Geochemistry of carbonate cements of ODP Leg 112 samples

The evolution of pore fluids migrating through the forearc basins, continental massif, and accretionary prism of the Peru margin is recorded in the sequence of carbonate cements filling intergranular and fracture porosities. Petrographic, mineralogic, and isotopic analyses were obtained from cemented clastic sediments and tectonic breccias recovered during Leg 112 drilling. Microbial decomposition of the organic-rich upwelling facies occurs during early marine diagenesis, initially by sulfate-reduction mechanisms in the shallow subsurface, succeeded by carbonate reduction at depth. Microcrystalline, authigenic cements formed in the sulfate-reduction zone are 13C-depleted (to -20.1 per mil PDB), and those formed in the carbonate-reduction zone are 13C-enriched (to +19.0 per mil PDB). Calcium-rich dolomites and near-stoichiometric dolomites having uniformly heavy d18O values (+2.7 to +6.6 per mil PDB) are typical organic decomposition products. Quaternary marine dolomites from continental-shelf environments exhibit the strongest sulfate-reduction signatures, suggesting that Pleistocene sea-level fluctuations created a more oxygenated water column, caused periodic winnowing of the sediment floor, and expanded the subsurface penetration of marine sulfate. We have tentatively identified four exotic cement types precipitated from advected fluids and derived from the following diagenetic environments: (1) meteoric recharge, (2) basalt alteration, (3) seafloor venting and (4) hypersaline concentration. Coarsely crystalline, low-magnesium (Lo-Mg) calcite cements having pendant and blocky-spar morphologies, extremely negative d18O values (to -7.5 per mil PDB), and intermediate d13C values (-0.4 per mil to +4.6 per mil PDB) are found in shallow-marine Eocene strata. These cements are evidently products of meteoric diagenesis following subaerial emergence during late Eocene orogenic movements, although the strata have since subsided to greater than 4,000 m below sea level. Lo-Mg calcite cements filling scaly fabrics in the late Miocene accretionary prism sediments are apparently derived from fluids having lowered magnesium/calcium (Mg/Ca) and 18O/16O ratios; such fluids may have reacted with the subducting oceanic crust and ascended through the forearc along shallow-dipping thrust faults. Micritic, high-magnesium (Hi-Mg) calcite cements having extremely depleted d13C values (to -37.3%c PDB), and a benthic fauna of giant clams (Calyptogena sp.) supported by a symbiotic, chemoautotrophic metabolism, provide evidence for venting of methane-charged waters at the seafloor. Enriched d18O values (to +6.6%c PDB) in micritic dolomites from the continental shelf may be derived from hypersaline fluids that were concentrated in restricted lagoons behind an outer-shelf basement ridge, reactivated during late Miocene orogenesis.

Isotopic and micropaleontological record of sediments of the Baffin Bay

The oxygen and carbon isotopic compositions of the planktonic foraminifer, Neogloboquadrina pachyderma (sinistral), were determined at 20-cm intervals through the 'composite' top ~ 22 m of sediments at ODP Site 645 (Holes 645B, 645C, 645F, and 645G) and at 10-cm intervals through a 9-m piston core (85-027-016) collected during the Hudson site survey. Quantitative analyses of palynomorphs, notably dinocysts, and of planktonic foraminifers were performed. Organic and nitrogen contents and isotopic composition of nitrogen and carbon in organic matter also were determined. These data provide a high-resolution record of changes that occurred in surface-water masses during the last glacial cycle in Baffin Bay. The basin experienced low planktonic productivity during most of the late Pleistocene, either from dilution in surface water by meltwater discharges from the surrounding ice-sheet or from the presence of a relatively dense sea-ice cover. Peaks of meltwater discharge are indicated by d18O values as low as about 1.5 per mil, correlative d13C- d18O shifts, low concentration of planktonic foraminifers, high concentrations of glacially reworked pre-Quaternary palynomorphs, and low-salinity dinocyst assemblages. As a whole, d18O values ranging between 4.5 and 2.5 per mil allow the establishment of an 18O stratigraphy spanning isotopic stages 5 to 1. Because of the poor core recovery, the general paucity of microflora and microfauna, and the possible occurrence of slumping or debris flow at Site 645, further interpretation remains problematic.

Chemical and isotopic composition of interstitial waters and hydrocarbon composition at ODP Site 184-1146

Bottom-simulating reflectors were observed beneath the southeastern slope of the Dongsha Islands in the South China Sea, raising the potential for the presence of gas hydrate in the area. We have analyzed the chemical and isotopic compositions of interstitial water, headspace gas, and authigenic siderite concretions from Site 1146. Geochemical anomalies, including a slight decrease of chlorine concentration in interstitial water, substantial increase of methane concentration in headspace gas, and 18O enrichment in the authigenic siderite concretion below 400 meters below seafloor are probably caused by the decomposition of gas hydrate. The low-chlorine pore fluids contain higher molecular-weight hydrocarbons and probably migrate to Site 1146 along faults or bedded planes.

Oxygen and carbon isotopes from foraminifers and benthic foraminiferal abundance at DSDP Holes 71-511 and 71-512

An Eocene-Oligocene oxygen and carbon isotope history based on planktonic and benthic foraminifers from Deep Sea Drilling Project Leg 71 cores has been constructed for the Maurice Ewing Bank of the eastern Falkland Plateau, Southwest Atlantic Ocean. Specifically, the cores cover portions of the middle Eocene, upper Eocene, and lower Oligocene. Surface water isotopic temperatures postulated for the middle Eocene at Site 512 fluctuated within about four degrees but generally averaged about 9°C. Bottom isotopic temperatures at Site 512 (water depth, 1846 m) were generally a degree lower than surface water temperatures. Surface water isotopic temperatures at Site 511 initially averaged about 11°C during the late Eocene, but dropped to an average of 7°C in the early Oligocene. Bottom isotopic temperatures at Site 511 (water depth, 2589 m) generally record temperatures between 12.5°C and 8°C, similar to the range in the surface water isotopic temperatures. During the early Oligocene, bottom isotopic temperatures dropped sharply and averaged about 2°C (very close to present-day values). Surface water temperature values also decreased to an average of about 7°C, therefore leading to a significant divergence between surface and bottom water isotopic temperatures during the early Oligocene. Comparisons among Southern Ocean DSDP Sites 511, 512, and 277, and between these and other DSDP sites from central and northern latitudes (Sites 44, 167, 171, 292, 357, 398, 119, and 401) show that much of the Eocene was characterized by relatively warm temperatures until sometime in either the middle Eocene, late Eocene, or early Oligocene. At each site, conspicuous 18O enrichments occur in both the benthic and planktonic foraminifers over a relatively short period of time. Although a general trend toward a climatic deterioration is evident, the density of data points among the various studies is still too sparse to determine either synchrony or time-transgression between the major isotopic events. A close correlation could be made between the Site 511 oxygen isotope temperature curve and paleoclimatic trends derived independently from radiolarian studies. The sharp temperature drop and the divergence between bottom and surface water temperatures during the early Oligocene apparently reflect a major expansion of the antarctic water mass. The migration of the boundary between the subantarctic and antarctic water masses over the site at this time would account in part for the sharp temperature changes. Sharp changes of this nature would not necessarily be noted in other geographic areas, particularly those to the north which have different oceanographic regimes.

Stable carbon and oxygen isotope ratios across the Cretaceous/Tertiary boundray on the Walvish Ridge

The isotopic composition and diversity of nannofossils were studied in cores from the Deep Sea Drilling Project (DSDP) Sites 525A, 527, 528, and 529 from the Walvis Ridge, South Atlantic to better understand the changes which occurred across the Cretaceous/Tertiary boundary (K/T boundary). The stratigraphic range of the samples is from the Arkhangelskiella cymbiformis Zone in the Maastrichtian to the Heliolithus kleinpelli Zone in the Danian. Nannofossil diversity was high (Shannon-Weaver diversity index, 'H= 2.5-3) in the late Cretaceous, but decreased sharply (H c. 1 ) across the K/T boundary. The delta13C values also decrease across the K/T boundary at the four sites, suggesting a reduction in surface productivity in the South Atlantic concomitant with the reduction in diversity. During the Danian, nannofossil diversity and delta13C show some recovery approximately 500-700 k.y. after the boundary event. However, not until 2.5 Ma after the boundary event did diversity become constant. Diversity values similar to those for the late Cretaceous were not attained again in the early Paleocene interval studied. Carbon isotopic compositions similar to those from the Cretaceous were not attained until 4.5 Ma after the K/T event.

Lithium concentrations and isotope composition of basalt samples from ODP/DSDP Sites from Costa Rica Rift

Ocean Drilling Program (ODP) Hole 504B near the Costa Rica Rift is the deepest hole drilled in the ocean crust, penetrating a volcanic section, a transition zone and a sheeted dike complex. The distribution of Li and its isotopes through this 1.8-km section of oceanic crust reflects the varying conditions of seawater alteration with depth. The upper volcanic rocks, altered at low temperatures, are enriched in Li (5.6-27.3 ppm) and have heavier isotopic compositions (delta7Li=6.6-20.8?) relative to fresh mid-ocean ridge basalt (MORB) due to uptake of seawater Li into alteration clays. The Li content and isotopic compositions of the deeper volcanic rocks are similar to MORB, reflecting restricted seawater circulation in this section. The transition zone is a region of mixing of seawater with upwelling hydrothermal fluids and sulfide mineralization. Li enrichment in this zone is accompanied by relatively light isotopic compositions (-0.8-2.1?) which signify influence of basalt-derived Li during mineralization and alteration. Li decreases with depth to 0.6 ppm in the sheeted dike complex as a result of increasing hydrothermal extraction in the high-temperature reaction zone. Rocks in the dike complex have variable isotopic values that range from -1.7 to 7.9?, depending on the extent of hydrothermal recrystallization and off-axis low-temperature alteration. Hydrothermally altered rocks are isotopically light because 6Li is preferentially retained in greenschist and amphibolite facies minerals. The delta7Li values of the highly altered rocks of the dike complex are complementary to those of high-temperature mid-ocean ridge vent fluids and compatible to equilibrium control by the alteration mineral assemblage. The inventory of Li in basement rocks permits a reevaluation of the role of oceanic crust in the budget of Li in the ocean. On balance, the upper 1.8 km of oceanic crusts remains a sink for oceanic Li. The observations at 504B and an estimated flux from the underlying 0.5 km of gabbro suggest that the global hydrothermal flux is at most 8*10**9 mol/yr, compatible with geophysical thermal models. This work defines the distribution of Li and its isotopes in the upper ocean crust and provides a basis to interpret the contribution of subducted lithosphere to arc magmas and cycling of crustal material in the deep mantle.

Chemical and isotopical analsyes of DSDP Hole 34-321 basalts

A blue-green smectite (iron-rich saponite) and green mica (celadonite) are the dominant sheet silicates in veins within the 10.5 m of basalt cored during DSDP Leg 34, Site 32l, in the Nazca plate. Oxygen isotopic analyses of these clays, and associated calcite, indicate a formation temperature of <25°C. Celadonite contains appreciable Fe2O3, K2O and SiO2, intermediate MgO, and very little Al2O3. Celadonite is commonly associated with goethite and hematite, which suggests that this phase formed by precipitation within a dominantly oxygenated environment of components leached from basalt and provided by seawater. A mass balance estimate indicates that celadonite formation can remove no more than 15% of the K annually transported to the oceans by rivers. In contrast, iron-rich saponite containing significant Al2O3 appears to have precipitated from a nonoxidizing, distinctly alkaline fluid containing a high Na/K ratio relative to unmodified seawater. Seawater-basalt interaction at low temperatures, resulting in the formation of celadonite and smectite may explain chemical gradients observed in interstitial waters of sediments overlying basalts.

Hydrogen and oxygen stable isotope analyses of precipitation sampled at Erlangen (southern Germany) between 2010 and 2013

Shallow groundwater aquifers are often influenced by anthropogenic contaminants or increased nutrient levels. In contrast, deeper aquifers hold potentially pristine paleo-waters that are not influenced by modern recharge. They thus represent important water resources, but their recharge history is often unknown. In this study groundwater from two aquifers in southern Germany were analyzed for their hydrogen and oxygen stable isotope compositions. One sampling campaign targeted the upper aquifer that is actively recharged by modern precipitation, whereas the second campaign sampled the confined, deep Benkersandstein aquifer. The groundwater samples from both aquifers were compared to the local meteoric water line to investigate sources and conditions of groundwater recharge. In addition, the deep groundwater was dated by tritium and radiocarbon analyses. Stable and radiogenic isotope data indicate that the deep-aquifer groundwater was not part of the hydrological water cycle in the recent human history. The results show that the groundwater is older than ~20,000 years and most likely originates from isotopically depleted melt waters of the Pleistocene ice age. Today, the use of this aquifer is strictly regulated to preserve the pristine water. Clear identification of such non-renewable paleo-waters by means of isotope geochemistry will help local water authorities to enact and justify measures for conservation of these valuable resources for future generations in the context of a sustainable water management.

Carbon chemistry of oceanic crust

Carbonate mineral precipitation in the upper oceanic crust during low-temperature, off-axis, hydrothermal circulation is investigated using new estimates of the bulk CO2 content of seven DSDP/ODP drill cores. In combination with previously published data these new data show: (i) the CO2 content of the upper ~ 300 m of the crust is substantially higher in Cretaceous than in Cenozoic crust and (ii) for any age of crust, there is substantially more CO2 in Atlantic (slow-spreading) than Pacific (intermediate- to fast-spreading) crust. Modelling the Sr-isotopic composition of the carbonates suggests that > 80% of carbonate mineral formation occurs within < 20 Myr of crust formation. This means that the higher CO2 content of Cretaceous crust reflects a secular change in the rate of CO2 uptake by the crust. Oxygen isotope derived estimates of carbonate mineral precipitation temperatures show that the average and minimum temperature of carbonate precipitation was ~10 °C higher temperatures in the Cretaceous than in the Cenozoic. This difference is consistent with previous estimates of secular change in bottom seawater temperature. Higher fluid temperature within the crust will have increased reaction rates potentially liberating more basaltic Ca and hence enhancing carbonate mineral precipitation. Additionally, if crustal fluid pH is controlled by fluid-rock reaction, the higher Ca content of the Cretaceous ocean will also have enhanced carbonate mineral precipitation. New estimates of the rate of CO2 uptake by the upper ocean crust during the Cenozoic are much lower than previous estimates.

Elemental and stable isotopic composition of some metalliferous and pelagic sediments at DSDP Leg 70 Holes

Nontronite, the main metalliferous phase of the Galapagos mounds, occurs at subsurface depths of about 2 to 20 meters; Mn-oxide material is limited to the upper 2 meters of the mounds. The nontronite forms intervals of up to a few meters' thickness, consisting essentially of 100% nontronite granules, which alternate with intervals of normal pelagic sediment. Electron microprobe analyses of nontronite granules from different core samples indicate that: (1) there is little difference in major element composition between nontronites from varying locations within the mounds, with adjacent granules from a given sample having very similar compositions; (2) individual granules show little internal variation in composition. This indicates that the granules are composed of a single mineral of essentially constant composition, consistent with relatively uniform conditions of Eh and composition during nontronite formation. Mn-oxide crusts have very low Fe contents, a feature characteristic of rapidly deposited Mn-oxide crusts formed under hydrothermal influences. The rare-earth element (REE) abundances of the nontronites are generally extremely low, totalling less than several ppm. Two samples have the negatively Ce anomaly typical of authigenic precipitates formed relatively rapidly from seawater. A Mn-oxide crust sample has low REE contents, typical of Mn-oxide crusts formed under hydrothermal influences, but no negative Ce anomaly. A sample of unusual Mn-Fe-oxide mud has relatively high REE concentrations and a seawater-type pattern; both of these features are also found for metalliferous sediments from the East Pacific Rise. The oxygen and hydrogen isotopic composition of the nontronites define a restricted field within a d18O-dD plot. In manganiferous sediments, d18O and dD appear to decrease with increase in the Mn-oxide content of the sediment. From the d18O values of the nontronites, formation temperatures in the range of about 20-30°C have been estimated. By comparison, temperatures of up to 11.5 °C at a 9-meter depth have been directly measured within the mounds (Corliss et al., 1979), and heat-flow data suggest present basement/sediment interface temperatures of 15-25°C. In a plot of Fe + Mn vs. d18O, the Mn-oxide crust and Mn-Fe-ooze plot near the tie-lines for authigenic Mn nodules and silicate phases, implying that they have formed in isotopic equilibrium with seawater at or close to bottom-water temperatures.

Metamorphic processes in sediments at DSDP Leg 65 Holes

Sites 482, 483, and 485 were drilled during Leg 65 on young oceanic crust south of the Tamayo Transform Fault. The Leg 65 drilling program was part of a multinational effort to study the East Pacific Rise (EPR) and complements sea bottom surveys conducted both in this area (Lewis, 1979; Cyamex Scientific Team and Pastouret, 1981) and farther south at 21 °N (Larson, 1971; Normark, 1976; Cyamex Scientific Team; Rise Project Group, 1980). These studies, which included deep-tow, Angus and submersible surveys, were recently complemented by sea-beam surveys conducted by the Jean Charcot on the Tamayo Fracture Zone and farther south along the EPR. They have led to a better understanding of the magmatic, tectonic, and sedimentary processes occurring on the East Pacific Rise between the Tamayo and Rivera fracture zones. The purpose of this chapter is to describe the metamorphic processes affecting Pliocene through Quaternary sediments found in contact, or inter layered, with basaltic units drilled during Leg 65 at the mouth of the Gulf of California.

Oxygen and carbon isotope stratigraphy of ODP Holes 107-653A and 107-654A

Stable isotope analysis of two species (or groups of species) of planktonic foraminifers: Globigerinoides ruber (or G. obliquus and G. obliquus extremus) and Globigerina bulloides (or G. falconensis and G. obesa) from ODP Hole 653A and Site 654 in the Tyrrhenian basin, records the Pliocene-Pleistocene glacial history of the Northern Hemisphere. The overall increase in mean d18O values through the interval 4.6-0.08 Ma is 1.7 per mil for G. bulloides and 1.5 per mil for G. ruber. The time interval 3.1-2.5 Ma corresponds to an important phase of 18O enrichment for planktonic foraminifers. In this interval, glacial d18O values of both species G. bulloides and G. ruber increase by about l per mil, this increase being more progressive for G. ruber than for G. bulloides. The increase of interglacial d18O values is higher for G. bulloides (1.5 per mil) than for the Gruber group (1 per mil). These data suggest a more pronounced seasonal stratification of the water masses during interglacial phases. Large positive d18O fluctuations of increasing magnitude are also recorded at 2.25 and 2.15 Ma by G bulloides and appear to be diachronous with those of Site 606 in the Atlantic Ocean. Other events of increasing d18O values are recorded between 1.55 and 1.3 Ma, at 0.9 Ma, 0.8 Ma, and near 0.34 Ma. In the early Pliocene the d18O variability recorded by the planktonic species G. bulloides was higher in the Mediterranean than in the Atlantic at the same latitude. This suggests that important cyclic variations in the water budget of the Mediterranean occurred since that time. Step increases in the d18O variability are synchronous with those of the open ocean at 0.9 and 0.34 Ma. The higher variability as well as the higher amplitude of the peaks of 18O enrichment may be partly accounted for by increase of dryness over the Mediterranean area. In particular the high amplitude d18O fluctuations recorded between 3.1 and 2.1 Ma are correlated with the onset of a marked seasonal contrast and a summer dryness, revealed by pollen analyses. Strong fluctuations towards d13C values higher than modern ones are recorded by the G. ruber group species before 1.7 Ma and suggest a high production of phytoplankton. When such episodes of high primary production are correlated with episodes of decreasing 13C content of G. bulloides, they are interpreted as the consequence of a higher stratification of the upper water masses resulting itself from a marked seasonality. Such episodes occur between 4.6 and 4.05 Ma, 3.9 and 3.6 Ma, and 3.25 and 2.66 Ma. The interval 2.66-1.65 Ma corresponds to a weakening of the stratification of the upper water layers. This may be related to episodes of cooling and increasing dryness induced by the Northern Hemisphere Glaciations. The Pleistocene may have been a less productive period. The transition from highly productive to less productive surface waters also coincides with a new step increase in dryness and cooling, between 1.5 and 1.3 Ma. The comparison of the 13C records of G ruber and G. bulloides in fact suggests that a high vertical convection became a dominant feature after 2.6 Ma. Increases in the nutrient input and the stratification of the upper water masses may be suspected, however, during short episodes near 0.86 Ma (isotopic stage 25), 0.57-0.59 Ma (isotopic stage 16), 0.49 Ma (isotopic stage 13), 0.4-0.43 Ma (isotopic stage 11), and 0.22 and 0.26 Ma (part of isotopic stage 7 and transition 7/8). In fact, changes in the C02 balance within the different water masses of the Tyrrhenian basin as well as in the local primary production did not follow the general patterns of the open ocean.

Oxygen, carbon and strontium isotope data for DSDP Hole 35-323

A downhole decrease in 18O, Mg(2+) and K+, an increase in Ca(2+) and a low 87Sr/86Sr ratio of 0.7067 in the pore fluids of DSDP site 323 were caused principally by the alteration of volcanic material. These chemical and isotopic patterns were produced by the alteration, in order of decreasing importance of: a 60-m thick basal layer of volcanic ash; the underlying basalts; and igneous components in the 640-m thick upper sequence composed largely of terrigenous material. A significant portion of the alteration of the ash in the basal sequence must have occurred before the deposition of the upper sediments, perhaps under the influence of advecting solutions. The rest of the alteration occurred during the deposition of the thick upper sediments. Mass balance considerations and the low d18O values of most of the alteration products suggest that much of the later alteration occurred progressively over the last 13 Myr. The principal alteration products were smectite, potassium feldspar, clinoptilolite and calcite.