Sulphur isotope analyses in the southern ocean and the central Dronning Maud Land, East Antarctica

Sulphur isotope analyses are an important tool for the study of the natural sulphur cycle. On the northern hemisphere such studies of the atmospheric part of the cycle are practically impossible due to the high emission rate of anthropogenic sulphur. Merely in remote areas of the world such as the Antarctic 34S analyses can be used to identify the various sulphur sources (sea spray, biogenic und volcanic sources). We report here results of 34S measurements on sulphates from recent atmospheric precipitations (snow), lake waters, and salt efflorescences sampled in the Schirmacher Oasis and the Gruber Mountains, central Dronning Maud Land, East Antarctica. By plotting the delta 34S of precipitation versus % sea-spray sulphate the isotopic composition of the excess sulphate (which is probably of marine-biogenic origin) is extrapolated to be +4 per mil. Lake water sulphate and atmospheric precipitations have a comparable sulphur isotope composition (about +5 per mil). The analyzed secondary sulphates from the salt efflorescences, mainly gypsum and a few water-soluble sulphatcs (hexahydrite, epsomite, burkeite. and pickeringite), vary in their isotopic composition between about -12 and +8 per mil. This wide scatter is probably due to chemical weathering of primary sulphides having different delta 34S values in the substratum.

(Table 1) 87Sr/86Sr and Sr/Ca ratios in foraminiferal calcite from DSDP Holes 3-21 and 39-357

The 87Sr/86Sr ratio of ancient seawater, as recorded in marine carbonates, is an important tracer of long-term variations in ocean chemistry (Burke et al., 1982, doi:10.1130/0091-7613(1982)10<516:VOSSTP>2.0.CO;2; Peterman et al., 1970, doi:10.1016/0016-7037(70)90154-7; Dasch and Biscaye, 1971, doi:10.1016/0012-821X(71)90164-6; Veizer and Compston, 1974, doi:10.1016/0016-7037(74)90099-4; Brass, 1976, doi:10.1016/0016-7037(76)90025-9). However, the Sr isotope balance of the oceans has been difficult to constrain; consequently, attempts to evaluate the temporal 87Sr/86Sr changes have been largely qualitative. To constrain the causes of these variations we have measured 87Sr/86Sr ratios in carefully cleaned unrecrystallized foraminifera from DSDP sites 21 and 357. The data presented here have been quantitatively modelled taking advantage of recent advances in understanding of the Sr geochemical cycle. They suggest that whereas hydrothermal fluxes and carbonate recycling are of major importance in defining the marine 87Sr/86Sr ratio, the major control over its variations through the Cenozoic has been changes in the isotope composition of Sr derived from the weathering of silicate rocks.

Elemental data for composites from DSDP Sites 417A, 417D, and 418A

While the input of river-alkalinity into seawater is relatively well known, the complementary acidity production is poorly understood. Using the major-element budget of seafloor alteration of the upper 500 m of 120-Ma-old oceanic crust at DSDP/ODP Sites 417A, 417D and 418A in the central western Atlantic, we estimate the acidity flux associated with the low-temperature weathering of the upper oceanic crust. The acidity flux is calculated based on major-element fluxes and charge-balance considerations. The relevant chemical fluxes from seawater to the upper crust are 4.1+-0.1; 1.4+-1.4; 2.2+-0.6 and -12+-2 10**11 mol/yr for K, Mg, Na and silicate-Ca, respectively. The associated acidity flux is (3.5+-3)10**11 eq/y. Relative to continental weathering, these fluxes are significant for K and silicate-Ca, but are minor for Na, Mg and acidity. Thus, riverine fluxes of alkalinity are not significantly balanced by acidity fluxes from low-temperature upper ocean crust alteration.

Microbialites and lipid biomarker from coral reefs off the volcanic islands Tahiti and Vanuatu and from the nonvolcanic sites Belize and the Maldives

The occurrence of microbialites in post-glacial coral reefs has been interpreted to reflect an ecosystem response to environmental change. The greater thickness of microbialites in reefs with a volcanic hinterland compared to thinner microbial crusts in reefs with a non-volcanic hinterland led to the suggestion that fertilization of the reefal environment by chemical weathering of volcanic rocks stimulated primary productivity and microbialite formation. Using a molecular and isotopic approach on reef-microbialites from Tahiti (Pacific Ocean), it was recently shown that sulfate-reducing bacteria favored the formation of microbial carbonates. To test if similar mechanisms induced microbialite formation in other reefs as well, the Tahitian microbialites are compared with similar microbialites from coral reefs off Vanuatu (Pacific Ocean), Belize (Caribbean Sea, Atlantic Ocean), and the Maldives (Indian Ocean) in this study. The selected study sites cover a wide range of geological settings, reflecting variable input and composition of detritus. The new lipid biomarker data and stable sulfur isotope results confirm that sulfate-reducing bacteria played an intrinsic role in the precipitation of microbial carbonate at all study sites, irrespective of the geological setting. Abundant biomarkers indicative of sulfate reducers include a variety of terminally-branched and mid chain-branched fatty acids as well as mono-O-alkyl glycerol ethers. Isotope evidence for bacterial sulfate reduction is represented by low d34S values of pyrite (-43 to -42 per mill) enclosed in the microbialites and, compared to seawater sulfate, slightly elevated d34S and d18O values of carbonate-associated sulfate (21.9 to 22.2 per mill and 11.3 to 12.4 per mill, respectively). Microbialite formation took place in anoxic micro-environments, which presumably developed through the fertilization of the reef environment and the resultant accumulation of organic matter including bacterial extracellular polymeric substances (EPS), coral mucus, and marine snow in cavities within the coral framework. ToF-SIMS analysis reveals that the dark layers of laminated microbialites are enriched in carbohydrates, which are common constituents of EPS and coral mucus. These results support the hypothesis that bacterial degradation of EPS and coral mucus within microbial mats favored carbonate precipitation. Because reefal microbialites formed by similar processes in very different geological settings, this comparative study suggests that a volcanic hinterland is not required for microbialite growth. Yet, detrital input derived from the weathering of volcanic rocks appears to be a natural fertilizer, being conductive for the growth of microbial mats, which fosters the development of particularly abundant and thick microbial crusts.

Alkenone stable carbon isotopes, carbonate stable carbon and oxygen isotopes, planktic foraminifera boron isotopes and atmospheric CO2 calculations and box model results from Ras il-Pellegrin section, Malta

The development of a permanent, stable ice sheet in East Antarctica happened during the middle Miocene, about 14 million years (Myr) ago. The middle Miocene therefore represents one of the distinct phases of rapid change in the transition from the "greenhouse" of the early Eocene to the "icehouse" of the present day. Carbonate carbon isotope records of the period immediately following the main stage of ice sheet development reveal a major perturbation in the carbon system, represented by the positive d13C excursion known as carbon maximum 6 ("M6"), which has traditionally been interpreted as reflecting increased burial of organic matter and atmospheric pCO2 drawdown. More recently, it has been suggested that the d13C excursion records a negative feedback resulting from the reduction of silicate weathering and an increase in atmospheric pCO2. Here we present high-resolution multi-proxy (alkenone carbon and foraminiferal boron isotope) records of atmospheric carbon dioxide and sea surface temperature across CM6. Similar to previously published records spanning this interval, our records document a world of generally low (~300 ppm) atmospheric pCO2 at a time generally accepted to be much warmer than today. Crucially, they also reveal a pCO2 decrease with associated cooling, which demonstrates that the carbon burial hypothesis for CM6 is feasible and could have acted as a positive feedback on global cooling.