Determination of 13C/12C Isotope Ratio in Alcohols of Different Origin by 1н Nuclei NMR-Spectroscopy

Russian Physics Journal - A new express method of indirect assessment of 13C/12C isotope ratio on 1H nuclei is developed to verify the authenticity of ethanol origin in alcohol-water-based fluids...     

Hansen Solubility Parameters in the Analysis of Solvent–Solvent Interactions by Inverse Gas Chromatography

The Flory–Huggins interaction parameters, for a solute with pure nonvolatile solvents and with binary mixtures of nonvolatile solvents were evaluated using Inverse Gas Chromatography (IGC) data at 403.15 K. The five solvents used have similar structure and nearly the same molar volume and their mixtures form regular solutions. The values were used to evaluate the Hansen solubility parameters (HSP) for the pure solvents and mixed solvent systems. The HSP are plotted as a function of composition of the polar solvent. The dispersion component, , and the polar component, , exhibited negative deviation whereas the hydrogen bonding component, , showed positive deviation in the four mixtures. However, the total solubility parameter was found to be almost linear with composition in the four binary systems. Further the total solubility parameter, , was used to calculate the molar excess heat of vaporization for the solvents (C78 + POH, C78 + PCN, C78 + TTF, and C78 + TMO) that was found to be negative for C78 (19,24-dioctadecyldotetracontane) + POH(18,23-dioctadecylhentetracontan-1-ol) and C78 + PCN(1-cyano-18,23-dioctadecylhentetracontane) systems and positive for C78 + TTF [19,24-bis(18,18,18-trifluorooctadecyl)-1,1,1,42,42,42-hexafluorodotetracontane), and C78 + TMO(17,22-bis-(16-methoxyhexadecyl)-1,38-dimethoxyoctatriacontane] and the other systems.     

Chemical Analysis of Historic Art and Painting Conservation Materials (19th and 20th Centuries) from the National Museum in Krakow by Gas Chromatography–Mass Spectrometry and Fourier Transform Infrared Spectroscopy

Chemical composition of varnishes Vernis a Tableaux Vibert by Lefranc & Cie, Schutzfirnis für Oelgemalde Schmincke's Retuschier-Firnis by Schmincke & Co. Düsseldorf, Tempera-Firnis by Schmincke & Co. Düsseldorf, Bernstein-Gemaldefirniss für Ludwig'sche Petroleumfarben by Dr. Schoenfeld Düsseldorf, and Vernis Martin Pour Laquer by Lefranc & Cie Paris; oil medium Copal en pâte by Duroziez; essential oils Oleum Cupressi by Polak & Schwarz and Oleum Calami by Polak & Schwarz; fixative for charcoal, crayons, and pastels Nr 840/4 by Iskra & Karmański; and restoring medium for paintings Prof. Dr. Büttner's Phobus by Schmincke Düsseldorf were analyzed with gas chromatography–mass spectrometry. The analyses were conducted to obtain information about the exact composition of these products, which are stored at the National Museum in Krakow and were used by conservators. The results of research facilitate understanding of processes used in paintings and planning methods for their conservation.     

Effect of preservation on the δ13C value of dissolved inorganic carbon in different types of water samples

Recent studies have shown that the stable carbon isotope compositions of dissolved inorganic carbon (δ¹³C_DIC) of water samples preserved with HgCl₂ and CuSO₄ vary. Furthermore, mercury and cuprum compounds are toxic to the human or biological system and require proper waste disposal. To test the effect of preservation on the δ¹³C value of DIC in different types of water samples, a set of water samples with different DIC concentrations was preserved using different methods, including preserving with inhibitors (CuSO₄ or HgCl₂), preserving under frozen conditions, filtering through a 0.4 μ m paper filter, and the DIC species precipitated in the form of solid BaCO₃. Our results show that δ¹³C_DIC values of the samples preserved with CuSO₄ and HgCl₂ become more positive with increased storage time. The δ¹³C_DIC of the water samples preserved under frozen conditions and the precipitated DIC as BaCO₃ are also more positive than original water samples. However, the δ¹³C values were relatively stable for up to 90 days in all water samples filtered through the 0.4 μ m paper filter and stored under cool conditions (0–4 °C). Therefore, we suggest that the better method for the storage of water samples is to filter the samples through a 0.4 μ m paper filter while out in the field and preserve them under cool conditions, thereby avoiding the use of preservatives.     

Determination of δ13 CV−PDB and δ15NAIR values of cocaine from a big seizure in Germany by stable isotope ratio mass spectrometry†

In this study, δ¹³C_{V? PDB} and δ¹⁵N_AIR values of 132 cocaine samples from a big seizure in Germany in 2002 were determined using elemental analyser isotope ratio mass spectrometry. The 1.2 tons of cocaine were packed in 1 kg packages and the cocaine bricks inside these packages showed certain logos. Twenty different logos could be identified. Results show a large variability among some samples, for δ¹⁵N_AIR values ranging from?17 to ?2 ‰. Furthermore, the possibility of linking samples with the same logo was checked. The results show that, in general, there is no relationship between the determined isotope ratio and a certain logo.     

The Effect of Diet Quality on δ(13)C and δ(15)N in the Tissues of Locusts, Locusta migratoria L

Abstract Locust nymphs were raised from hatching to adult locusts on either seedling wheat (C(3)) or maize (C(4)), to determine whether relative enrichments/depletions of (15)N and (13)C within body tissues are influenced by diet. The maize contained less hexose sugars and protein per gram than wheat. The isotopic spacing between the food and the whole insect was found to differ between the two diets. The lower quality maize diet showed an overall +5.1‰ enrichment in δ(15)N compared to + 2.8‰ for wheat, possibly due to increased fractionation due to protein recycling. The maize diet resulted in increased depletion in lipid and trehalose and depletion in chitin relative to diet. The results for both δ(15)N and δ(13)C suggest that substrate recycling was occurring on the low quality maize diet. Therefore diet quality determines the enrichment/depletion in δ(15)N and δ(13)C within organisms.     

δ13C and δD Values of Opuntia Atacamensis Depending on Different Environmental Conditions in the Atacama Desert of Northern Chile

Abstract

We analysed ¹³carbon and deuterium discrimination in Opuntia atacamensis Phil, at three different sites in the Atacama desert in Northern Chile: At the western Andean slopes, influenced by summer rainfall, in the very arid Chilean central valley, and at coastal fog mountains.

At the most arid site, the central valley, discrimination of ¹³C and D was less (δ-values less negative) and also discrimination more against deuterium. This is an aridity, not an altitude effect.

The differences in ¹³C content may be due to some carbon fixation via the C3 photosynthetic pathway at the more humid sites. Deuterium enrichment at the arid sites might be due to greater discrimination of HDO against H₂O during transpirational water loss.     

Study on the chemical composition features of Longquan celadon excavated from the Chuzhou site of Huai'an City in Jiangsu Province by EDXRF

A mass of Longquan celadon shards were excavated from the Chuzhou site of Huai'an City in Jiangsu Province, China. These celadon shards were fired during the period of the Late Yuan Dynasty to the Tianshun era of the Ming Dynasty, as identified by archaeologists at Nanjing Museum. In order to research the chemical composition features of this ancient celadon porcelain, energy dispersive X-ray fluorescence (EDXRF) for non-destructive analysis was used to determine the chemical composition of the porcelain body and glaze in these shards. The results indicate that Ti and Fe in the body of Longquan celadon are characteristic elements which can distinguish porcelain produced during the Late Yuan Dynasty from those produced in the Ming Dynasties. The results of the principal component analysis (PCA) show that different body and glaze raw materials were used for the production of porcelain in different periods and the raw materials of the body and glaze are also different for various vessel shapes. The chemical compositions in the porcelain body of civilian ware are slightly different. The imperial and civilian Longquan celadon porcelains produced during the Hongwu era to the Tianshun era of the Ming Dynasty are distinguishable by the MnO, Fe₂O₃, Rb₂O and SrO content in their porcelain glaze.     

Comparison of δ13C and δ18O from cellulose,whole wood,and resin-free whole wood from an old high elevation Pinus uncinata in the Spanish central Pyrenees*

δ¹³C and δ¹⁸O values from sapwood of a single Pinus uncinata tree, from a high elevation site in the Spanish Pyrenees, were determined to evaluate the differences between whole wood and resin-free whole wood. This issue is addressed for the first time with P. uncinata over a 38-year long period. Results are also compared with published isotope values of α-cellulose samples from the same tree. The differences in δ¹³C and δ¹⁸O between whole wood and resin-free whole wood vary within the analytical uncertainty of 0.3 and 0.5?‰, respectively, indicating that resin extraction is not necessary for sapwood of P. uncinata. Mean differences between cellulose and whole wood are 0.9?‰ (δ¹³C) and 5.0?‰ (δ¹⁸O), respectively. However, further analyses of different species and other sites are needed to evaluate whether the findings reported here are coherent more generally.     

Ecophysiological Studies on the Vegetation of Madagascar: A δ13C and δD Survey for Incidence of Crassulacean Acid Metabolism (Cam) Among Orchids From Montane Forests and Succulents from the Xerophytic Thorn-Bush

Abstract

The incidence of Crassulacean acid metabolism (CAM) in plants collected at various habitats in Madagascar was investigated by survey of carbon and hydrogen isotope ratios ((δ¹³C and δD values). In about 50% of the epiphytic orchids from evergreen higher and lower montane forests the δ¹³C values were indicative for CAM. The remainder of the species are presumably C₃ plants. In all samples of malagasy epiphytic leafless orchids comprising 9 species, the δ¹³C values suggest extreme CAM with CO₂ uptake proceeding entirely during the night. All terrestrial orchids collected in the lower montane forests obviously acquire external carbon by C₃-photosynthesis, whereas Lissochilus decaryi, a terrestrial orchid from the semi-arid south of Madagascar and various other species of this genus are CAM plants. This is the first report of CAM occurrence in sympodial terrestrial orchids.

Judged by the δ¹³C values, all succulents (mainly Didiereaceae, Euphorbiaceae, Crassulaceae and Asclepiadaceae) collected at the xerophytic thorn-bush of the semi-arid south perform pronounced CAM. Where it applies, our δ¹³C measurements in the thorn-bush succulents revealed values being practically identical with those found by K. Winter in samples of the same species collected at the same site nearly 10 years earlier. This shows extreme constancy over long duration of time in the mode of CAM performed by the succulents of the malagasy thorn-bush vegetation. Since the δ¹³C survey now comprises all 11 known species of the Didiereaceae, it is unequivocally clear that all members of this family are CAM plants. Most of the individuals of the species of the Didiereaceae grown in a glass-house had slightly more negative δ¹³C values compared with those grown at the natural stands suggesting some contribution of C₃-photosynthesis to carbon acquisition under the evaporatively less demanding glass-house conditions (and perhaps higher CO₂ concentrations in the gas phase).

Despite of the fact that the hydrogen isotope composition of meteoric waters depends to a large extent on the altitude and temperature-climate of the site where the concerned plants grow, it was found that in samples obtained in the cooler higher evergreen montane forest as well as in the warmer lower evergreen montane forest and the lowland thorn-bush of the hot, semiarid south of Madagascar the δ values found in the organic matter (δD^org) were in the same range (between about - 10‰ to about - 90‰). This suggests that in our case the hydrogen isotope compositions of the meteoric waters were of minor importance in bringing about the δD^org values found in the plants.     

Effect of different ratios of wheat to corn flour in the diet on the development and isotopic composition (δ13C, δ15N) of the red flour beetle Tribolium castaneum

The back-calculation of the diet is a common application of stable isotopes in animal ecology. The method is based on a predictable relation between the isotopic signature of the diet and the animal’s tissues. Frequently, the assumption of a constant difference in isotopic signatures (trophic shift) is made. Carbon isotopic ratios of C₃ and C₄ plants differ by approximately 10 ‰, making wheat (C₃-plant) and corn (C₄-plant) ideal materials for isotopic studies in nutritional ecology and especially for testing the back-calculation method. In this experiment, red flour beetles, Tribolium castaneum, were reared on wheat flour, corn flour and three different mixtures thereof, either in pure flour or with the addition of yeast inoculum or yeast grains. Development of T. castaneum on these experimental diets was monitored, and isotopic signatures of carbon and nitrogen in emerging adults were analysed. The values of trophic shift of C and N isotopes for wheat and corn flour were different, and the values for the mixtures did not correspond to those expected from a linear mixing model. The latter can be taken as an indication that the tiny larvae of T. castaneum may be capable of differentiating between particles of wheat and corn flour, making this animal model unsuitable for testing the back-calculation method.     

Effect of the Length and Pressure of a Gas Jet on Optical Harmonics Generation by 4.5-μm Femtosecond Laser Radiation of a Fe:ZnSe Laser System

JETP Letters - The effect of the length and pressure of an argon gas jet on low-order harmonics (5th, 7th, 9th, and 11th) generation by 4.5-μm femtosecond laser radiation of a Fe:ZnSe laser...     

Neutron Background from the (α, n) Reaction on 13C in the EDELWEISS-II experiment on direct search for weakly interacting particles of nonbaryonic cold dark matter

The purpose of the work is to evaluate the neutron background from an additional neutron source, the (α, n) reaction on ¹³C, in the polyethylene neutron shielding of the EDELWEISS-II experiment on the search for weakly interacting cold matter particles. The characteristic length of radon diffusion into polyethylene is obtained, the neutron energy spectrum is constructed, and the neutron flux from the (α, n) reaction is evaluated.     

On the significant relativistic heavy atom effect on 13C NMR chemical shifts of β- and γ-carbons in seleno- and telluroketones

Unexpectedly large ‘Heavy Atom on Light Atom’ (HALA) effects have been found in ¹³C NMR (Nuclear Magnetic Resonance) chemical shifts of β- and γ-carbons of seleno- and telluroketones established by means of the high-accuracy calculations of ¹³C NMR chemical shifts in three representative real-life compounds, 2,2,5,5-tetramethyl-3-cyclopentene-1-selone, selenofenchone and 1,1,3,3-tetramethyl-1,3-dihydro-2H-indene-2-tellurone. The proposed computational scheme consists of the combination of accurately correlated coupled-cluster singles and doubles model approach for the non-relativistic calculations of shielding constants taking into account the solvent, vibrational and relativistic corrections, the latter obtained within the 4-component fully relativistic gauge-including atomic orbitals KT2 approach resulting in a very good agreement of the performed calculations with the experiment. The stereochemical dependence of the ‘long-range’ γ-HALA effect on the dihedral angle has been established in the model seleno- and telluroketones providing the largest shielding effect in the orthogonal orientation of the X=C_α–C_β–C_γ (X=Se, Te) moiety.     

Neutralization of an ion beam from the end-Hall ion source by a plasma electron source based on a discharge in crossed E × H fields

The possibility of using a plasma electron source (PES) with a discharge in crossed E × H field for compensating the ion beam from an end-Hall ion source (EHIS) is analyzed. The PES used as a neutralizer is mounted in the immediate vicinity of the EHIS ion generation and acceleration region at 90° to the source axis. The behavior of the discharge and emission parameters of the EHIS is determined for operation with a filament neutralizer and a plasma electron source. It is found that the maximal discharge current from the ion source attains a value of 3.8 A for operation with a PES and 4 A for operation with a filament compensator. It is established that the maximal discharge current for the ion source strongly depends on the working gas flow rate for low flow rates (up to 10 ml/min) in the EHIS; for higher flow rates, the maximum discharge current in the EHIS depends only on the emissivity of the PES. Analysis of the emission parameters of EHISs with filament and plasma neutralizers shows that the ion beam current and the ion current density distribution profile are independent of the type of the electron source and the ion current density can be as high as 0.2 mA/cm² at a distance of 25 cm from the EHIS anode. The balance of currents in the ion source-electron source system is considered on the basis of analysis of operation of EHISs with various sources of electrons. It is concluded that the neutralization current required for operation of an ion source in the discharge compensation mode must be equal to or larger than the discharge current of the ion source. The use of PES for compensating the ion beam from an end-Hall ion source proved to be effective in processes of ion-assisted deposition of thin films using reactive gases like O₂ or N₂. The application of the PES technique makes it possible to increase the lifetime of the ion-assisted deposition system by an order of magnitude (the lifetime with a Ti cathode is at least 60 h and is limited by the replacement life of the deposited cathode insertion).