Cnoc Coig: a Mesolithic shell midden assemblage

Recent work on a sample of the chipped stone from one of the late Mesolithic shell midden sites on the Inner Hebrides island of Oronsay has shown that the assemblage was created using bipolar and platform technologies, with an unexpected element of narrow blade technology shown in cores and core trimming elements, suggesting that there may have been links between this classic ‘Obanian’ assemblage and the more typical Mesolithic narrow blade technology. Findings raise questions about the relationship of settlement on the island to Mesolithic settlement rounds and to the transition to the Neolithic.

Optical emission and electron capture of rare-earth trivalent ions located at distinct sites in SnO(2) thin films

We present photoluminescence and decay of photo excited conductivity data for sol-gel SnO(2) thin films doped with rare earth ions Eu(3+) and Er(3+), a material with nanoscopic crystallites. Photoluminescence spectra are obtained under excitation with several monochromatic light sources, such as Kr(+) and Ar(+) lasers, Xe lamp plus a selective monochromator with UV grating, and the fourth harmonic of a Nd: YAG laser (4.65eV), which assures band-to-band transition and energy transfer to the ion located at matrix sites, substitutional to Sn(4+). The luminescence structure is rather different depending on the location of the rare-earth doping, at lattice symmetric sites or segregated at grain boundary layer, where it is placed in asymmetric sites. The decay of photo-excited conductivity also shows different trapping rate depending on the rare-earth concentration. For Er-doped films, above the saturation limit, the evaluated capture energy is higher than for films with concentration below the limit, in good agreement with the different behaviour obtained from luminescence data. For Eu-doped films, the difference between capture energy and grain boundary barrier is not so evident, even though the luminescence spectra are rather distinct.

Impacts of seawater acidification on mantle gene expression patterns of the Baltic Sea blue mussel: implications for shell formation and energy metabolism, link to supplementary material

Marine organisms have to cope with increasing CO2 partial pressures and decreasing pH in the oceans. We elucidated the impacts of an 8-week acclimation period to four seawater pCO2 treatments (39, 113, 243 and 405 Pa/385, 1,120, 2,400 and 4,000 µatm) on mantle gene expression patterns in the blue mussel Mytilus edulis from the Baltic Sea. Based on the M. edulis mantle tissue transcriptome, the expression of several genes involved in metabolism, calcification and stress responses was assessed in the outer (marginal and pallial zone) and the inner mantle tissues (central zone) using quantitative real-time PCR. The expression of genes involved in energy and protein metabolism (F-ATPase, hexokinase and elongation factor alpha) was strongly affected by acclimation to moderately elevated CO2 partial pressures. Expression of a chitinase, potentially important for the calcification process, was strongly depressed (maximum ninefold), correlating with a linear decrease in shell growth observed in the experimental animals. Interestingly, shell matrix protein candidate genes were less affected by CO2 in both tissues. A compensatory process toward enhanced shell protection is indicated by a massive increase in the expression of tyrosinase, a gene involved in periostracum formation (maximum 220-fold). Using correlation matrices and a force-directed layout network graph, we were able to uncover possible underlying regulatory networks and the connections between different pathways, thereby providing a molecular basis of observed changes in animal physiology in response to ocean acidification.

Radiocarbon and stable isotopes in the shell organic matrix: a new approach for the use of mollusk shells in the study of human evolution

Mollusk shells are often found in archeological sites, given their great preservation potential and high value as a multipurpose resource. They are often the only available material to use for radiocarbon dating, due to a lack of well-preserved bones in many archeological sites, especially for the key period of the Middle to Upper Paleolithic transition. However, radiocarbon dating on mollusk shells is often regarded as less reliable compared to bones, wood, or charcoals due to the various factors influencing their radiocarbon content (e.g., Isotope fractionation, marine reservoir effect etc.). For the development of more accurate chronologies using shells, it is fundamental to continue improving the precision of the techniques applied, as has been done for other materials (wood and bones). Thus, improving the chemical pretreatment on mollusk shells might allow researchers to obtain more reliable radiocarbon determinations allowing for the construction of new radiocarbon chronologies in archeological sites where so far it has not been possible. Furthermore, mollusk shells can provide information on the climatic and environmental variables present during their growth. Using shells for paleoclimatic reconstruction adds more evidence helpful for the interpretation of scenarios of human migration, adaptation, and behavior. Standard methods for both radiocarbon and stable isotope studies use the carbonate fraction of the shell. However, being biogenic structures, mollusk shells also consist of a minor organic fraction. The shell organic matrix has an important role in the formation of the calcium carbonate structure and is still not fully understood. This thesis explores the potential of using the shell organic matrix for radiocarbon dating and paleoenvironmental studies. The results of the work performed for this thesis represent a starting point for future research to build on, and further develop the approach and methodology proposed here.

Matrix elements of U(2n) generators in a multishell spin-orbit basis. I. The del-operator MEs in a two-shell composite Gelfand-Paldus basis

This is the first in a series of three articles which aimed to derive the matrix elements of the U(2n) generators in a multishell spin-orbit basis. This is a basis appropriate to many-electron systems which have a natural partitioning of the orbital space and where also spin-dependent terms are included in the Hamiltonian. The method is based on a new spin-dependent unitary group approach to the many-electron correlation problem due to Gould and Paldus [M. D. Gould and J. Paldus, J. Chem. Phys. 92, 7394, (1990)]. In this approach, the matrix elements of the U(2n) generators in the U(n) x U(2)-adapted electronic Gelfand basis are determined by the matrix elements of a single Ll(n) adjoint tensor operator called the del-operator, denoted by Delta(j)(i) (1 less than or equal to i, j less than or equal to n). Delta or del is a polynomial of degree two in the U(n) matrix E = [E-j(i)]. The approach of Gould and Paldus is based on the transformation properties of the U(2n) generators as an adjoint tensor operator of U(n) x U(2) and application of the Wigner-Eckart theorem. Hence, to generalize this approach, we need to obtain formulas for the complete set of adjoint coupling coefficients for the two-shell composite Gelfand-Paldus basis. The nonzero shift coefficients are uniquely determined and may he evaluated by the methods of Gould et al. [see the above reference]. In this article, we define zero-shift adjoint coupling coefficients for the two-shell composite Gelfand-Paldus basis which are appropriate to the many-electron problem. By definition, these are proportional to the corresponding two-shell del-operator matrix elements, and it is shown that the Racah factorization lemma applies. Formulas for these coefficients are then obtained by application of the Racah factorization lemma. The zero-shift adjoint reduced Wigner coefficients required for this procedure are evaluated first. All these coefficients are needed later for the multishell case, which leads directly to the two-shell del-operator matrix elements. Finally, we discuss an application to charge and spin densities in a two-shell molecular system. (C) 1998 John Wiley & Sons.

Matrix elements of U(2n) generators in a multishell spin-orbit basis. II. The two-shell nonzero shift ACCs and U(2n) generator MEs

This is the second in a series of articles whose ultimate goal is the evaluation of the matrix elements (MEs) of the U(2n) generators in a multishell spin-orbit basis. This extends the existing unitary group approach to spin-dependent configuration interaction (CI) and many-body perturbation theory calculations on molecules to systems where there is a natural partitioning of the electronic orbital space. As a necessary preliminary to obtaining the U(2n) generator MEs in a multishell spin-orbit basis, we must obtain a complete set of adjoint coupling coefficients for the two-shell composite Gelfand-Paldus basis. The zero-shift coefficients were obtained in the first article of the series. in this article, we evaluate the nonzero shift adjoint coupling coefficients for the two-shell composite Gelfand-Paldus basis. We then demonstrate that the one-shell versions of these coefficients may be obtained by taking the Gelfand-Tsetlin limit of the two-shell formulas. These coefficients,together with the zero-shift types, then enable us to write down formulas for the U(2n) generator matrix elements in a two-shell spin-orbit basis. Ultimately, the results of the series may be used to determine the many-electron density matrices for a partitioned system. (C) 1998 John Wiley & Sons, Inc.

Boron contents and boron, carbon, and oxygen isotope data for ODP Sites 160-970 and 160-971

Products of two mud volcanoes from the distal part of the Mediterranean Ridge accretionary complex have been investigated regarding their B, C, and O stable isotope signatures. The mud breccias have been divided into mud matrix, lithified clasts, biogenic deposits, and authigenic cements and crusts related to fluid flow and cementation. Isotope geochemistry is used to evaluate the depth of mobilization of each phase in the subduction zone. B contents and isotope ratios of the mud and mud clasts show a general trend of B enrichment and decreasing d11B values with increasing consolidation (i.e., depth). However, the majority of the clast and matrix samples relate to moderate depths of mobilization within the wedge (1-2 km below seafloor). The carbonate cements of most of these clasts as well as the authigenic crusts, however, provide evidence for a deep fluid influence, probably associated with the décollement at 5-6 km depth. This interpretation is supported by d13C ratios of the crust, which indicate precipitation of C from thermogenic methane, and by the d11B ratios of pore-water samples of mud-breccia drill cores. Clams (Vesicomya sp.) living adjacent to fluid vents have d11B and d18O values corresponding to brines known in the area, which acted as the parent solution for shell precipitation. Such brines are most likely Miocene pore waters trapped at deep levels within the backstop to the accretionary prism, probably prior to desiccation of the Mediterranean in the Messinian (6-5 Ma). Combining all results, deep fluid circulation and expulsion are identified as the main processes triggering mud liquefaction and extrusion, whereas brines contribute only locally. Given the high B contents, mud extrusion has to be considered a major backflux mechanism of B into the hydrosphere.

Grain counts and relative abundances of volcaniclastic sands and sandstones of ODP Leg 180 sites

Modal analysis of middle Miocene to Pleistocene volcaniclastic sands and sandstones recovered from Sites 1108, 1109, 1118, 1112, 1115, 1116, and 1114 within the Woodlark Basin during Leg 180 of the Ocean Drilling Program indicates a complex source history for sand-sized detritus deposited within the basin. Volcaniclastic detritus (i.e., feldspar, ferromagnesian minerals, and volcanic rock fragments) varies substantially throughout the Woodlark Basin. Miocene sandstones of the inferred Trobriand forearc succession contain mafic and subordinate silicic volcanic grains, probably derived from the contemporary Trobriand arc. During the late Miocene, the Trobriand outerarc/forearc (including Paleogene ophiolitic rocks) was subaerially exposed and eroded, yielding sandstones of dominantly mafic composition. Rift-related extension during the late Miocene-late Pliocene led to a transition from terrestrial to neritic and finally bathyal deposition. The sandstones deposited during this period are composed dominantly of silicic volcanic detritus, probably derived from the Amphlett Islands and surrounding areas where volcanic rocks of Pliocene-Pleistocene age occur. During this time terrigenous and metamorphic detritus derived from the Papua New Guinea mainland reached the single turbiditic Woodlark rift basin (or several subbasins) as fine-grained sediments. At Sites 1108, 1109, 1118, 1116, and 1114, serpentinite and metamorphic grains (schist and gneiss) appear as detritus in sandstones younger than ~3 Ma. This is thought to reflect a major pulse of rifting that resulted in the deepening of the Woodlark rift basin and the prevention of terrigenous and metamorphic detritus from reaching the northern rift margin (Site 1115). The Paleogene Papuan ophiolite belt and the Owen Stanley metamorphics were unroofed as the southern margin of the rift was exhumed (e.g., Moresby Seamount) and, in places, subaerially exposed (e.g., D'Entrecasteaux Islands and onshore Cape Vogel Basin), resulting in new and more proximal sources of metamorphic, igneous, and ophiolitic detritus. Continued emergence of the Moresby Seamount during the late Pliocene-early Pleistocene bounded by a major inclined fault scarp yielded talus deposits of similar composition to the above sandstones. Upper Pliocene-Pleistocene sandstones were deposited at bathyal depths by turbidity currents and as subordinate air-fall ash. Silicic glassy (high-K calc-alkaline) volcanic fragments, probably derived from volcanic centers located in Dawson and Moresby Straits, dominated these sandstones.

Matrix elements of U(2n) generators in a multishell spin-orbit basis. III. General formulas

This is the third and final article in a series directed toward the evaluation of the U(2n) generator matrix elements (MEs) in a multishell spin/orbit basis. Such a basis is required for many-electron systems possessing a partitioned orbital space and where spin-dependence is important. The approach taken is based on the transformation properties of the U(2n) generators as an adjoint tensor operator of U(n) x U(2) and application of the Wigner-Eckart theorem. A complete set of adjoint coupling coefficients for the two-shell composite Gelfand-Paldus basis (which is appropriate to the many-electron problem) were obtained in the first and second articles of this series. Ln the first article we defined zero-shift coupling coefficients. These are proportional to the corresponding two-shell del-operator matrix elements. See P. J. Burton and and M. D. Gould, J. Chem. Phys., 104, 5112 (1996), for a discussion of the del-operator and its properties. Ln the second article of the series, the nonzero shift coupling coefficients were derived. Having obtained all the necessary coefficients, we now apply the formalism developed above to obtain the U(2n) generator MEs in a multishell spin-orbit basis. The methods used are based on the work of Gould et al. (see the above reference). (C) 1998 John Wiley & Sons, Inc.

Surface modification of metals by calcium carbonate thin films on a layer-by-layer polyelectrolyte matrix

A multilayer organic film containing poly(acrylic acid) and chitosan was fabricated on a metallic support by means of the layer-by-layer technique. This film was used as a template for calcium carbonate crystallization and presents two possible binding sites where the nucleation may be initiated, either calcium ions acting as counterions of the polyelectrolyte or those trapped in the template gel network formed by the polyelectrolyte chains. Calcium carbonate formation was carried out by carbon dioxide diffusion, where CO, was generated from ammonium carbonate decomposition. The CaCO3 nanocrystals obtained, formed a dense, homogeneous, and continuous film. Vaterite and calcite CaCO3 crystalline forms were detected. (c) 2007 Elsevier B.V All rights reserved.