Atomistic simulation of the mechanisms of noble gas incorporation in minerals

Atomistic simulations have been carried out to investigate the mechanisms of noble gas incorporation in minerals using both the traditional two-region approach and the “supercell” method. The traditional two-region approach has been used to calculate defect energies for Ne, Ar, Kr and Xe incorporation in MgO, CaO, diopside and forsterite in the static limit and at one atmosphere pressure. The possibilities of noble gas incorporation via both substitution and interstitial mechanisms are studied. The favored mechanism varies from mineral to mineral and from noble gas to noble gas. In all minerals studied, the variation of the solution energies of noble gas substitution with atomic radius appears approximately parabolic, analogous to those for 1⁺, 2⁺, 3⁺ and 4⁺ trace element incorporation on crystal lattice sites. Noble gas solution energies thus also fall on a curve, similar to those previously observed for cations with different charges, but with much lower curvature.The “supercell” method has been used to investigate the pressure dependence of noble gas incorporation in the same systems. Results indicate a large variation of the solubility of the larger noble gases, Kr and Xe with pressure. In addition, explicit simulation of incorporation at the (0 0 1) surface of MgO shows that the solubility of the heavier noble gases may be considerably enhanced by the presence of interfaces.     

Anaerobic oxidation of methane (AOM) in marine sediments from the Skagerrak (Denmark): II. Reaction-transport modeling

A steady-state reaction-transport model is applied to sediments retrieved by gravity core from two stations (S10 and S13) in the Skagerrak to determine the main kinetic and thermodynamic controls on anaerobic oxidation of methane (AOM). The model considers an extended biomass-implicit reaction network for organic carbon degradation, which includes extracellular hydrolysis of macromolecular organic matter, fermentation, sulfate reduction, methanogenesis, AOM, acetogenesis and acetotrophy. Catabolic reaction rates are determined using a modified Monod rate expression that explicitly accounts for limitation by the in situ catabolic energy yields. The fraction of total sulfate reduction due to AOM in the sulfate-methane transition zone (SMTZ) at each site is calculated. The model provides an explanation for the methane tailing phenomenon which is observed here and in other marine sediments, whereby methane diffuses up from the SMTZ to the top of the core without being consumed. The tailing is due to bioenergetic limitation of AOM in the sulfate reduction zone, because the methane concentration is too low to engender favorable thermodynamic drive. AOM is also bioenergetically inhibited below the SMTZ at both sites because of high hydrogen concentrations (∼3-6 nM). The model results imply there is no straightforward relationship between pore water concentrations and the minimum catabolic energy needed to support life because of the highly coupled nature of the reaction network. Best model fits are obtained with a minimum energy for AOM of ∼11 kJ mol⁻¹, which is within the range reported in the literature for anaerobic processes.     

Characterization and cycling of atmospheric mercury along the central US Gulf Coast

Concentrations of atmospheric Hg species, elemental Hg (Hg^°), reactive gaseous Hg (RGM), and fine particulate Hg (Hg-PM_2.5) were measured at a coastal site near Weeks Bay, Alabama from April to August, 2005 and January to May, 2006. Mean concentrations of the species were 1.6 ± 0.3 ng m⁻³, 4.0 ± 7.5 pg m⁻³ and 2.7 ± 3.4 pg m⁻³, respectively. A strong diel pattern was observed for RGM (midday maximum concentrations were up to 92.7 pg m⁻³), but not for Hg^° or Hg-PM_2.5. Elevated RGM concentrations (>25 pg m⁻³) in April and May of 2005 correlated with elevated average daytime O₃ concentrations (>55 ppbv) and high light intensity (>500 W m⁻²). These conditions generally corresponded with mixed continental-Gulf and exclusively continental air mass trajectories. Generally lower, but still elevated, RGM peaks observed in August, 2005 and January–March, 2006 correlated significantly (p < 0.05) with peaks in SO₂ concentration and corresponded to periods of high light intensity and lower average daytime O₃ concentrations. During these times air masses were dominated by trajectories that originated over the continent. Elevated RGM concentrations likely resulted from photochemical oxidation of Hg^° by atmospheric oxidants. This process may have been enhanced in and by the near-shore environment relative to inland sites. The marine boundary layer itself was not found to be a significant source of RGM.     

A seismic refraction study of cretaceous oceanic lithosphere in the Northwest Pacific Basin

A seismic refraction study on old (110 Myr) lithosphere in the northwest Pacific Basin has placed constraints on crustal and uppermantle seismic structure of old oceanic lithosphere, and lithospheric aging processes. No significant lateral variation in structure other than azimuthally anisotropic mantle velocities was found, allowing the application of powerful amplitude modeling techniques. The anisotropy observed is in an opposite sense to that expected, suggesting the tectonic setting of the area may be more complex than originally thought. Upper crustal velocities are generally larger than for younger crust, supporting current theories of decreased porosity with crustal aging. However, there is no evidence for significant thickening of the oceanic crust with age, nor is there any evidence of a lower crustal layer of high or low velocity relative to the velocity of the rest of Layer 3. The compressional and shear wave velocities rule out a large component of serpentinization of mantle materials. The only evidence for a basal crustal layer of olivine gabbro cumulates is a 1.5 km thick Moho transition zone. In the slow direction of anisotropy, upper mantle velocities increase from 8.0 km s^-1 to 8.35 km s^-1 in the upper 15 km below the Moho. This increase is inconsistent with an homogeneous upper mantle and suggests that compositinal or phase changes occur near the Moho.     

Instrument calibration of ocean bottom seismographs

To increase the accuracy of measuring sea floor motion with ocean bottom seismometers, we calibrate the seismometer system on the ocean floor. Data from the sea floor calibration, augmented with electronic and land calibration data, enables us to find the OBS transfer function to an accuracy of 0.5% in the frequency range of 0.1 to 32 Hz. We are able to distinguish between temperature, instrument and OBS ground coupling effects, all of which alter the transfer function. This paper reviews our method of calibration and discusses the effects of temperature and some of the instrument design features on the vertical seismometer transfer function.     

Freezing as a method of sample preservation for the analysis of dissolved inorganic nutrients in seawater

It is often desirable or necessary to store collected seawater samples prior to analysis for dissolved inorganic nutrients. It is therefore important to establish preservation and storage techniques that will ensure sample integrity and will not alter the precision or accuracy of analysis. We have performed a series of experiments on the storage of nutrient samples collected at the oligotrophic North Pacific benchmark Station ALOHA, using both standard autoanalyses and low-level techniques. Our results reveal that for oligotrophic oceanic waters, the immediate freezing of an unfiltered water sample in a clean polyethylene bottle is a suitable preservation method. This procedure is simple, it avoids potentially contaminating sample manipulations and chemical additions, and it adequately preserves the concentrations of nitrate + nitrite, soluble reactive phosphate, and soluble reactive silicate within a single water sample.     

Dynamics of the long-period tides

The long-period tides are a tool for understanding oceanic motions at low frequencies and large scales. Here we review observations and theory of the fortnightly, monthly and pole tide constitutents. Observations have been plagued by low signal-to-noise ratios and theory by the complex lateral geometry and great sensitivity to bottom slopes. A new spectral element model is used to compute the oceanic response to tidal forcing at 2-week and monthly periods. The general response is that of a heavily damped (Q ≈ 5) system with both the energy input from the moon and the dissipation strongly localized in space. The high dissipation result is probably generally applicable to all low frequency barotropic oceanic motions. Over much of the ocean, the response has both the character of a large-scale and a superposed Rossby wave-like character, thus vindicating two apparently conflicting earlier interpretations. To the extent that free waves are excited they are consistent with their being dominated by Rossby and topographic Rossby wave components, although gravity modes are also necessarily excited to some degree. In general, a modal representation is not very helpful. The most active regions are the Southern Ocean and the western and northern North Atlantic. These results are stable to changes in geometry, topography, and tide period. On a global average basis, the dynamical response of Mm is closer to equilibrium than is Mf.