Radionuclides measured on three sediment cores from the Weddell Sea, Antarctica

High resolution 230Thex and 10Be and biogenic barium profiles were measured at three sediment gravity cores (length 605-850 cm) from the Weddell Sea continental margin. Applying the 230Thex dating method, average sedimentation rates of 3 cm/kyr for the two cores from the South Orkney Slope and of 2.4 cm/kyr for the core from the eastern Weddell Sea were determined and compared to delta18O and lithostratigraphic results. Strong variations in the radionuclide concentrations in the sediments resembling the glacial/interglacial pattern of the delta18O stratigraphy and the 10Be stratigraphy of high northern latitudes were used for establishing a chronostratigraphy. Biogenic Ba shows a pattern similar to the radionuclide profiles, suggesting that both records were influenced by increased paleoproductivity at the beginning of the interglacials. However, 230Thex0 fluxes (0 stands for initial) exceeding production by up to a factor of 4 suggest that sediment redistribution processes, linked to variations in bottom water current velocity, played the major role in controlling the radionuclide and biogenic barium deposition during isotope stages 5e and 1. The correction for sediment focusing makes the 'true' vertical paleoproductivity rates, deduced from the fluxes of proxy tracers like biogenic barium, much lower than previously estimated. Very low 230Thex0 concentrations and fluxes during isotope stage 6 were probably caused by rapid deposition of older, resedimented material, delivered to the Weddell Sea continental slopes by the grounded ice shelves and contemporaneous erosion of particles originating from the water column.

Growth rates and possible age of a North Pacific manganese nodule

The rate of accumulation of a ferromanganese coating on a fragment of pillow basalt was estimated using a variety of techniques. Unsupported 230 Th activity decrease in the oxide layer, K/A dating of the basalt, fission tracks dating of the glassy layer around the basalt, thickness of the palagonitization rind, and integrated 230 Th activity give ages from approximately 3 x 10-6 years to 5 x 10-3 years. Data suggest that the ferromanganese material formed rapidly (33 mm/10-6 years) and by hydrothermal or volcanic processes.

Potassium and Argon data for dating the core, and radiochemical data of a series of measurements made on layers inside various manganese nodules from the Pacific Ocean

Although various models have been proposed to explain the origin of manganese nodules (see Goldberg and Arrhenius), two major hypotheses have received extensive attention. One concept suggests that manganese nodules form as the result of interaction between submarine volcanic products and sea water. The common association of manganese nodules with volcanic materials constitutes the main evidence for this theory. The second theory involves a direct inorganic precipitation of manganese from sea water. Goldberg and Arrhenius view this process as the oxidation of divalent manganese to tetravalent manganese by oxygen under the catalytic action of particulate iron hydroxides. Manganese accumulation by the Goldberg and Arrhenius theory would be a relatively slow and comparatively steady process, whereas Bonatti and Nayudu believe manganese nodule formation takes place subsequent to the eruption of submarine volcanoes by the acidic leaching of lava.

Radiological characterization of clay mixed red mud in particular as regards its leaching features

The reuse of industrial by-products such as red mud is of great importance. In the case of the building material industry the reuse of red mud requires a cautious attitude, since the enhanced radionuclide content of red mud can have an effect on human health. The natural radionuclide content of red mud from the Ajka red mud reservoir and the clay sample from a Hungarian brick factory were determined by gamma spectrometry. It was found that maximum 27.8% red mud content can be added to fulfil the conditions of the EU-BSS. The effect of heat treatment was investigated on a red mud-clay mixture and it was found that in the case of radon and thoron exhalation the applied heat reduced remarkably the exhalation capacities. The leaching features of red mud and different mixtures were studied according to the MSZ-21470-50 Hungarian standard, the British CEN/TS 14429 standard and the Tessier sequential extraction method. The Tessier method and the MSZ-21470-50 standard are suitable for the characterization of materials; however, they do not provide enough information for waste deposition purposes. To this end, we propose using the CEN/TS 14429 method, because it is easy to use, and gives detailed information about the material's behaviour under different pH conditions, however, further measurements are necessary.

Determination of 210Po content of vietnamese tobacco samples

Smoking is one of the leading causes of preventable death. In recent years, numerous countries have initiated the prohibition of smoking in restaurants, workplaces and public spaces. The Vietnamese government intends to follow the precautions against public smoking as well. Over and above the number of some hazardous chemical components found in tobacco, ²¹⁰Po isotope content could enhance the probability of the development of lung cancer. In this study 14 Vietnamese tobacco products (commercial cigarettes and pipe tobacco) ²¹⁰Po activity concentration were determined using PIPS semiconductor alpha spectrometry. The results showed that the 210Po activity concentration of the investigated samples varied between 7.40 ± 1.09 - 128.64 ± 11.22 mBq g^-1. The average ²¹⁰Po content of commercial cigarettes was 15.5 mBq g^-1, whilst the average of pipe tobacco was 20.4 mBq g^-1. To estimate the risk of inhalation of ²¹⁰Po isotopes originating as a result of smoking, dose estimations were carried out. © Versita Sp. z o.o.

Detection of alpha(2u)-globulin and its bound putative pheromones in the preputial gland of the Indian commensal rat (Rattus rattus) using mass spectrometry

The role of pheromones and pheromone-binding proteins in the laboratory rat has been extensively investigated. However, we have previously reported that the preputial gland of the Indian commensal rat produces a variety of pheromonal molecules and preputial glands would seem to be the predominant source for pheromonal communication. The presence of pheromone-binding proteins has not yet been identified in the preputial gland of the Indian commensal rat; therefore, the experiments were designed to unravel the alpha(2u)-globulin (alpha 2u) and its bound volatiles in the commensal rat. Total preputial glandular proteins were first fractionated by sodium dodecyl sulfate/polyacrylamide gel electrophoresis (SDS-PAGE) and subsequently analyzed by mass spectrometry. Further, we purified alpha 2u and screened for the presence of bound pheromonal molecules with the aid of gas chromatography/mass spectrometry (GC/MS). A novel alpha 2u was identified with a high score and this protein has not been previously described as present in the preputial gland of Indian commensal rats.This novel alpha 2u was then characterized by tandem mass spectrometry (MS/MS). Peptides with m/z values of 969, 1192, 1303 and 1876 were further fragmented with the aid of MS/MS and generated de novo sequences which provided additional evidence for the presence of alpha 2u in the preputial gland. Finally, we identified the presence of farnesol 1 and 2 bound to alpha 2u. The present investigation confirms the presence of alpha 2u (18.54 kDa) in the preputial gland of the Indian commensal rat and identifies farnesol 1 and 2 as probably involved in chemo-communication by the Indian commensal rat.Copyright (C) 2010 John Wiley & Sons, Ltd.

Chemical functionalities of high and low sulfur Australian coals : a case study using micro attenuated total reflectance–fourier transform infrared (ATR–FTIR) spectrometry

The macerals in bituminous coals with varying organic sulfur content from the Early Permian Greta Coal Measures at three locations (Southland Colliery, Drayton Colliery and the Cranky Corner Basin), in and around the Sydney Basin (Australia), have been studied using light-element electron microprobe (EMP) analysis and micro-ATR–FTIR. Electron microprobe analysis of individual macerals reveals that the vitrinite in both the Cranky Corner Basin and Drayton Colliery (Puxtrees seam) samples have similar carbon contents (ca. 78% C in telocollinite), suggesting that they are of equivalent rank. However, the Cranky Corner coals have anomalously low vitrinite reflectance (down to 0.45%) vs. the Drayton materials (ca. 0.7%). They also have very high organic S content (3–6.5%) and lower O content (ca. 10%) than the equivalent macerals in the Drayton sample (0.7% S and 15.6% O). A study was carried out to investigate the impacts of the high organic S on the functional groups of the macerals in these two otherwise iso-rank, stratigraphically-equivalent seams. An iso-rank low-S coal from the overlying Wittingham Coal Measures near Muswellbrook and coals of slightly higher rank from the Greta Coal Measures at Southland Colliery near Cessnock were also evaluated using the same techniques to extend the data set. Although the telocollinite in the Drayton and Cranky Corner coals have very similar carbon content (ca.78% C), the ATR–FTIR spectra of the vitrinite and inertinite macerals in these respectively low S and high S coals show some distinct differences in IR absorbance from various aliphatic and aromatic functional groups. The differences in absorbance of the aliphatic stretching bands (2800–3000 cm−1) and the aromatic carbon (CC) peak at 1606 cm−1 are very obvious. Compared to that of the Drayton sample (0.7% S and 15% O), the telocollinite of the Cranky Corner coal (6% S and 10% O) clearly shows: (i) less absorbance from OH groups, represented by a broad region around 3553 cm−1, (ii) much stronger aliphatic C–H absorbance (stretching modes around 3000–2800 cm−1 and bending modes around 1442 cm−1) and (iii) less absorbance from aromatic carbon functional groups (peaking at 1606 cm−1). Evaluation of the iso-rank Drayton and Cranky Corner coals shows that: (i) the aliphatic C–H absorbances decrease with increasing oxygen content but increase with increasing organic S content and (ii) the aromatic H to aliphatic H ratio (Har/Hali) for the telocollinite increases with (organic) O%, but decreases progressively with increasing organic S. The high organic S content in the maceral appears to be accompanied by a greater proportion of aliphatic functional groups, possibly as a result of some of the O within maceral ring structures in the high S coal samples being replaced.

Tandem mass spectrometry of deprotonated iodothyronines

In order to assist with the development of more selective and sensitive methods for thyroid hormone analysis the \[M-H](-) anions of the iodothyronines T4, T3, rT3, (3,5)-T2 and the non-iodinated thyronine (TO) have been generated by negative ion electrospray mass spectrometry. Tandem mass spectra of these ions were recorded on a triple-quadrupole mass spectrometer and show a strong analogy with the fragmentation pathways of the parent compound, tyrosine. All iodothyronines also show significant abundances of the iodide anion in their tandem mass spectra, which represents an attractive target for multiple reaction monitoring (MRM) analysis, given that iodothyronines are the only iodine bearing endogenous molecules. Characteristic fragments are observed at m/z 359.7 and 604.5 for rT3 but are absent in the spectrum of T3, thus differentiating the two positional isomers. The striking difference in the fragmentation patterns of these regioisomeric species is attributed to the increased acidity of the phenol moiety in rT3 compared with T3. Copyright (C) 2005 John Wiley & Sons, Ltd.

Analysis of the extreme diversity of salivary alpha-amylase isoforms generated by physiological proteolysis using liquid chromatography-tandem mass spectrometry

Saliva is a crucial biofluid for oral health and is also of increasing importance as a non-invasive source of disease biomarkers. Salivary alpha-amylase is an abundant protein in saliva, and changes in amylase expression have been previously associated with a variety of diseases and conditions. Salivary alpha-amylase is subject to a high diversity of post-translational modifications, including physiological proteolysis in the oral cavity. Here we developed methodology for rapid sample preparation and non-targeted LC-ESI-MS/MS analysis of saliva from healthy subjects and observed an extreme diversity of alpha-amylase proteolytic isoforms. Our results emphasize the importance of consideration of post-translational events such as proteolysis in proteomic studies, biomarker discovery and validation, particularly in saliva. (C) 2012 Elsevier B.V. All rights reserved.

Identification of alpha- and beta-Hydroxy Acid Containing Cyclodepsipeptides in Natural Peptide Mixtures Using Negative Ion Mass Spectrometry

Natural peptide libraries often contain cyclodepsipeptides containing alpha or beta hydroxy residues. Extracts of fungal hyphae of Isaria yield a microheterogenous cyclodepsipeptide mixture in which two classes of molecules can be identified by mass spectral fragmentation of negative ions. In the case of isaridins, which contain an alpha-hydroxy residue and a beta-amino acid residue, a characteristic product ion corresponding to a neutral loss of 72 Da is obtained. hi addition, neutral loss of water followed by a 72 Da loss is also observed. Two distinct modes of fragmentation rationalize the observed product ion distribution. The neutral loss of 72 Da has also been obtained for a roseotoxin component, which is also an alpha-hydroxy residue containing cyclodepsipeptide. In the case of isariins, which contain a beta-hydroxy acid residue, ring opening and subsequent loss of the terminal residue as an unsaturated ketene fragment, rationalizes the observed product ion formation. Fragmentation of negative ions provide characteristic neutral losses, which are diagnostic of the presence of alpha-hydroxy or beta-hydroxy residues.