Microwave-supported preparation of alpha-cellulose for analysis of delta13C in tree rings

The microwave technique is found to be very applicable for the preparation of alpha-cellulose from wood samples and can be recommended for analyzing the stable carbon isotopes in tree rings. At a reaction temperature of 80 degrees C, the extraction time can be decreased from 36 h to 15 min. Microwave-supported prepared cellulose contains more amorphous constituents, resulting in a relatively higher reactivity and amenability for a following nitration with regard to determination of nonexchangeable hydrogen. The delta18O values of microwave-enhanced extracted cellulose remain significantly lighter than reference values, possibly as a result of an increased oxygen isotope exchange between bleaching solution and cellulose under conditions of high energy input. Therefore, this technique cannot be recommended for oxygen isotope analyses in wood cellulose.     

High-precision continuous-flow measurement of delta13C and deltaD of atmospheric CH4

We describe our development of a CH4 preconcentration system for use with continuous-flow gas chromatograph combustion isotope ratio mass spectrometry (GC/C/IRMS). Precision of measurement of delta13C-CH4 is 0.05/1000 (1sigma) on multiple 60-mL aliquots of the same ambient air sample. The same front-end on-line CH4 preconcentration system allows us to measure deltaD of CH4 by gas chromatography IRMS when the combustion furnace is replaced with a pyrolysis oven (GC/P/IRMS). Precision of measurement for deltaD-CH4 is 1.5/1000 (1sigma) using 120 mL of ambient air based on multiple aliquots of the same air sample. These are the first reported measurements of atmospheric CH4 using GC/P/IRMS methodology. Each isotope analysis can be made much more rapidly (30-40 min) than they could using off-line combustion of an air sample (1-6 h) followed by conventional dual-inlet IRMS measurements (12-20 min), while requiring much less total volume and retaining a comparable level of precision and accuracy. To illustrate the capabilities of our preconcentration GC/C/IRMS system, we compare the results of measurement of 24 background air samples made using both GC/C/IRMS and conventional vacuum line/dual-inlet IRMS methodology. The air samples were collected on a shipboard air sampling transect made across the Pacific Ocean in July 2000 and are part of an ongoing atmospheric CH4 research program. The average difference between the two methods of IRMS analyses on these 24 samples is 0.01 +/- 0.03/1000 (95% confidence interval) for delta3C-CH4. These are the first measurements to be reported of air samples directly intercompared for delta13C-CH4 using both GC/C/IRMS and dual-inlet IRMS measurement methodology. Measurement of deltaD-CH4 of these air samples is also presented as an illustration of the ability of this system to resolve small isotopic differences in remote air. High-precision measurement of delta13C and deltaD of atmospheric CH4 made using our coupled preconcentration GC/IRMS system will greatly improve our ability to utilize isotopic data in understanding spatial and temporal changes in atmospheric CH4 and the biogeochemistry of its sources and sinks.     

Comparative analysis of cellulose preparation techniques for use with 13C, 14C, AND 18O isotopic measurements

A number of operationally defined methods exist for pretreating plant tissues in order to measure C, N, and O isotopes. Because these isotope measurements are used to infer information about environmental conditions that existed at the time of tissue growth, it is important that these pretreatments remove compounds that may have exchanged isotopes or have been synthesized after the original formation of these tissues. In stable isotope studies, many pretreatment methods focus on isolating "cellulose" from the bulk tissue sample because cellulose does not exchange C and O isotopes after original synthesis. We investigated the efficacy of three commonly applied pretreatment methods, the Brendel method and two variants of the Brendel method, the Jayme-Wise method and successive acid/base/acid washes, for use on three tissue types (wood, leaves, roots). We then compared the effect of each method on C and O isotope composition (13C, 14C, 18O), C and N content, and chemical composition of the residue produced (using 13C nuclear magnetic resonance (NMR)). Our results raised concerns over use of the Brendel method as published, as it both added C and N to the sample and left a residue that contains remnant lipids and waxes. Furthermore, this method resulted in 18O values that are enriched relative to the other methods. Modifying the Brendel method by adding a NaOH step (wash) solved many of these problems. We also found that processed residues vary by tissue type. For wood and root tissues, the 13C NMR spectra and the 18O and 13C data showed only small differences between residues for the Jayme-Wise and modified Brendel methods. However, for leaf tissue, 13C NMR data showed that Jayme-Wise pretreatments produced residues that are more chemically similar to cellulose than the other methods. The acid/base/acid washing method generated 13C NMR spectra with incomplete removal of lignin for all tissues tested and both isotopic, and 13C NMR results confirmed that this method should not be used if purified cellulose is desired.     

Magnetic susceptibility measurements in PrBe13

The temperature dependent complex magnetic susceptibility of the Van Vleck paramagnet PrBe ₁₃ has been measured at temperatures below 20 mK in zero magnetic field. We observe an antiferromagnetic Curie-Weiss behaviour of the nuclear spin susceptibility with a Weiss temperature = -2.2 mK.     

Wood cellulose preparation methods and mass spectrometric analyses of delta13C, delta18O, and nonexchangeable delta2H values in cellulose, sugar, and starch: an interlaboratory comparison

Interlaboratory comparisons involving nine European stable isotope laboratories have shown that the routine methods of cellulose preparation resulted in data that generally agreed within the precision of the isotope ratio mass spectrometry (IRMS) method used: +/-0.2 per thousand for carbon and +/-0.3 per thousand for oxygen. For carbon, the results suggest that holocellulose is enriched up to 0.39 per thousand in 13C relative to the purified alpha-cellulose. The comparisons of IRMS measurements of carbon on cellulose, sugars, and starches showed low deviations from -0.23 to +0.23 per thousand between laboratories. For oxygen, IRMS measurements varied between means from -0.39 to 0.58 per thousand, -0.89 to 0.42 per thousand, and -1.30 to 1.16 per thousand for celluloses, sugars, and starches, respectively. This can be explained by different effects arising from the use of low- or high-temperature pyrolysis and by the variation between laboratories in the procedures used for drying and storage of samples. The results of analyses of nonexchangeable hydrogen are very similar in means with standard deviations between individual methods from +/-2.7 to +/-4.9 per thousand. The use of a one-point calibration (IAEA-CH7) gave significant positive offsets in delta2H values up to 6 per thousand. Detailed analysis of the results allows us to make the following recommendations in order to increase quality and compatibility of the common data bank: (1) removal of a pretreatment with organic solvents, (2) a purification step with 17% sodium hydroxide solution during cellulose preparation procedure, (3) measurements of oxygen isotopes under an argon hood, (4) use of calibration standard materials, which are of similar nature to that of the measured samples, and (5) using a two-point calibration method for reliable result calculation.     

New seeding methodology for gas concentration measurements

This paper presents the first demonstration of the pulsed laser ablation technique to seed a laminar non-reacting gaseous jet at atmospheric pressure. The focused, second harmonic from a pulsed Nd : YAG laser is used to ablate a neutral indium rod at atmospheric pressure and temperature. The ablation products generated with the new seeding method are used to seed the jet, as a marker of the scalar field. The neutral indium atoms so generated are found to be stable and survive a convection time of the order of tens of seconds before entering the interrogation region. The measurements of planar laser-induced fluorescence (PLIF) with indium and laser nephelometry measurements with the ablation products are both reported. The resulting average and root mean square (RMS) of the measurements are found to agree reasonably well although some differences are found. The results show that the pulsed laser ablation method has potential to provide scalar measurement for mixing studies.     

Development of N-acetyl methyl ester derivatives for the determination of delta13C values of amino acids using gas chromatography-combustion- isotope ratio mass spectrometry

A novel derivatization procedure, N-acetyl methyl (NACME) esterification, was developed to improve the accuracy and precision of amino acid delta13C value determination using gas chromatography-combustion-isotope ratio mass spectrometry (GC/C/IRMS). Standard mixtures of 15 protein amino acids were converted to NACME and N-acetyl-isopropyl (NAIP) esters; the latter established derivative was employed for comparison purposes. Both procedures yielded baseline-resolved peaks for all 15 amino acids when GC columns coated with polar stationary phases were employed. For NACME esters, the methylation conditions governed reaction yields, with highest yields observed when a 1 h, 70 degrees C methylation procedure (anhydrous MeOH/acetyl chloride, 25:4, v/v) was performed. The mean derivatization yields expressed relative to an underivatized coinjected standard (n-nonadecane) for both NACME and NAIP esters were identical. Likewise, the mean kinetic isotope effects (KIEs) were not significantly different (KIE(NACME) = 1.036; KIE(NAIP) = 1.038) and were shown in both cases to be reproducible. The mean reproducibility obtained from 15 replicates (3 x batches of 5) of both derivatives was strong (mean STDV(NACME) = 0.3 per thousand and STDV(NAIP) = 0.4 per thousand). The isotopic robustness of both derivatization procedures was observed over a concentration range of 52,500 microg of amino acid. NACME esters displayed low errors (+/-0.6 per thousand for phenylalanine to +/-1.1 per thousand for serine) due to the higher sample-to-derivative carbon ratio of this derivative. Finally, the integrity of the new NACME procedure was confirmed through analysis of diet and bone collagen amino acids of rats reared on C3 or C4 diets, which indicated the high degree of both accuracy and precision of the delta13C values obtained for individual amino acids.     

New proposal for uncertainty evaluation in indirect measurements

This paper deals with the uncertainty evaluation in indirect measurements. The attention is mainly paid to measurement models whose input quantities are modeled as correlated random variates. Moving from a past proposal related to the use of the unscented transform to overcome key limitations of current guide to the expression of uncertainty in measurement recommendations in the presence of the input quantities modeled as uncorrelated random variates, the authors are going to present a new proposal capable of extending the advantages of the cited transform when correlated input random variates are also concerned. The new proposal is, in particular, addressed to nonlinear and/or nonanalytical measurement models. After describing the key features and implementation issues of the proposal, the results obtained in a number of tests on simulated and actual measurement data are given, which assess its reliability and effectiveness.     

New method for data treatment in polarization measurements

Precise formulae are obtained for the expectation values E(ξ), E(η) and variances V(ξ), V(η) of random variables ξ, η describing the spin asymmetry in the same reaction when a background process contribution is zero and appreciable, respectively. The variances of ξ and η are proved to be finite. It is shown that E(ξ) is equal to the physical asymmetry. This property of ξ and the finiteness of V(ξ) allows to find the asymmetry from experimental data without studying in detail the detector efficiency as a function of all kinematic variables essential for a process under investigation. This is the base of the proposed method of data treatment which is illustrated by Monte Carlo calculations. The formula for E(η) can be used to estimate the systematic uncertainty of the obtained asymmetry due to the background contribution. The high statistics limits for E(η) and V(η) are also considered for a nonzero value of the signal-to-background ratio.     

13C enrichment of fullerenes

It is shown experimentally that fullerenes can be enriched with ¹³C as a constituent of CO₂ gas molecules. A qualitative model of the processes that correctly reflects the experimental laws is proposed. Center for Laser Technology, Scientific-Research Institute for Electrophysical Apparatus Pis’ma Zh. Tekh. Fiz. 25, 12–18 (September 26, 1999)     

Comparison of delta18O measurements in nitrate by different combustion techniques

Three different KNO3 salts with delta18O values ranging from about -31 to +54 per thousand relative to VSMOW were used to compare three off-line, sealed glass tube combustion methods (widely used for isotope studies) with a more recently developed on-line carbon combustion technique. All methods yielded roughly similar isotope ratios for KNO3 samples with delta18O values in the midpoint of the delta18O scale near that of the nitrate reference material IAEA-NO-3 (around +21 to +25 per thousand). This reference material has been used previously for one-point interlaboratory and intertechnique calibrations. However, the isotope ratio scale factors by all of the off-line combustion techniques are compressed such that they are between 0.3 and 0.7 times that of the on-line combustion technique. The contraction of the 6180 scale in the off-line preparations apparently is caused by O isotope exchange between the sample and the glass combustion tubes. These results reinforce the need for nitrate reference materials with delta18O values far from that of atmospheric O2, to improve interlaboratory comparability.     

New VNIIM comparator for measurements of line scales for length

An interference comparator is described for measuring line scales and gratings in which total conformity is provided for the sections being compared, the effect of water vapor in the refractometer chamber is overcome, and a laser confocal microscope and digital processing of signals are used. In comparisons, the length-dependent divergence is 1·10⁻⁸L, and independent of length the standard divergence is 2 nm. __________ Translated from Izmeritel’naya Tekhnika, No. 5, pp. 31–35, May, 2007.     

A New, 13C-Based Material for Neutron Targets

A ¹³C-based neutron-target material is investigated using x-ray diffraction, IR absorption and Raman scattering spectroscopies, transmission electron microscopy, and electrical (conductivity, magnetoresistance, and Hall effect) measurements before and after high-power electron irradiation for various lengths of time.__________Translated from Neorganicheskie Materialy, Vol. 41, No. 5, 2005, pp. 531–539.Original Russian Text Copyright © 2005 by Romanenko, Anikeeva, Gorbachev, Zhmurikov, Gubin, Logachev, Avilov, Tsybulya, Kryukova, Burgina, Tecchio.