Abstract: We use observations of the mass-independent oxygen isotopic composition (?17O) of sulfate in the marine boundary layer (MBL) to quantify the sulfate source from aqueous SO2 (S(IV)) oxidation by O3 in alkaline sea-salt aerosols. Oxidation by O3 imparts a large ?17O signature to the resulting sulfate (8.8‰) relative to oxidation by H2O2 (0.9‰) or by OH or O2 (0‰). Ship data from two Indian Ocean Experiment (INDOEX) cruises in the Indian Ocean indicate ?17O values usually <1‰ in the submicron sulfate aerosol but considerable variability in the supermicron sulfate with frequent occurrences above 1‰ and up to 6.7‰. The large ?17O values are associated with high concentrations of sea-salt aerosols, providing evidence for the S(IV) + O3 pathway. We use a global chemical transport model (GEOS-CHEM) to interpret quantitatively the INDOEX observations and to assess the global importance of sulfate production in sea-salt aerosols. The model accounts for titration of sea-salt alkalinity in the MBL by uptake of acid gases (SO2, H2SO4, and HNO3), shutting down the S(IV) + O3 pathway. We find that this titration occurs rapidly over much of the oceans except at high latitudes (strong sea-salt emission) and is due to both the S(IV) + O3 reaction and HNO3 (g) condensation; that is, sulfate formation in sea-salt aerosols is limited by the alkalinity flux from the ocean and by competition for this alkalinity supply from HNO3 (g). The model is consistent with the ?17O magnitudes and patterns in the INDOEX data. Titration of alkalinity is critical for the success of the model simulation. Regeneration of sea-salt aerosol alkalinity by OH uptake is inconsistent with the ?17O observations in INDOEX. Model results indicate that sulfate production in sea-salt aerosols decreases MBL SO2 concentrations and gas phase H2SO4 production rates by typically 10–30% (up to >70%) and increases MBL sulfate concentrations by typically >10% (up to 30%). Globally, this mechanism contributes 9% of atmospheric sulfate production and 1% of the sulfate burden. The impact on H2SO4 (g) formation and implications for the potential formation of new particles in the MBL warrants inclusion in models examining the radiative effects of sulfate aerosols.

Abstract: The adsorption isotherms of acetone on ice were measured at 193, 203 and 213 K using a volumetric method with mass spectrometric detection. Henry's law applies for values of the acetone partial pressure, Pacetone, lower than 10?3 Pa. Where Henry's law applies, the number of acetone molecules adsorbed per cm2 of ice, is: nads = 90.53 × Pacetone × exp (6610.2/T), with Pacetone in Pa and T in K. The measured enthalpy of adsorption of acetone on ice is ?Hads = ?55±7 kJ/mol. Acetone values previously measured in Arctic snow are too high to be due to adsorbed acetone. Acetone was then probably dissolved in ice or in organic aerosols contained in snow. Adsorption of acetone in the snowpack or on ice crystals in cirrus clouds is insufficient to affect Pacetone above the snow or in the clouds.

Abstract: Many peridotite xenoliths sampled at ocean islands appear to have strongly refractory major element and modal compositions. To better constrain the chemistry, abundance and origin of these ultra-refractory rocks we compiled a large number of data for xenoliths from nine groups of ocean islands. The xenoliths were filtered petrographically for signs of melt infiltration and modal metasomatism, and the samples affected by these processes were excluded. The xenolith suites from most ocean islands are dominated by ultra-refractory harzburgites. Exceptions are the Hawaii and Tahiti peridotites, which are more fertile and contain primary clinopyroxene, and the Cape Verde suite, which contains both ultra-refractory and more fertile xenoliths. Ultra-refractory harzburgites are characterized by the absence of primary clinopyroxene, low whole-rock Al2O3, CaO, FeO/MgO and heavy rare earth element (HREE) concentrations, low Al2O3 in orthopyroxene (generally < 3 wt %), high Cr-number in spinel (0{middle dot}3-0{middle dot}8) and high forsterite contents in olivine (averages > 91{middle dot}5). They are therefore on average significantly more refractory than peridotites dredged and drilled from mid-ocean ridges and fracture zones. Moreover, their compositions resemble those of oceanic forearc peridotites. The formation of ultra-refractory ocean island harzburgites requires potential temperatures above those normally observed at modern mid-ocean ridges, and/or fluid fluxed conditions. Some ultra-refractory ocean island harzburgites give high Os model ages (up to 3300 Ma), showing that their formation significantly pre-dates the oceanic crust in the area. A genetic relationship with the host plume is considered unlikely based on textural observations, equilibration temperatures and pressures, inferred physical properties, and the long-term depleted Os and Sr isotope compositions of some of the harzburgites. Although we do not exclude the possibility that some ultra-refractory ocean island harzburgites have formed at mid-ocean ridges, we favor a model in which they formed in a process spatially and temporally unrelated to the formation of the oceanic plate and the host plume. As a result of their whole-rock compositions, ultra-refractory harzburgites have a very high solidus temperature at a given pressure, low densities and very high viscosities, and will tend to accumulate at the top of the convecting mantle. They may be preserved as fragments in the convecting mantle over long periods of time and be preferentially incorporated into newly formed lithosphere.

Abstract: A classical method for understanding the coupling between northern and southern hemispheres during millennial-scale climate events is based on the correlation between Greenland and Antarctic ice core records of atmospheric composition. Here we present a new approach based on the use of a single Antarctic ice core in which measurements of methane concentration and inert gas isotopes place constraints on the timing of a rapid climate change in the North and of its Antarctic counterpart. We applied it to the Marine Isotope Stage (MIS) 5d/c transition early in the last glaciation ?108 ky BP. Our results indicate that the Antarctic temperature increase occurred 2 ky before the methane increase, which is used as a time marker of the warming in the Northern Hemisphere. This result is in agreement with the “bipolar seesaw” mechanism used to explain the phase relationships documented between 23 and 90 ky BP [
Blunier and Brook, 2001].