Carbon and nitrogen stable isotope ratio analysis of freshwater, brackish and marine fish from Belgian archaeological sites (1st and 2nd millennium AD)

Carbon and nitrogen stable isotope ratios were measured in 157 fish bone collagen samples from 15 different archaeological sites in Belgium which ranged in ages from the 3rd to the 18th c. AD. Due to diagenetic contamination of the burial environment, only 63 specimens produced results with suitable C:N ratios (2.9–3.6). The selected bones encompass a wide spectrum of freshwater, brackish, and marine taxa (N = 18), and this is reflected in the δ13C results (−28.2‰ to −12.9%). The freshwater fish have δ13C values that range from −28.2‰ to −20.2‰, while the marine fish cluster between −15.4‰ and −13.0‰. Eel, a catadromous species (mostly living in freshwater but migrating into the sea to spawn), plots between −24.1‰ and −17.7‰, and the anadromous fish (living in marine environments but migrating into freshwater to spawn) show a mix of freshwater and marine isotopic signatures. The δ15N results also have a large range (7.2‰ to 16.7‰) indicating that these fish were feeding at many different trophic levels in these diverse aquatic environments. The aim of this research is the isotopic characterization of archaeological fish species (ecology, trophic level, migration patterns) and to determine intra-species variation within and between fish populations differing in time and location. Due to the previous lack of archaeological fish isotope data from Northern Europe and Belgium in particular, these results serve as an important ecological backdrop for the future isotopic reconstruction of the diet of human populations dating from the historical period (1st and 2nd millennium AD), where there is zooarchaeological and historical evidence for an increased consumption of marine fish.

In situ preservation of wetland heritage: hydrological and chemical change in the burial environment of the Somerset Levels, UK.

In Situ preservation is a core strategy for the conservation and management of waterlogged remains at wetland sites. Inorganic and organic remains can, however, quickly become degraded, or lost entirely, as a result of chemical or hydrological changes. Monitoring is therefore crucial in identifying baseline data for a site, the extent of spatial and or temporal variability, and in evaluating the potential impacts of these variables on current and future In Situ preservation potential. Since August 2009, monthly monitoring has taken place at the internationally important Iron Age site of Glastonbury Lake Village in the Somerset Levels, UK. A spatial, stratigraphic, and analytical approach to the analysis of sediment horizons and monitoring of groundwater chemistry, redox potential, water table depth and soil moisture (using TDR) was used to characterize the site. Significant spatial and temporal variability has been identified, with results from water-table monitoring and some initial chemical analysis from Glastonbury presented here. It appears that during dry periods parts of this site are at risk from desiccation. Analysis of the chemical data, in addition to integrating the results from the other parameters, is ongoing, with the aim of clarifying the risk to the entire site.

Interaction of anthocyanins with human serum albumin: influence of pH and chemical structure on binding

The affinity of anthocyanins for human serum albumin (HSA) was determined by a fluorescence quenching method. The effects of pH and structure of anthocyanins on the binding constants were studied. The constants for binding of anthocyanins to HSA ranged from 1.08 x 10^5 M-1 to 13.16 x 10^5 M-1. A hydrophobic effect at acidic pH was shown by the relatively high positive entropy values under the conditions studied. Electrostatic interactions including hydrogen bonding contributed to the binding at pH 7.4. The effect of structure of anthocyanins on the affinity was pH dependent, particularly the effect of additional hydroxyl substituents. Hydroxyl substituents and glycosylation of anthocyanins decreased the affinity for binding to HSA at lower pH (especially pH 4), but increased the strength of binding at pH 7.4. In contrast, methylation of a hydroxyl group enhanced the binding at acidic pH, while this substitution reduced the strength of binding at pH 7.4. This paper has shown that changes in anthocyanin structure or reductions in pH, which may occur in the region of inflammatory sites, have an effect of the binding of anthocyanins to HSA.

Effects of high hydrostatic pressure and chemical reduction on the emulsification properties of gum arabic

Gum arabic is widely used in the food industry as an additive, both as a thickener and an emulsifier. This study has compared the emulsification properties of two types of gums, KLTA (Acacia senegal) and GCA (Acacia seyal), both in their native/untreated forms and after exposure to high pressure (800 MPa). Further studies were undertaken to chemically modify the disulphide linkages present and to investigate the effects of their reduction on the diffusion of the carbohydrate materials. The emulsification properties of the gum samples were examined by determining the droplet size distribution in a ‘‘model’’ oil-in-water system. Results showed that high pressure treatment and chemical reduction of gums changed the emulsification properties of both gums. The high molecular weight component in arabinogalactanproteins (AGP/GP), and more ‘‘branched’’ carbohydrates present in gum arabic, may be responsible for the emulsification properties of GCA gum, indicating that the emulsification mechanisms for KLTA and GCA were different.

Diet and lifestyle in Bronze Age Northwest Spain: the collective burial of Cova do Santo

A multidisciplinary investigation of the collective burial of Cova do Santo is presented as a novel approach to understand daily life during the Bronze Age in Northwest Iberia. The research is focused on three main aspects: i) taphonomy and patterns of disposal, ii) paleopathology and -demography as indicators of health status and lifestyle, and iii) stable isotope analysis to reconstruct paleodiet and to investigate the timing of the introduction of millet to the Iberian Peninsula. Osteological analyses were performed on 64 bones (61 human and 3 animal); additionally, bone collagen was extracted from 15 samples (13 human and 2 animal) and analyzed for its carbon and nitrogen stable isotopes composition. The radiocarbon age of the human remains is consistent with the Middle Bronze Age (c. 1890 to 1600 cal BC). The recovered remains belonged to a minimum number of 14 individuals with an estimated age at death of forty years or younger. This relatively young age is in contrast to a high prevalence of degenerative joint disease in the group. The isotopic results suggest a very homogeneous diet, which was almost exclusively based on C3 plants and terrestrial animal products. Overall, the data suggest that the studied population belonged to a period prior to the introduction of spring or summer-grown crops such as millets. The collective burial from the cave of Cova de Santo, Galicia, currently represents the largest assemblage of prehistoric human remains from Northwest Spain and the relatively good preservation of the bones offers a unique opportunity to investigate daily life in Northern Iberia during the Bronze Age.

PHYSICAL AND CHEMICAL CHARACTERISTICS OF FROZEN GROUND BEEF AND AGED BEEF MEAT FROM BOS INDICUS STEERS SUPPLEMENTED WITH alpha-TOCOPHEROL ACETATE

The objective of this study was to evaluate the effects of diet supplementation with vitamin E on the physical and chemical characteristics of ground, frozen and stored or aged Quadriceps femoris (QF) and Longissimus dorsi (LD) muscles from Nellore steers fed high concentrate diets. Muscles were obtained from 24 animals that were 30 months old with a mean live weight of 279 kg. Half of the animals received daily doses of 1,000 mg of alpha-tocopherol acetate (VIT E) per head per day that was added to 100 g of corn meal. The other half received 100 g of corn meal without the antioxidant. Twenty-four hours after slaughtering, QF samples from each animal were ground, frozen and stored for up to 6 months. In addition, 4 samples from the LD of each animal were vacuum packed individually and kept for 21 days. All samples were analyzed to determine the pH, color and water-holding-capacity. The VIT E supplementation improved only the water loss characteristics of frozen ground QF and did not have any positive effect on the physical-chemical characteristics of the aged LD.

Anisotropy and chemical composition of ultra-high energy cosmic rays using arrival directions measured by the Pierre Auger Observatory

The Pierre Auger Collaboration has reported. evidence for anisotropy in the distribution of arrival directions of the cosmic rays with energies E > E(th) = 5.5 x 10(19) eV. These show a correlation with the distribution of nearby extragalactic objects, including an apparent excess around the direction of Centaurus A. If the particles responsible for these excesses at E > E(th) are heavy nuclei with charge Z, the proton component of the sources should lead to excesses in the same regions at energies E/Z. We here report the lack of anisotropies in these directions at energies above E(th)/Z (for illustrative values of Z = 6, 13, 26). If the anisotropies above E(th) are due to nuclei with charge Z, and under reasonable assumptions about the acceleration process, these observations imply stringent constraints on the allowed proton fraction at the lower energies.

Polymethine cyanine dyes in beta-cyclodextrin solution: multiple equilibria and chemical oxidation

Absorption and fluorescence spectroscopy, electrochemical techniques, and semiempirical calculations were employed to characterize the multiple complexation equilibria between two polymethine cyanine dyes (IR-786 and Indocyanine green-ICG, 5) and beta-cyclodextrin (beta-CD, L), as well as the chemical reactivity of the complexed and uncomplexed species against the oxidizing agents hypochlorite (HC) and hydrogen peroxide (HP). IR-786 dimerization is favored with the increase in beta-CD concentration in the form of (SL)(2) complexes. In the case of ICG, free dimers (D) and SL complexes are favored. Both IR-786 and ICG react and discolor in the presence of HC and HP. For IR-786, the reaction with HP and HC proceeds with observed rate constants of 10(-3) and 0.28 s(-1) and second-order rate constants (k(2)) of similar to 10(-3) and 10(4) M(-1) s(-1), respectively. The intermediate species observed in the bleaching reactions of IR-786 and ICG were shown, by cyclic voltammetry and VIS absorption, to result from one electron oxidation. IR-786 complexed with beta-CD is protected against bleaching in the presence of HP and HC by factors of 20 and 4, respectively. This protection was not observed in ICG complexes. Superdelocalizability profile of both dyes and frontier orbital analysis indicates that beta-CD does not protect ICG from oxidation by HP or HC, whereas the 2:2 IR-786/beta-Cd complex is able to avoid the oxidation of IR-786. We concluded that the decrease in the chemical reactivity of the dyes against oxidant agents in the presence of beta-CD is due to the formation of (SL)(2) complexes. Copyright (C) 2010 John Wiley & Sons, Ltd.

Electronic structure and chemical bonding in W(2) molecule

The electronic structure of the lowest-lying electronic states of W(2) were investigated at the CASPT2 level. The ground state is a X(1)Sigma(+)(g) state, followed by the a(3)Delta(u), b(3)Sigma(+)(u) and A(1)Delta(u) electronic states. Seven low-lying Omega-states were computed: (1)0(g)(+), (2)3(u), (3)2(u), (4)1(u), (5)0(u)(-), (6)1(u), and (7)2(u), with the ground state corresponding to the (1)0(g)(+)(X(1)Sigma(+)(g)) state. Comparison with the other VIB transition metal group dimers indicates a common pattern of electronic structure and spectroscopic properties. (C) 2010 Elsevier B.V. All rights reserved.

Electronic Structure and Chemical Bonding in the Lowest Electronic States of TcN

Multiconfiguration second-order perturbation theory, with the inclusion of relativistic effects and spin-orbit Coupling, was employed to investigate the nature of the ground and low-lying Lambda-S and Omega states of the TcN molecule. Spectroscopic constants, effective bond order, and potential energy curves for 13 low-lying Lambda-S states and 5 Omega states are given, The computed ground state of TcN is of Omega = 3 symmetry (R(e) = 1.605 angstrom and omega(e) = 1085 cm(-1)), originating mainly from the (3)Delta Lambda-S ground state. This result is contrasted with the nature of the ground state for other VIIB transtion-metal mononitrides, including X(3)Sigma(-) symmetry for MnN and Omega = 0(+) symmetry for ReN, derived also from a X(3)Sigma(-) state.

Electronic structure and chemical bonding in the ground states of Tc(2) and Re(2)

Multiconfiguration second-order perturbation theory, including relativistic effects and spin-orbit coupling, has been employed to investigate the nature of the chemical bonding in the ground state of Tc(2) and Re(2). The Tc(2) ground state is found to be a 0(g)(+) state, with an effective bond order (EBO) of 4.4, and a dissociation energy of 3.25 eV. The Re(2) ground state is a 1(g) state, with EBO = 4.3. Almost degenerate to it, is a 0(g)(+) state (T(e) = 77 cm(-1)), with EBO = 4.1. Experimental evidence also indicates that the ground state is of 1(g) nature. The dissociation energy is computed to be 5.0 eV in agreement with an experimental estimate of 4 +/- 1 eV.

Electronic Structure and Chemical Bonding in the Ground and Low-Lying Electronic States of Ta(2)

The electronic structure and chemical bonding of the ground and low-lying Lambda - S and Omega states of Ta(2) were investigated at the multiconfiguration second-order perturbation theory (CASSCF//CASPT2) level. The ground state of Ta(2) is computed to be a X(3)Sigma(-)(g) state (R(e) = 2.120 angstrom, omega(e) = 323 cm(-1), and D(e) = 4.65 eV), with two low-lying singlet states close to it (a(1) Sigma(+)(g) : T(e) = 409 cm(-1), R(e) = 2.131 angstrom, and omega(e) = 313 cm(-1); b(1) Gamma(g): T(e) = 1, 038 cm(-1), R(e) = 2.127 angstrom, and omega(e) = 316 cm(-1)). These electronic states are derived from the same electronic configuration: vertical bar 13 sigma(2)(g)14 sigma(2)(g)7 delta(2)(g)13 pi(4)(u)>. The effective bond order of the X(3) Sigma(-)(g) state is 4.52, which indicates that the Ta atoms are bound by a quintuple chemical bond. The a(1) Sigma(+)(g) state interacts strongly with the X(3)Sigma(-)(g) g ground state by a second-order spin-orbit interaction, giving rise to the (1)0(g)(+) (ground state) (dominated by the X(3)Sigma(-)(g) Lambda - S ground state) and (9)0(g)(+) (dominated by the a(1) Sigma(+)(g) Lambda - S state) Omega states. These results are in line with those reported for the group 5B homonuclear transition metal diatomics. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 111: 1306-1315, 2011