Oxidation of pyrite during extraction of carbonate associated sulfate

The sulfur isotopic composition of carbonate associated sulfate (CAS) has been used to investigate the geochemistry of ancient seawater sulfate. However, few studies have quantified the reliability of δ³⁴S of CAS as a seawater sulfate proxy, especially with respect to later diagenetic overprinting. Pyrite, which typically has depleted δ³⁴S values due to authigenic fractionation associated with bacterial sulfate reduction, is a common constituent of marine sedimentary rocks. The oxidation of pyrite, whether during diagenesis or sample preparation, could thus adversely influence the sulfur isotopic composition of CAS. Here, we report the results of CAS extractions using HCl and acetic acid with samples spiked with varying amounts of pyrite. The results show a very strong linear relationship between the abundance of fine-grained pyrite added to the sample and the resultant abundance and δ³⁴S value of CAS. This data represents the first unequivocal evidence that pyrite is oxidized during the CAS extraction process. Our mixing models indicate that in samples with much less than 1 wt.% pyrite and relatively high δ³⁴S_pyrite values, the isotopic offset imparted by oxidation of pyrite should be much less than ? 4‰. A wealth of literature exists on the oxidation of pyrite by Fe³⁺ and we believe this mechanism drives the oxidation of pyrite during CAS extraction, during which the oxygen used to form sulfate is taken from H₂O, not O₂. Consequently, extracting CAS under anaerobic conditions would only slow, but not halt, the oxidation of pyrite. Future studies of CAS should attempt to quantify pyrite abundance and isotopic composition.     

Lateral structural variability in zone of eocene island-arc-continent collision,Kamchatka

The lateral variability of structural elements in the collision zone of the Cretaceous-Paleocene Achaivayam-Valagin island arc with the northeastern Asian margin is considered. The similarity and difference of Eocene collision structural elements in the north and the south of Kamchatka are shown. In northern Kamchatka, the continent-arc boundary is traced along the Lesnaya-Vatyn Thrust Fault, which completed its evolution about 45 Ma ago. The thin, near-horizontal allochthon of this thrust, composed of island-arc rocks, overlies the deformed but unmetamorphosed terrigeneous sequences of the Asian margin. The general structure of this suture in the Kamchatka Isthmus and southern Koryakia is comparable with the uppermost subduction zone, where a thin lithospheric wedge overlaps intensely deformed sediments detached from the plunging plate. In southern Kamchatka (Malka Uplift of the Sredinny Range), the arc-continent collision started 55–53 Ma ago with thrusting of island-arc complexes over terrigenous rocks of continental margin. However, the thickness of the allochthon was much greater than in the north. Immediately after this event, both the autochthon and lower part of allochthon were deformed and subsided to a significant depth. This subsidence gave rise to metamorphism of both the autochthon (Kolpakov and Kamchatka groups, Kheivan Formation) and lower allochthon (Andrianovka and Khimka formations). The anomalously fast heating of the crust was most likely related to the ascent of asthenospheric masses due to slab breakoff, when the Eurasian Plate was plunging beneath the Achaivayam-Valagin arc.     

Stratigraphic constraints on suture models for eastern Indonesia

Although collision in eastern Indonesia is now accreting the Australian continent to Southeast Asia, the small North and South Banda oceanic basins within the suture zone are interpreted as Late Cenozoic extensional features. Stratigraphic columns from the surrounding islands conform to one of three generalised patterns, two of which can be related to the margins of SE Asia (Sundaland) and the Australian continent, respectively. The third system, which is dominant in the outer Banda Arc and eastern Sulawesi, is associated with a microcontinent that was rifted from Australia in the Jurassic, drifted northwards ahead of Australia in the Cretaceous and collided with the Sundaland Margin in the Paleogene. Subsequent collapse of the resulting collision orogen led to rapid extension and the formation of the Banda Sea behind the Outer Banda Arc thrust belt. Eastern Indonesia thus duplicates a pattern familiar in the Mediterranean. The Tertiary compressional structures of the region cannot be explained solely in terms of the most recent collision, which began only in the Pliocene.     

A renaissance in studies of ancient life

In the Origin of Species, published a century‐and‐a‐half ago, Darwin was mystified by the lack of a ‘pre‐Cambrian’ fossil record, the existence of which he regarded as pivotal to his theory of evolution. For the next 100 years, this ‘missing’ fossil record—unknown and thought unknowable'stood out as arguably the single greatest blemish to Darwin's theory. Beginning in the 1950s, the answer to Darwin's problem began to be unearthed, a Precambrian record of flourishing communities of microscopic organisms now known to extend to 3500 million years ago. During recent years, studies of such ancient microbes have markedly increased, spurred by an influx of new workers and, especially, by the introduction of new analytical techniques, three of which are featured here: confocal laser scanning microscopy, and Raman‐spectral and fluorescence‐spectral imagery. Used together, these techniques provide evidence of the three‐dimensional form, cellular anatomy, and molecular structure of rock‐embedded microscopic fossils and of the minerals in which they are entombed that is unavailable by any other means.     

Role of land-surface temperature feedback on model performance for the stable boundary layer

At present a variety of boundary-layer schemes is in use in numerical models and often a large variation of model results is found. This is clear from model intercomparisons, such as organized within the GEWEX Atmospheric Boundary Layer Study (GABLS). In this paper we analyze how the specification of the land-surface temperature affects the results of a boundary-layer scheme, in particular for stable conditions. As such we use a well established column model of the boundary layer and we vary relevant parameters in the turbulence scheme for stable conditions. By doing so, we can reproduce the outcome for a variety of boundary-layer models. This is illustrated with the original set-up of the second GABLS intercomparison study using prescribed geostrophic winds and land-surface temperatures as inspired by (but not identical to) observations of CASES-99 for a period of more than two diurnal cycles. The model runs are repeated using a surface temperature that is calculated with a simple land-surface scheme. In the latter case, it is found that the range of model results in stable conditions is reduced for the sensible heat fluxes, and the profiles of potential temperature and wind speed. However, in the latter case the modelled surface temperatures are rather different than with the original set-up, which also impacts on near-surface air temperature and wind speed. As such it appears that the model results in stable conditions are strongly influenced by non-linear feedbacks in which the magnitude of the geostrophic wind speed and the related land-surface temperature play an important role.     

Accelerated initial stiffness schemes for elastoplasticity

Iterative methods for the solution of non‐linear finite element equations are generally based on variants of the Newton–Raphson method. When they are stable, full Newton–Raphson schemes usually converge rapidly but may be expensive for some types of problems (for example, when the tangent stiffness matrix is unsymmetric). Initial stiffness schemes, on the other hand, are extremely robust but may require large numbers of iterations for cases where the plastic zone is extensive. In most geomechanics applications it is generally preferable to use a tangent stiffness scheme, but there are situations in which initial stiffness schemes are very useful. These situations include problems where a nonassociated flow rule is used or where the zone of plastic yielding is highly localized. This paper surveys the performance of several single‐parameter techniques for accelerating the convergence of the initial stiffness scheme. Some simple but effective modifications to these procedures are also proposed. In particular, a modified version of Thomas' acceleration scheme is developed which has a good rate of convergence. Previously published results on the performance of various acceleration algorithms for initial stiffness iteration are rare and have been restricted to relatively simple yield criteria and simple problems. In this study, detailed numerical results are presented for the expansion of a thick cylinder, the collapse of a rigid strip footing, and the failure of a vertical cut. These analyses use the Mohr–Coulomb and Tresca yield criteria which are popular in soil mechanics. Copyright © 2000 John Wiley & Sons, Ltd.