Surface chemistry and relative Ni sorptive capacities of synthetic hydrous Mn oxyhydroxides under variable wetting and drying regimes

The surface binding site characteristics and Ni sorptive capacities of synthesized hydrous Mn oxyhydroxides experimentally conditioned to represent three hydrological conditions—MnO_XW, freshly precipitated; MnO_XD, dried at 37°C for 8 d; and MnO_XC, cyclically hydrated and dehydrated (at 37°C) over a 24-h cycle for 7 d—were examined through particle size analysis, surface acid-base titrations and subsequent modelling of the pK_a spectrum, and batch Ni sorption experiments at two pH values (2 and 5). Mineralogical bulk analyses by XRD indicate that all three treatments resulted in amorphous Mn oxyhydroxides; i.e., no substantial bulk crystalline phases were produced through drying. However, drying and repeated wetting and drying resulted in a non-reversible decrease in particle size. In contrast, total proton binding capacities determined by acid-base titrations were reversibly altered with drying and cyclically re-wetting and drying from 82 ± 5 μmol/m² for the MnO_XW to 21 ± 1 μmol/m² for the MnO_XD and 37 ± 5 μmol/m² for the MnO_XC. Total proton binding sites measured decreased by ≈75% with drying from the MnO_XW and then increased to ≈50% of the MnO_XW value in the MnO_XC. Thus, despite a trend of higher surface area for the MnO_XD, a lower total number of sites was observed, suggesting a coordinational change in the hydroxyl sites. Surface site characterization identified that changes also occurred in the types and densities of surface sites for each hydrologically conditioned Mn oxyhydroxide treatment (pH titration range of 2-10). Drying decreased the total number of sites as well as shifted the remaining sites to more acidic pK_a values. Experimentally determined apparent pH_zpc values decreased with drying, from 6.82 ± 0.06 for the MnO_XW to 3.2 ± 0.3 for the MnO_XD and increased again with rewetting to 5.05 ± 0.05 for the MnO_XC. Higher Ni sorption was observed at pH 5 for all three Mn oxyhydroxide treatments compared to pH 2. However, changes in relative sorptive capacities among the three treatments were observed for pH 2 that are not explainable simply as a function of total binding site density or apparent pH_zpc values. These results are the first to our knowledge, to quantitatively link the changes induced by hydrologic variability for surface acid base characteristics and metal sorption patterns. Further, these results likely extend to other amorphous minerals, such as Fe oxyhydroxides, which are commonly important geochemical solids for metal scavenging in natural environments.     

Shore platform morphology on a rapidly uplifting coast,Wellington, New Zealand

The coast of Wellington, New Zealand, is tectonically active and contains a series of uplifted and contemporary shore platforms that are developed in Triassic Greywacke. The platform profiles are rugged with relief of metre scale common. The surveyed platforms were formed at, and at two distinct levels 1–1·5 and 2–2·5 m above, mean sea level. They range in width up to 70 m and are highly fractured with fracture densities in excess of 20[sol ]m² common. The rate of development of these platforms is rapid, with lateral erosion rates of up to 0·15 m[sol ]yr calculated, allowing platform development to occur over centennial scales. Even given this rapid development, continued instantaneous uplift of the coast has meant they are unable to reach an equilibrium state, whereby the effectiveness of wave processes in removing material is reduced by platform extension. The co‐seismic uplift means that the rear of the platforms is raised beyond the limits of marine process and has become an area of deposition. Although no direct process measurements were made the highly fractured nature of the bedrock appears to play a major role in platform evolution, with wave processes being easily able to pluck blocks as evidenced by fresh erosion scars and active gravel beaches at the rear of many platforms. This coast therefore represents an extremely dynamic youthful shore platform environment, where the processes of marine abrasion can be observed over historical timescales. Copyright © 2005 John Wiley & Sons, Ltd.     

Synchrony of Southern Hemisphere Late Pleistocene arid episodes: A review of luminescence chronologies from arid aeolian landscapes south of the Equator

Luminescence-dating chronologies that have been reported in various studies of Late Pleistocene arid-land aeolian sequences from Australia, southern Africa and South America are reviewed with the objective of determining whether any pan-hemispheric synchroneity existed in the timing of landscape responses to Late Quaternary climate changes south of the equator. The results broadly show that contemporaneous regional arid-land aeolian activity occurred in Australia and southern Africa during the periods ca 65–41 and 36–9 ka. The relatively limited luminescence data from the South American subcontinent also point to recurrent arid-land aeolian deposition between 63 and 8 ka, with increasing frequency in the period ca 32–8 ka. Records from all three continents suggest a period of reduced aeolian activity between 41 and 36 ka. Overall, the data are indicative of extensive landscape instability of the low to mid-latitudes in the Southern Hemisphere during the last glacial period, particularly at the Last Glacial Maximum, which accords with mainstream opinions. Aeolian activity during the Holocene has generally been localised. The rigour with which comparisons can be made between the different studies, however, is constrained by variations in practices between laboratories and changes that have occurred to luminescence dating procedures over the years.     

Lithological control on the elevation of shore platforms in a microtidal setting

The shore platforms on Shag Point, southern New Zealand, are quasi‐horizontal surfaces and are developed between supratidal and low water spring levels. A range of morphologies occur, with more exposed platforms having a distinct low‐tide cliff, in contrast to low‐tide surfaces where the seaward edge is buried beneath rubble and macro‐algal growth. The platforms range in width from 20 to 80 m and are eroded into Late Cretaceous/Early Tertiary fine marine sandstones and mudstones. Shore platforms have formed in two principal lithological units: a homogeneous unit that is characterized by few discontinuities, and a fractured unit with joints spaced about 0·5 m apart. Rock hardness is low in both units (L‐type Schmidt hammer rebound values of 31 ± 4), and there is little systematic variation in values between the two units in which platforms have developed. Case‐hardened concretions within the sandstone are significantly harder than surrounding rock and cause local relief of metre scale as the spherical diagenetic features are eroded from the bedrock. They do not, however, appear to affect broad‐scale platform geometry. Joints within the bedrock are a primary control on platform elevation. Platforms formed in jointed rock occur at the lower portion of the intertidal zone, in contrast to platforms formed in unjointed bedrock, in which horizontal surfaces occur at or above mean high water spring tide level. Rock structure, therefore, appears to be the primary determinant factor of platform geometry at Shag Point. Copyright © 2006 John Wiley & Sons, Ltd.     

Uncertainties in p-MODE POWER AND LINEWIDTH

A statistical approach implies that the commonly accepted derivation for the stochastic variation in line power leads to a 67% underestimate. The 'lifetime of a mode should be defined in terms of the reciprocal of the linewidth, not the e-folding time of the mode. The ratio of positive to negative measurement uncertainties in observed linewidth data is essentially constant. Modeling the distribution of the linewidth measurement values as an exponential produces self-consistent estimates of the standard deviation, and can be useful in examining error propagation. The ratio of the line-power uncertainties is also nearly constant. However, the measurement distribution is more complex. It exhibits behavior similar to an exponential, but has more components.     

Composite titanomagnetite-ferrian ilmenite grains and correlative magnetic components in a dacite with self-reversed TRM

Electron microprobe and reflected light microscopic examinations confirm the presence of composite grains of ferrian ilmenite with X_ilm = 0.53 and titanomagnetite with X_usp = 0.13 in a dacite with self-reversed TRM. A parallel TRM component associated with titanomagnetite and a reversed component associated with self-reversing ferrian ilmenite are the principal NRM components. A subordinate, parallel component is associated with ferrian ilmenite which is not magnetically coupled to an “χ-phase”. The natural self-reversing properties are mainly a consequence of the dacite's high quenching temperature, calculated at 862–864°C using the Fe—Ti oxide geothermometer, and are most consistent with the self-reversal mechanism proposed by Lawson et al. [9].The conduction of thermal demagnetization and TRM induction tests in air had a much greater effect on the Fe—Ti oxides than did natural cooling, and resulted in significant oxidation with the consequent modification of some magnetic properties and the formation of another reversed TRM component. The subdivision of titanomagnetite grains by oxidation along fractures decreased its effective grain size and caused an apparent increase in its magnetic intensity, in addition to a slight increase in its resistance to alternating field demagnetization. The χ-phase associated with the reversed NRM component, with 0.42 > X_ilm 0.31, became Fe-enriched during the earlier stages of heat treatment. It is suggested that after heating at 600°C for two hours or more, this χ-phase exsolves as titanohematite with X_ilm < 0.33. The ferrian ilmenite host is consequently enriched in Ti, and another χ-phase much closer in composition to the host generates a reversed TRM component with T_b < 200°C.     

Zircons from Syros, Cyclades, Greece--Recrystallization and Mobilization of Zircon During High-Pressure Metamorphism

Zircons were studied from high-pressure/low-temperature metamorphosedmeta-igneous lithologies from Syros. These rocks carry severalzircon generations related to each other by dissolution–reprecipitationprocesses. One generation is pristine zircon that shows growthzoning, relatively elevated contents of trivalent cations andhigh Th/U ratios. The other end-member is a skeletal zircongeneration with negligible trivalent cation contents and lowTh/U ratios (     

Influence of Mn oxides on the reduction of uranium(VI) by the metal-reducing bacterium Shewanella putrefaciens

The potential for Mn oxides to modify the biogeochemical behavior of U during reduction by the subsurface bacterium Shewanella putrefaciens strain CN32 was investigated using synthetic Mn(III/IV) oxides (pyrolusite [β-MnO₂], bixbyite [Mn₂O₃] and K⁺-birnessite [K₄Mn₁₄O₂₇ · 8H₂O]). In the absence of bacteria, pyrolusite and bixbyite oxidized biogenic uraninite (UO₂[s]) to soluble U(VI) species, with bixbyite being the most rapid oxidant. The Mn(III/IV) oxides lowered the bioreduction rate of U(VI) relative to rates in their absence or in the presence of gibbsite (Al[OH]₃) added as a non-redox-reactive surface. Evolved Mn(II) increased with increasing initial U(VI) concentration in the biotic experiments, indicating that valence cycling of U facilitated the reduction of Mn(III/IV). Despite an excess of the Mn oxide, 43 to 100% of the initial U was bioreduced after extended incubation. Analysis of thin sections of bacterial Mn oxide suspensions revealed that the reduced U resided in the periplasmic space of the bacterial cells. However, in the absence of Mn(III/IV) oxides, UO₂(s) accumulated as copious fine-grained particles external to the cell. These results indicate that the presence of Mn(III/IV) oxides may impede the biological reduction of U(VI) in subsoils and sediments. However, the accumulation of U(IV) in the cell periplasm may physically protect reduced U from oxidation, promoting at least a temporal state of redox disequilibria.