B/Ca ratios in planktonic foraminifera

Boron isotope systematics indicate that boron incorporation into foraminiferal CaCO3 is determined by the partition coefficient, KD = [B/Ca](CaCO3)/[B(OH)4**-/HCO3**-](seawater), and [B(OH)4?/HCO3?](seawater), providing, in principle, a method to estimate seawater pH and PCO2. We have measured B/Ca ratios in Globigerina bulloides and Globorotaliainflata for a series of core tops from the North Atlantic and the Southern Ocean and in Globigerinoides ruber (white) from Ocean Drilling Program (ODP) site 668B on the Sierra Leone Rise in the eastern equatorial Atlantic. B/Ca ratios in these species of planktonic foraminifera seem unaffected by dissolution on the seafloor. KD shows a strong species-specific dependence on calcification temperature, which can be corrected for using the Mg/Ca temperature proxy. A preliminary study of G. inflata from Southern Ocean sediment core CHAT 16K suggests that temperature-corrected B/Ca was ~30% higher during the last glacial. Correspondingly, pH was 0.15 units higher and aqueous PCO2 was 95 ?atm lower at this site at the Last Glacial Maximum. The covariation between reconstructed PCO2 and the atmospheric pCO2 from the Vostok ice core demonstrates the feasibility of using B/Ca in planktonic foraminifera for reconstructing past variations in pH and PCO2.

Carbonate fraction, magnesium and strontium concentration, oxygen and carbon isotopes at DSDP Hole 92-600C

Strontium, magnesium, oxygen, and carbon isotope profiles of the carbonate fraction of Hole 600C sediments support the lithologic and petrographic observations of extensive CaCO3 dissolution and recrystallization in the Pliocene basal section. Convective fluid flow through the sediments during the first 1 to 1.5 m.y. of the sedimentary history of these sediments may explain these observations.

Geochemistry of phosphate and glauconites of ODP Leg 128 samples

Glauconites and phosphates have been detected in almost all investigated samples at Sites 798 (uppermost Miocene or lower Pliocene to Pleistocene) and 799 (early middle Miocene to Pleistocene). Autochthonous occurrences appear in very minor quantities (generally below 0.2%) throughout the drilled sequences, whereas allochthonous accumulations are limited to the lower Pliocene or uppermost Miocene sequence at Site 798 (glauconites) and to the upper and middle Miocene sequence at Site 799 (upper and middle Miocene: glauconites; middle Miocene: phosphates). X-ray fluorescence, microprobe, and bulk chemical analyses indicate high variabilities in cations and anions and generally low oxide totals. This is probably related to the substitution of phosphate and fluoride aniors by hydroxide and carbonate anions in phosphates and to the depletion of iron, aluminum, and potassium cations and the enrichment in hydroxide and crystal water in glauconites. Gradients in pore-water contents of dissolved phosphate and fluoride at Sites 798 and 799 suggest a depth of phosphate precipitation between 30 and 50 mbsf, with fluoride as the limiting element for phosphate precipitation at Site 798. Phosphate and fluoride appear to be balanced at Site 799. Crude extrapolations indicate that the Japan-Sea sediments may have taken up approximately 7.2*10**10 g P total/yr during the Neogene and Pleistocene. This amount corresponds to approximately 0.3% of the estimated present-day global transfer of phosphorus into the sediments and suggests that the Japan Sea constitutes an average sink for this element. The two main carriers of phosphorus into the present Japan Sea are the Tshushima and the Liman currents, importing approximately 6.6*10**10 g P and 5.7*10**10 g P per year, respectively. Bulk chemical analyses suggest that at least 36% of P total in the sediments is organically bound phosphorus. This rather high value, which corresponds to the measured Japan-Sea deep-water P organic/P total ratios, probably reflects rapid transport of organic phosphorus into the depth of the Japan Sea.

Geochemsitry of minerals and glass shards at DSDP Leg 67 Holes

During Leg 67, the Middle-America Trench transect off Guatemala was drilled across the convergent margin of southern Mexico and Central America south of the Tehuantepec Ridge. The data of Leg 66, north of the Tehuantepec Ridge, and that of Leg 67 provided the opportunity to establish a continuous chronology of airborne volcanic ashes intercalated within the sediments (Aubouin et al., 1979; von Huene et al., 1980). Sites of both expeditions are favorably located for obtaining a good record of the explosive volcanicity of these areas, given the proximity of the volcanic sources and the position of the sites under the prevailing winds.

Magnesium/calcium ratio of the foraminifera Oridorsalis umbonatus in surface sediment samples off Namibia

A laser ablation system connected to an inductively coupled plasma mass spectrometer was used to determine Mg/Ca ratios of the benthic foraminifera Oridorsalis umbonatus. A set of modern core top samples collected along a depth transect on the continental slope off Namibia (320-2300 m water depth; 2.9° to 10.4°C) was used to calibrate the Mg/Ca ratio against bottom water temperature. The resulting Mg/Ca-bottom water temperature relationship of O. umbonatus is described by the exponential equation Mg/Ca = 1.528*e**0.09*BWT. The temperature sensitivity of this equation is similar to previously published calibrations based on Cibicidoides species, suggesting that the Mg/Ca ratio of O. umbonatus is a valuable proxy for thermocline and deep water temperature.

Minerals and geochemistry abundance and occurance, as well as K-Ar determinations for DSDP Site 92-597 basalts

Preliminary studies of hydrothermally altered massive basalts formed at the fast-spreading Mendoza Rise and recovered from DSDP Holes 597B and 597C indicate the presence of three secondary mineral assemblages which formed in the following order: (1) trioctahedral chlorite and talc, (2) goethite and smectite, and (3) calcite and celadonite. The sequential precipitation of these mineral assemblages denotes high water:rock ratios and time-varying conditions of temperature (early >200°C to late <30°C) and state of oxidation (early nonoxidative to late oxidative). A decrease in the relative proportion of oxidative mineral assemblages with depth to 70 m in Site 597 basement indicates a zone of oxidative alteration that became shallower with time as the deeper, more constricted fracture systems were filled by secondary mineralization. In this report we present the first results of the K-Ar dating of celadonite formation age; celadonite formation reflects end-stage hydrothermal alteration in Site 597 basement. Three celadonite dates obtained from Site 597 samples include 13.1 ± 0.3 m.y. from 17 m basement depth (Hole 597B), 19.9 ± 0.4 m.y. from 18 m basement depth (Hole 597C), and 19.3 ± 1.6 m.y. from 60 m basement depth (Hole 597C). The age of host rock crystallization (28.6 m.y.) and the K-Ar dates of celadonite formation establish that hydrothermal alteration in the upper 70 m of Site 597 basement continued for at least 10 m.y. and possibly as long as 16 m.y. after basalt crystallization at the ridge crest. Assuming a half-spreading rate of 55 km/m.y., we calculate that hydrothermal circulation was active in shallow basement at a distance of at least 550 km off ridge crest and possibly as far as 1000 km off ridge crest.

Geochemistry and minerals of glass shards at DSDP Leg 66 Holes

Deep Sea Drilling Project Leg 66 drilled eight sites along a transect across the Middle America Trench off Mexico, including continental (Sites 493 and 489), oceanic (Site 487), and trench (Site 486) reference sites and four sites (490, 492, 491, 488) in the trench inner wall. Because of their location - close to volcanic sources and subject to prevailing winds and marine currents (N to S, NW to SE) - analysis of airborne ashes intercalated within the sediments at these sites provides a reliable record of explosive volcanism in the area. Intense onshore volcanic activity in Mexico during the Oligo-Miocene has been well documented by the andesites and ignimbrites of the Sierra Madre Occidental and Sierra Madre del Sur and in the Plio-Quaternary by the andesites and basalts from the Trans-Mexican Neovolcanic Belt and the eastern border of Baja California.

Heavy metal concentrations in fauna from hydrothermal fields of the Mid-Atlantic Ridge

Distributions of Fe, Mn, Zn, Cu, Ni, Co, Cr, Pb, As, Ag, Cd, Se, Sb, and Hg in 128 samples of tissues of organisms that inhabit hydrothermal vent fields of the Mid-Atlantic Ridge (Menez Gwen, Snake Pit, and Rainbow) depending on the abiotic environmental parameters were studied. The majority of the elements studied showed direct correlations between their concentrations in fluids released and in tissues of hydrothermal organisms. A higher degree of bioaccumulation of metals was revealed in Bathymodiolus mussels and Rimicaris shrimps from the Rainbow hydrothermal vent field as compared to their analogues from the Menez Gwen and Snake Pit fields. This corresponds to maximal concentrations of the majority of the metals studied in the Rainbow high-temperature hydrothermal fluids. The highest degree of bioaccumulation of heavy metals was found in gills of symbiotrophic mussels Bathymodiolus and in maxillipeds of ectosymbiotic shrimps Rimicaris, i.e., in organs that function in dependence on chemosynthetic bacteria. Within the Rainbow vent field, the shrimps, which inhabit in biotopes with more high-temperature conditions and therefore are more strongly subjected to influence of fluids, were found to contain higher metal contents than mollusks. Fe-Mn hydroxide films that cover mussel shells might serve as important reservoirs of other metals related to Fe and Mn.

Magnesium isotope ratios of pore-fluids and dolomites

Magnesium concentrations in deep-sea sediment pore-fluids typically decrease down core due to net precipitation of dolomite or clay minerals in the sediments or underlying crust. To better characterize and differentiate these processes, we have measured magnesium isotopes in pore-fluids and sediment samples from Ocean Drilling Program sites (1082, 1086, 1012, 984, 1219, and 925) that span a range of oceanographic settings. At all sites, magnesium concentrations decrease with depth. At sites where diagenetic reactions are dominated by the respiration of organic carbon, pore-fluid d26Mg values increase with depth by as much as 2 per mil. Because carbonates preferentially incorporate 24Mg (low d26Mg), the increase in pore-fluid d26Mg values at these sites is consistent with the removal of magnesium in Mg-carbonate (dolomite). In contrast, at sites where the respiration of organic carbon is not important and/or weatherable minerals are abundant, pore-fluid d26Mg values decrease with depth by up to 2 per mil. The decline in pore-fluid d26Mg at these sites is consistent with a magnesium sink that is isotopically enriched relative to the pore-fluid. The identity of this enriched magnesium sink is likely clay minerals. Using a simple 1D diffusion-advection-reaction model of pore-fluid magnesium, we estimate rates of net magnesium uptake/removal and associated net magnesium isotope fractionation factors for sources and sinks at all sites. Independent estimates of magnesium isotope fractionation during dolomite precipitation from measured d26Mg values of dolomite samples from sites 1082 and 1012 are very similar to modeled net fractionation factors at these sites, suggesting that local exchange of magnesium between sediment and pore-fluid at these sites can be neglected. Our results indicate that the magnesium incorporated in dolomite is 2.0-2.7 per mil depleted in d26Mg relative to the precipitating fluid. Assuming local exchange of magnesium is minor at the rest of the studied sites, our results suggest that magnesium incorporated into clay minerals is enriched in d26Mg by 0 per mil to +1.25 per mil relative to the precipitating fluid. This work demonstrates the utility of magnesium isotopes as a tracer for magnesium sources/sinks in low-temperature aqueous systems.