Eocene (circa 61-57 Ma), but apparently did not extend into the western basins of the Atlantic. This pattern suggests a supply of Antarctic source water for the Cape Basin and possible tectonic isolation of the western Atlantic basins during at least part of the late Paleocene. Carbon isotope comparisons show that bottom water supply to the Cape Basin was reduced in the early Eocene. Eolian grain size data suggest that a decrease in zonal wind intensity occurred at the end of the Paleocene. These late Paleocene climatic changes (bottom water warming and decreased wind intensity) correspond with evidence for an important global tectonic reorganization and extensive subaerial volcanism, which may have contributed to climatic warming through increased supply of CO2.

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Six soft sediment cores, up to and over 9 m in length, and additional surface samples were selected for study of their planktonic foraminifera to provide information on the Holocene and Pleistocene stratigraphy of the West African continental margin south of the present boundary of the Sahara. The material was collected by the German research vessel "Meteor" during Cruise 25 in 1971. The residues larger than 160 microns determined, counted and statistically evaluated. Stratigraphical correlations with trans- Antlantic regions are given by occurrence of Truncorotalidoides hexagonus and Globorotalia tumidula flexuosa which mark the last interglacial stage. According to the climatic record the two deep-sea cores extend down to the V-zone, considered here as equivalent to the Mindel-Riss-interglacial time, as there are three distinctly warm and two cold periods indicated in the cores by planktonic foraminiferal faunas. Z-zone = Holocene is present in all cores, Y-zone = Wuermian glacial can be divided into five section, three cold and two warm stages; the X-zone can be divided into three warm stages, separated into two cool periods. The earliest warm stage is indicated to be the warmest one. There are excellent correlations to the Camp century ice core from Greenland, to the Mediterranean, to the Carribean and to the tropical Atlantic as well as to the Barnados stage. The W-zone was correlated to the Riss-glacial. V-zone is a warm period, the upper limit of which being not sufficiently defined, which contains also some cool sections. Increasing sedimentation rates from the deep-sea to the upper slope reveal climatic and regional details in Holocene and Late Pleistocene history of the continental margin. These were based mainly on different parameters of planktonic foraminiferal thanatocoenoses which are the main components of the size fraction >160 microns of the pelagic core. They become incerasingly diluted by other faunal and terrigenous components with decreasing slope depths. Estimates of absolute abundances, ranging from 25000 specimens/gm of sediment in the deep sea to less than 100, indicate various sedimentary processes at the continental margin. An ecological correlation by dominant species is possible. Readily computed temperature indices of different scales are presented which indicate, for instance, three distinctly cold sections within the last glacial and seven warm sections within the last interglacial lime. These are used for estimates of sedimentation rates. During cold periods sedimentation rates are higher than during warmer periods. Stratigraphic correlation and faunal record, combined with absolute abundances and sedimentation rates, indicated that in the deep sea turbidity currents not only cause high sedimentation rates for short periods of time, but also that material is occasionally eroded. Effects of upwelling may be detected in the surfacc sediment samples as well as in late Pleistocene and early Holocene samples of the slope by planktonic foraminiferal data which are not influenced by sedimentary processes.

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Benthic oxygen and carbon isotopic results from a depth transect on Maud Rise, Antarctica, provide the first evidence for Warm Saline Deep Water (WSDW) in the Paleogene oceans. Distinct reversals occur in the oxygen isotopic gradient between the shallower Hole 689B (Eocene depth ~1400 m; present-day depth 2080 m) and the deeper Hole 690B (Eocene depth ~2250 m; present-day depth 2914 m). The isotopic reversals, well developed by at least 46 Ma (middle middle Eocene), existed for much of the remaining Paleogene. We do not consider these reversals to be artifacts of differential diagenesis between the two sites or to have resulted from other potentially complicating factors. This being so, the results show that deep waters at Hole 690B were significantly warmer than deep waters at the shallower Hole 689B. A progressive decrease and eventual reversal in benthic to planktonic delta18O gradients in Hole 690B, demonstrate that the deeper waters became warmer relative to Antarctic surface waters during the Eocene. The warmer deep waters of the Paleogene are inferred to have been produced at middle to low latitudes, probably in the Tethyan region which contained extensive shallow-water platforms, ideal sites for the formation of high salinity water through evaporative processes. The ocean during the Eocene, and perhaps the Paleocene, is inferred to have been two-layered, consisting of warm, saline deep waters formed at low latitudes and overlain by cooler waters formed at high latitudes. This thermospheric ocean, dominated by halothermal circulation we name Proteus. The Neogene and modern psychrospheric ocean Oceanus is dominated by thermohaline circulation of deep waters largely formed at high latitudes. An intermediate condition existed during the Oligocene, with a three-layered ocean that consisted of cold, dense deep waters formed in the Antarctic (Proto-AABW), overlain by warm, saline deep waters from low latitudes, and in turn overlain by cool waters formed in the polar regions. This we name Proto-oceanus which combined both halothermal and thermohaline processes. The sequence of high latitude, major, climatic change inferred from the oxygen isotopic records is as follows: generally cooler earlier Paleocene; warming during the late Paleocene; climax of Cenozoic warmth during the early Eocene and continuing into the early middle Eocene; cooling mainly in a series of steps during the remainder of the Paleogene. Superimposed upon this Paleogene pattern, the Paleocene/Eocene boundary is marked by a brief but distinct warming that involved deep to surface waters and a reduction in surface to deep carbon and oxygen isotopic gradients. This event coincided with major extinctions among the deep-sea benthic foraminifers as shown by Thomas (1990 doi:10.2973/odp.proc.sr.113.123.1990). Salinity has played a major role in deep ocean circulation, and thus paleotemperatures cannot be inferred directly from the oxygen isotopic composition of Paleogene benthic foraminifers without first accounting for the salinity effect.

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Stable Cl isotope ratios, measured in marine pore waters associated with the Barbados and Nankai subduction zones, extend significantly (to ~-8 per mil) the range of d37Cl values reported for natural waters. These relatively large negative values, together with geologic and chemical evidence from Barbados and Nankai and recent laboratory data showing that hydrous silicate minerals (i.e., those with structural OH sites) are enriched up to 7.5 per mil in 37Cl relative to seawater, strongly suggest that the isotopic composition of Cl in pore waters from subduction zones reflects diagenetic and metamorphic dehydration and transformation reactions. These reactions involve clays and/or other hydrous silicate phases at depth in the fluid source regions. Chlorine therefore cannot be considered geochemically conservative in these systems. The uptake of Cl by hydrous phases provides a mechanism by which Cl can be cycled into the mantle through subduction zones. Thus, stable Cl isotopes should help in determining the extent to which Cl and companion excess volatiles like H2O and CO2 cycle between the crust and mantle.