Coincident seismic reflection/refraction studies of the continental lithosphere: a global review

Summary. Vertical-incidence reflection profiling has identified several characteristic features of the continental Iithosphere including a generally transparent upper crust, a reflective lower crust, reflections from the crust-mantle boundary, and a commonly transparent upper mantle. The underlying physical causes of these characteristic features remain poorly understood. This review summarizes additional information brought to bear on the physical properties of these characteristic crustal structures through the use of coincident wide-angle refraction profiling.     

Fresnel modeling of hematite crystal surfaces and application to martian hematite spherules

The gray crystalline hematite at Meridiani Planum first discovered by the Mars Global Surveyor Thermal Emission Spectrometer (MGS-TES) instrument occurs as spherules that have been interpreted as concretions. Analysis of the TES and mini-TES spectra shows that no 390 cm⁻¹ feature is present in the characteristic martian hematite spectrum. Here, we incorporate the mid-IR optical constants of hematite into a simple Fresnel reflectance model to understand the effect of emission angle and crystal morphology on the presence or absence of the 390 cm⁻¹ feature in an IR hematite spectrum. Based on the results we offer two models for the internal structure of the martian hematite spherules.     

Decomposition of Hudson estuary macrophytes: Photosynthetic pigment transformations and decay constants

Plant pigment decay constants were determined for four macrophytes collected from the Hudson Estuary.Typha angustifolia andScirpus fluviatilis were used as representatives of emergent aquatic vegetation (EAV), andPotamogeton sp. andVallisneria americana were used to represent submerged aquatic vegetation (SAV). Litter bags were maintained in an environmental chamber in the dark for 104 d. The fastest rate of total mass loss was in the SAVV. americana and slowest in the EAVT. angustifolia. Changes in carotenoid and chloropigment concentration resulting from microbial and meiofaunal heterotrophy in each of the macrophytes were quantified using reverse-phase, high-performance liquid chromatography (RP-HPLC) techniques. Chlorophyllc and the carotenoid, fucoxanthin, provided useful biomarkers in determining the presence of epiphytic diatom growth, which only occurred on the SAV. The highest concentrations of phaeophorbidea, commonly used as an indication of metazoan grazing, were found in the SAVV. americana. Low concentrations of phaeophorbidea in the SAVPotamogeton sp. indicate inefficient use of this SAV by meiofaunal grazers. Lutein decayed slower than all other carotenoids in both EAV and SAV. Microcosm studies such as this are necessary to further understand the mechanisms and kinetics of photosynthetic pigment transformations in natural systems.     

Potential for localized groundwater contamination in a porous pavement parking lot setting in Rhode Island

The control of polluted surface runoff and the assessment of possible impacts on groundwater is a concern at the local and regional scale. On this background, a study investigates possible impacts of organic and inorganic pollutants (including bacteria) originating from a permeable asphalt parking lot on the water quality immediately beneath it. The functioning of the permeable pavement, including clogging and restricted vertical percolation, was also evaluated. Four nested sample ports (shallow and deep) were installed below low- and high-traffic areas, including one port outside the parking lot. At least initially there was a good hydraulic connection between the parking surface and the shallow sample ports. The presence of a geotextile layer at the base of the parking lot structure, however, was identified in lab tests as one factor restricting vertical percolation to the deeper ports. Clogging of the permeable surface was most pronounced in heavy traffic areas and below snow pile storage areas. Corroborated by high electric conductivity and chloride measurements, sand brought in by cars during winter was the principal cause for clogging. No bacteria or BOD were found in percolating water. Polycyclic aromatic hydrocarbons (PAH) were present at concentrations near minimum detection limit. Nutrients (nitrate and phosphate) were being leached into the ground via the permeable parking lot surface at annual flux rates of 0.45–0.84 g/m²/year. A multi-species tracer test demonstrated a retention capacity of the permeable parking lot structure of >90% for metals and 27% for nutrients, respectively.     

Experimental investigation of the effects of temperature and ionic strength on Mo isotope fractionation during adsorption to manganese oxides

The Mo stable isotope system is being applied to study changes in ocean redox. Such applications implicitly assume that Mo isotope fractionation in aqueous systems is relatively insensitive to frequently changing environmental variables such as temperature (T) and ionic strength (I). A major driver of fractionation is the adsorption of Mo to Mn oxyhydroxide surfaces [Barling J. and Anbar A. D. (2004) Molybdenum isotope fractionation during adsorption by manganese oxides. Earth Planet. Sci. Lett.217(3-4), 315-329]. Here, we report the results of experiments that determine the extent to which Mo isotope fractionation during adsorption of Mo to the Mn oxyhydroxide mineral birnessite is sensitive to T and I. The results are compared to new predictions from quantum chemical computations. We measured fractionation from 1 to 50 °C at I = 0.1 m and found that Δ^97/95Mo_{dissolved-adsorbed} varies from 1.9‰ to 1.6‰ over this temperature range. Experiments were also performed at 25 °C in synthetic seawater (I = 0.7); fractionation at this condition was the same within analytical error as in low ionic strength experiments. These findings confirm that the Mo isotope fractionation during adsorption to Mn oxyhydroxides is relatively insensitive to variations and T and I over environmentally relevant ranges. To relate these findings to potential mechanisms of Mo isotope fractionation, we also report results for density functional theory computations of the fractionation between and various possible structures of molybdic acid as a function of temperature. Because no plausible species fractionates from with a magnitude matching the experiments, we are left with three possibilities to explain the fractionation: (1) solvation effects on the vibrational frequencies of aqueous species considered thus far are significant, such that our calculations in vacuo yield inaccurate fractionations; (2) a trace aqueous species not yet considered fractionates from and then adsorbs to birnessite; or (3) a surface complex not present in solution forms on birnessite in which Mo is not tetrahedrally coordinated. Our findings help validate assumptions underlying paleoceanographic applications of the Mo isotope system and also lead us closer to understanding the mechanism of isotope fractionation during adsorption of Mo to Mn oxyhydroxides.     

Microbial mass-dependent fractionation of chromium isotopes

Mass-dependent fractionation of Cr isotopes occurs during dissimilatory Cr(VI) reduction by Shewanella oneidensis strain MR-1. Cells suspended in a simple buffer solution, with various concentrations of lactate or formate added as electron donor, reduced 5 or 10 μM Cr(VI) to Cr(III) over days to weeks. In all nine batch experiments, ⁵³Cr/⁵²Cr ratios of the unreacted Cr(VI) increased as reduction proceeded. In eight experiments covering a range of added donor concentrations up to 100 μM, isotopic fractionation factors were nearly invariant, ranging from 1.0040 to 1.0045, with a mean value somewhat larger than that previously reported for abiotic Cr(VI) reduction (1.0034). One experiment containing much greater donor concentration (10 mM lactate) reduced Cr(VI) much faster and exhibited a lesser fractionation factor (1.0018). These results indicate that ⁵³Cr/⁵²Cr measurements should be effective as indicators of Cr(VI) reduction, either bacterial or abiotic. However, variability in the fractionation factor is poorly constrained and should be studied for a variety of microbial and abiotic reduction pathways.     

Stability at high-pressure,elastic behaviour and pressure-induced structural evolution of CsAlSi<Subscript>5</Subscript>O<Subscript>12</Subscript>, a potential host for nuclear waste

The elastic and structural behaviour of the synthetic zeolite CsAlSi₅O₁₂ (a = 16.753(4), b = 13.797(3) and c = 5.0235(17) Å, space group Ama2, Z = 2) were investigated up to 8.5 GPa by in situ single-crystal X-ray diffraction with a diamond anvil cell under hydrostatic conditions. No phase-transition occurs within the P-range investigated. Fitting the volume data with a third-order Birch–Murnaghan equation-of-state gives: V ₀ = 1,155(4) ų, K _T0 = 20(1) GPa and K′ = 6.5(7). The “axial moduli” were calculated with a third-order “linearized” BM-EoS, substituting the cube of the individual lattice parameter (a ³, b ³, c ³) for the volume. The refined axial-EoS parameters are: a ₀ = 16.701(44) Å, K _T0a = 14(2) GPa (β_a = 0.024(3) GPa^?1), K′ _a = 6.2(8) for the a-axis; b ₀ = 13.778(20) Å, K _T0b = 21(3) GPa (β_b = 0.016(2) GPa^?1), K′ _b = 10(2) for the b-axis; c ₀ = 5.018(7) Å, K _T0c = 33(3) GPa (β_c = 0.010(1) GPa^?1), K′ _c = 3.2(8) for the c-axis (K _T0a:K _T0b:K _T0c = 1:1.50:2.36). The HP-crystal structure evolution was studied on the basis of several structural refinements at different pressures: 0.0001 GPa (with crystal in DAC without any pressure medium), 1.58(3), 1.75(4), 1.94(6), 3.25(4), 4.69(5), 7.36(6), 8.45(5) and 0.0001 GPa (after decompression). The main deformation mechanisms at high-pressure are basically driven by tetrahedral tilting, the tetrahedra behaving as rigid-units. A change in the compressional mechanisms was observed at P ≤ 2 GPa. The P-induced structural rearrangement up to 8.5 GPa is completely reversible. The high thermo-elastic stability of CsAlSi₅O_12, the immobility of Cs at HT/HP-conditions, the preservation of crystallinity at least up to 8.5 GPa and 1,000°C in elastic regime and the extremely low leaching rate of Cs from CsAlSi₅O₁₂ allow to consider this open-framework silicate as functional material potentially usable for fixation and deposition of Cs radioisotopes.     

Trace element diagenesis in pyrite-rich sediments of the Achterwasser lagoon, SW Baltic Sea

The early diagenesis of trace elements (V, Cr, Co, Cu, Zn, As, Cd, Ba, U) in anoxic sediments of the Achterwasser, a shallow lagoon in the non-tidal Oder estuary in the Baltic Sea, was investigated in the context of pyrite formation. The dissolved major redox parameters show a two-tier distribution with transient signals in the occasionally re-suspended fluid mud layer (FM) and a permanently established diagenetic sequence in the sediment below. Intense microbial respiration leads to rapid depletion of O₂ within the uppermost mm of the FM. The reduction zones of Mn, Fe and sulfate overlap in the FM and in the permanently anoxic sediment section which appears to be a typical feature of estuarine sediments, under low-sulfate conditions. Degrees of pyritization (DOP) range from 50% in the FM to remarkably high values > 90% at 50 cm depth. Pyrite formation at the sediment surface is attributed to the reaction of Fe-monosulfides with intermediate sulfur species via the polysulfide pathway. By contrast, intense pyritization in the permanently anoxic sediment below is attributed to mineral growth via adsorption of aqueous Fe-sulfide complexes onto pyrite crystals which had originally formed in the surface layer.The studied trace elements show differential behavior patterns which are closely coupled to the diagenetic processes described above: (i) Zn, Cu and Cd are liberated from organic matter in the thin oxic layer of the sediment and diffuse both upwards across the sediment/water boundary and downwards to be trapped as monosulfides, (ii) V, Cr, Co and As are released during reductive dissolution of Mn- and Fe-oxyhydroxides, (iii) U removal from pore water occurs concomitantly to Fe reduction in the FM and is attributed to reduction of U(VI) to U(IV), (iv) the Ba distribution is controlled by reductive dissolution of authigenic barite in the sulfate reduction zone coupled with upward diffusion and re-precipitation. The incorporation of trace elements into pyrite is most intense for Co, Mn and As, intermediate for Cu and Cr and little to negligible for U, Zn, Cd, V and Ba. The observed trend is largely in agreement with previous studies and may be explained with differing rates for ligand exchange. Slow and fast ligand exchange and thus precipitation kinetics are also displayed by downcore increasing (Mn, Cr, Co and As) or constantly low (Zn, Cu, Cd) pore water concentrations. The downward increasing degrees of trace metal pyritization (DTMP) for Co, Cu, Zn and As are, in analogy to pyrite growth, assigned to adsorption of sulfide complexes or As oxyanions onto preexisting pyrite minerals.