On the potential of Raman‐spectroscopy‐based carbonate mass spectrometry

The potential for using Raman spectroscopy to measure stable oxygen isotope ratios (¹⁸O/¹⁶O) in carbonates is evaluated by measuring the Raman spectra and isotope ratios of a suite of 60 synthesized, ¹⁸O‐enriched calcite crystals ranging in composition from natural abundance (0.2 mole‐% ¹⁸O) to 1.2 mole‐% ¹⁸O. We determined the Raman‐inferred isotopic ratios (R_Raman) by fitting curves to the ν₁ symmetric stretching peak at 1086 cm⁻¹ and the smaller satellite peak, associated with the ν₁ stretching mode of singly substituted carbonate groups (C¹⁶O₂¹⁸O) at 1065 cm⁻¹. The ratio of the two peak areas shows a 1:1 correspondence with the ¹⁸O/¹⁶O ratios derived from standard mass spectrometry methods, confirming that the relative intensities of the ν₁ symmetric stretching peaks is a direct measure of the isotopic ratio in the carbonates. The 1‐sigma uncertainties of the R_Raman values of the individual crystals were 0.00079 (384‰ PDB) and 0.00043 (210‰ PDB) for the four‐crystal sample means. This level of uncertainty is much too high to provide significant estimates of natural variability; however, there are multiple prospects for improving the accuracy and precision of the technique. Carbon isotope ratios in carbonates cannot be measured by our approach, but our results highlight the potential of Raman‐based isotope ratio measurement for C and other elements in minerals and organic compounds. Copyright © 2012 John Wiley & Sons, Ltd.     

Effect of different lipid extraction methods on δ13C of lipid and lipid-free fractions of fish and different fish feeds

For many ecological applications of stable carbon isotope techniques, it is necessary to separate the lipid and lipid-free fractions. The effect of different lipid extraction methods on the isotope signature of the remaining lipid-free matter as well as the lipid fraction was tested. A hot extraction form of the Soxhlet method using petrol-ether was compared with two liquid-liquid extraction methods for lipid determination described by Bligh and Dyer and Smedes. Solid samples of fish and different natural food items were subjected to extraction and the carbon isotope ratios in lipid and lipid-free matter determined by IRMS. All methods were suitable for lipid extraction from all samples analysed here and did not cause biologically relevant differences (>1) in carbon isotopic ratios, except the Bligh and Dyer extraction method using chloroform which caused systematic errors for δ ¹³C when applied to diatoms.     

Stable isotope deltas: tiny,yet robust signatures in nature

Although most of them are relatively small, stable isotope deltas of naturally occurring substances are robust and enable workers in anthropology, atmospheric sciences, biology, chemistry, environmental sciences, food and drug authentication, forensic science, geochemistry, geology, oceanography, and paleoclimatology to study a variety of topics. Two fundamental processes explain the stable isotope deltas measured in most terrestrial systems: isotopic fractionation and isotope mixing. Isotopic fractionation is the result of equilibrium or kinetic physicochemical processes that fractionate isotopes because of small differences in physical or chemical properties of molecular species having different isotopes. It is shown that the mixing of radioactive and stable isotope end members can be modelled to provide information on many natural processes, including ¹⁴C abundances in the modern atmosphere and the stable hydrogen and oxygen isotopic compositions of the oceans during glacial and interglacial times. The calculation of mixing fractions using isotope balance equations with isotope deltas can be substantially in error when substances with high concentrations of heavy isotopes (e.g. ¹³C, ²H, and ¹⁸O ) are mixed. In such cases, calculations using mole fractions are preferred as they produce accurate mixing fractions. Isotope deltas are dimensionless quantities. In the International System of Units (SI), these quantities have the unit 1 and the usual list of prefixes is not applicable. To overcome traditional limitations with expressing orders of magnitude differences in isotope deltas, we propose the term urey (symbol Ur), after Harold C. Urey, for the unit 1. In such a manner, an isotope delta value expressed traditionally as?25 per mil can be written as?25 mUr (or?2.5 cUr or?0.25 dUr; the use of any SI prefix is possible). Likewise, very small isotopic differences often expressed in per meg ‘units’ are easily included (e.g. either+0.015 ‰ or+15 per meg can be written as+15 μUr.     

Continuous measurements of stable isotopes of carbon dioxide and water vapour in an urban atmosphere: isotopic variations associated with meteorological conditions

Isotope ratios of carbon dioxide and water vapour in the near-surface air were continuously measured for one month in an urban area of the city of Nagoya in central Japan in September 2010 using laser spectroscopic techniques. During the passages of a typhoon and a stationary front in the observation period, remarkable changes in the isotope ratios of CO₂ and water vapour were observed. The isotope ratios of both CO₂ and water vapour decreased during the typhoon passage. The decreases can be attributed to the air coming from an industrial area and the rainout effects of the typhoon, respectively. During the passage of the stationary front, δ¹³C–CO₂ and δ¹⁸O–CO₂ increased, while δ²H–H₂Ov and δ¹⁸O–H₂Ov decreased. These changes can be attributed to the air coming from rural areas and the air surrounding the observational site changing from a subtropical air mass to a subpolar air mass during the passage of the stationary front. A clear relationship was observed between the isotopic CO₂ and water vapour and the meteorological phenomena. Therefore, isotopic information of CO₂ and H₂Ov could be used as a tracer of meteorological information.     

Raman investigation of defective SiC nanocrystals

Phonon confinement effect and surface optical mode in SiC nanocrystal have been investigated through Raman spectroscopy. Considering high density of stacking faults in SiC grains, the correlation length of RWL (proposed by Richter, Wang, Li to explain phonon confinement in nano silicon) model is determined as a distance between nearby stacking faults. Thus, homogeneous region becomes thin slices in cylindrical SiC grains, which redefines weighting function. Effect of anisotropy of phonon dispersion curve is also analyzed during calculation. The additional 875‐cm⁻¹ band is attributed to defects and amorphous SiC, which is confirmed by transmission electron microscopy. SiC grains are approximated as column array with grain boundary substances regarded as surrounding medium, which explains surface optical phonon mode at 915 cm⁻¹. Copyright © 2015 John Wiley & Sons, Ltd.     

Use of the optogalvanic effect (OGE) for isotope ratio spectrometry of 13CO2 and 14CO2

The use of isotopic carbon dioxide lasers for determination of carbon (and oxygen) isotope ratios was first demonstrated in 1994. Since then a commercial device called LARA^?, has been manufactured and used for Helicobacter pylori breath tests using ¹³C-labelled urea. The major advantages of the optogalvanic effect compared with other infrared absorption isotope ratio measurement techniques are its lack of optical background and its high sensitivity resulting from a signal gain proportional to laser power. Continuous normalisation using two cells, a standard and sample, lead to high accuracy as well as precision. Recent advances in continuous flow measurement of ¹³C/¹²C ratios of CO₂ in air and extensions of the technique to ¹⁴C, which can be analysed as a stable isotope, are described.     

13CO2/12CO2 isotopic ratio measurements using a difference frequency-based sensor operating at 4.35 micrometers

A portable modular gas sensor for measuring the ¹³C/¹²C isotopic ratio in CO₂ with a precision of 0.8‰(±1σ) was developed for volcanic gas emission studies. This sensor employed a difference frequency generation (DFG)-based spectroscopic source operating at 4.35 μm (∼2300 cm^-1) in combination with a dual-chamber gas absorption cell. Direct absorption spectroscopy using this specially designed cell permitted rapid comparisons of isotopic ratios of a gas sample and a reference standard for appropriately selected CO₂ absorption lines. Special attention was given to minimizing undesirable precision degrading effects, in particular temperature and pressure fluctuations. Received: 16 April 2002 / Revised version: 28 May 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +1-713/5245237, E-mail: fkt@rice.edu     

High quality CVD diamond: a Raman scattering and photoluminescence study

High quality synthetic diamonds were grown on single-crystal silicon by microwave plasma enhanced chemical vapour deposition (CVD). A careful optimisation of both the experimental setup and the growth parameters was necessary before that the achievement of the best results was made possible. The films were deposited using a CH₄-H₂ gas mixture at methane concentrations variable in the range 0.6-2.2%, while the substrate temperature was fixed at 750 ^°C. Raman spectroscopy and photoluminescence (PL) were utilised to monitor the quality of the deposited films and to study the spatial distribution of defects, respectively. Micro-Raman analysis shows that linewidths of the diamond peak lower than 2.4 cm^-1 can be easily measured at the growth surface, indicating that the crystalline quality of individual grains is comparable to that of the best natural diamonds. The excellent phase purity of the diamond microcrystals at the growth surface is witnessed by the complete absence of any non-diamond carbon feature and by a very weak luminescence background in the 1.6-2.4 eV spectral range. A worsening of the quality of the diamond particles is found moving from the growth surface towards the film-substrate interface. A photoluminescence feature at about 1.68 eV, commonly associated to Si impurities, is distinctly observed as the exciting laser beam is focused close to the interface. A progressive degradation of the global quality of the films is found with increasing methane concentration in the gas mixture, as witnessed by an increased PL background in the films grown at higher methane concentrations. Received 24 November 2000     

PB- Und Sr-Isotopensignaturen AlS Herkunftsindikatoren Für Anthropogene Und Geogene Kontaminationen

Abstract

In isotope geochemistry, natural differences in isotope abundance ratios of heavy elements (e.g. Sr, Nd, Pb) allow the use of specific isotopic signatures as tracers for these and genetically related elements. Examples of such applications in the field of anthropogeochemistry will be presented for lead and strontium.     

Stable isotope determination of ester and ether methyl moieties in plant methoxyl groups

Plant methoxyl groups of lignin and pectin have both distinct stable hydrogen isotope (δ²H) and carbon isotope (δ¹³C) values that can be used for studying environmental processes and for investigating the origin and authenticity of biomaterials. Up to now, the reported methods have been applied only to determine isotope values of the bulk plant methoxyl pool. In this work, we have applied several methods to distinguish between stable isotope ratios of methoxyl groups of pectin and the bulk plant methoxyl pool. Our results demonstrate that by applying alkaline hydrolysis to specifically cleave off the ester methyl moiety (pectin-like), we can distinguish δ²H and δ¹³C values of the pectin methoxyl pool from the bulk methoxyl pool. No measureable isotope discrimination was observed either during sample preparation or during analytical measurement. Furthermore, using this method, no major isotope difference in either the hydrogen or carbon isotope signature of the methoxyl groups of plant pectin and bulk matter from plant species such as leaves from trees, apples, carrots and potatoes was noted. We show the methanol released during alkaline hydrolysis of plant material and subsequently treated with hydriodic acid to be an excellent procedure to measure specifically and precisely the δ¹³C and δ²H isotope values of plant pectin-like methoxyl groups. This method is particularly advantageous when plant matter with a low methoxyl content has to be analysed.     

Using Stable Isotope Analyses to Identify Allochthonous Inputs to Lake Naivasha Mediated via the Hippopotamus Gut

Abstract

The hippopotamus grazes nocturnally on land and resides in water during the day. Much of the ingested material must therefore be defecated directly into the aquatic system and can thus be considered an allochthonous resource available to aquatic consumers. The utility of stable isotope analyses of carbon and nitrogen to distinguish hippo faecal matter from other potential basal resources was tested at Lake Naivasha, Kenya. Hippopotami proved faithful to a short grass diet although supplementary grazing of aquatic macrophytes was observed. The typical isotopic ratios of C4 grasses ingested were not altered substantially by gut processes, and were clearly distinct from algal and aquatic macrophyte isotopic ratios. However, marginal plants such as Cyperus papyrus exhibit C4 ratios, and so the technique is suitable only for use in localities where ‘contamination’ from such sources is negligible.     

Anisotropy of phosphorous electron donor state in strained clusters in silicon at low temperatures

An anisotropic EPR spectrum at T = 4 K was observed in silicon samples irradiated by phosphorus ions and subsequently annealed at 1000°C. Epitaxial silicon layers with a natural isotope composition and enriched by ²⁸Si isotope grown on a natural silicon wafer were investigated. The spectrum consisted of three lines corresponding to different g-factor components: g _x ,g _y , and g _z . The central line was overlapped by the isotropic line coinciding by its g-factor with the line of the conduction electrons in silicon. The shape of the spectral lines indicated that the spectrum was due to the paramagnetic centers which belong to the randomly oriented clusters with the anisotropic g-factor. The nature of the anisotropic EPR spectrum is due to the electrons localized on donors located in the strained phosphorous clusters. The strains were caused by either incompletely annealed defects after the phosphorous implantation (E = 40 keV, D = 2 × 10¹⁴ cm⁻², T _ann = 1000°C, 1 h) or phosphorous atoms in clusters. The distance between the components strongly depended on the temperature and microwave power and decreased as they increased.     

Stable Isotope Ratios and Uric Acid Preservation in Termites Belonging to Three Feeding Habits in Thailand

Abstract

Nitrogen and carbon stable isotope ratios and uric acid concentrations in termites sampled from a dry evergreen forest in Thailand, were determined across three kinds of feeding habits. Feeding habits of Microcerotermes crassus, which is an abundant woodfeeder, and Dicuspiditermes makhamensis, a common soil-feeding termite, were confirmed by isotopic signatures. Lichen feeding termites (Hospitalitermes birmanicus, H. bicolor and H. ataramensis) were characterized by low δ¹⁵N values, suggesting that they assimilated nitrogen deposited from the atmosphere. There was also a significant difference in uric acid concentrations between termites representing different feeding habits. No significant relationships were found between uric acid concentrations and δ¹⁵N or δ¹³C in Hospitalitermes. However, δ¹⁵N values were correlated with C/N ratios in H. birmanicus, except in one colony of H. ataramensis. δ¹³C values in both species were negatively correlated with C/N ratios.     

Towards 0.99999 28Si

A new approach for producing high-purity silicon with isotopic enrichment of ²⁸Si isotope is reported. The methods of centrifugal enrichment were modified to obtain the initial gaseous silicon tetrafluoride with a record-breaking enrichment of 0.99999664(11) with respect to ²⁸Si. The effective conversion of silicon tetrafluoride into elementary silicon with minimal isotopic dilution was achieved in an electron cyclotron resonance discharge plasma, sustained by gyrotron microwave radiation with a frequency of 24 GHz. We have experimentally demonstrated the deposition of the layers of microcrystalline ²⁸Si with enrichment of 0.999986 ± 0.000003, which is the best result at the present time.     

Laser Stark Spectroscopy and Isotopic Separation

A potentially useful scheme for photoselective isotope enrichment is presented. The selective laser excitation step is accomplished by utilizing the Stark effect to shift molecular transitions into resonance with laser frequencies. The method is demonstrated for isotope separation of ¹³C, ¹⁵N and ²H. Laser Stark spectroscopy can sensitively detect as few as 10⁹ molecules in the optical path, thus the isotopic separation can be achieved from industrial sample mixtures containing natural abundances. A comparison of the isotopic enrichment efficiency using the present method of “exact” resonance and the previously used method of “near” resonance excitation is also given.     

Boron isotope enrichment in nanosecond pulsed laser-ablation plume

Boron isotopic enrichment is observed in the laser ablation of B₄C target using nanosecond (ns) wide 532 nm laser beam of a Nd-YAG laser. B¹⁰/B¹¹ ratio of 0.9 against the natural abundance of 0.25 is obtained at a laser power density of 8×10⁸ W/cm² (fluence of 6.4 J/cm²). The enrichment as a function of laser power density is demonstrated using a quadrupole mass spectrometer. Apart from higher enrichment factor, only singly charged ions are found in the laser plume from the B₄C target, in contrast to the multiply charged ions from the BN target reported in a recent report using femtosecond (fs) laser pulses. This study indicates the possibility of using less expensive, widely used ns lasers, which can also yield a higher throughput per pulse than a fs laser for isotope enrichment. Received: 28 September 2001 / Accepted: 4 February 2002 / Published online: 3 June 2002 RID="*" ID="*"Corresponding author. Fax: +91-4114/480-065, E-mail: mj@igcar.ernet.in     

Detection of C–H bonds in crystalline α-SiC by IR-absorption measurements

In SiC epilayers sp ³ C-H bond vibration bands were detected by infrared transmittance measurements. The absorption constants of the transmission peaks are related to the temperature at which the layers were grown and decrease with increasing growth temperature. The absorption centers vanish when the epilayer is removed or after annealing the sample at temperatures very much lower than the growth temperatures in a hydrogen-free atmosphere. These absorption centers are connected to hydrogen on silicon lattice sites.     

High-dose carbon implantations into silicon: fundamental studies for new technological tricks

Depending on the implantation temperature, the implantation of carbon ions into silicon at high doses results in the formation of either amorphous SiC_x or crystalline 3C-SiC precipitates. Various aspects of the precipitation behaviour observed, such as the impeded nucleation, the limited growth and the resulting sensitivity to ballistic destruction are attributed to the large interfacial energy between crystalline silicon and 3C-SiC. Periodically arranged amorphous SiC_x nanoclusters, which are formed at lower temperatures, are shown to promote amorphisation by their surrounding stress field and to represent sinks for silicon self-interstitials, which can be activated by annealing at 900 °C. By control of the depth distribution of equally sized, oriented 3C-SiC precipitates formed at higher implantation temperatures, it is possible to establish suitable starting conditions for the formation of buried homogeneous, single-crystalline 3C-SiC layers during a post-implantation anneal. The properties of these ion-beam-synthesised SiC layers are described and attempts to combine them with insulating and metallic layers are reviewed. A survey is given of the emerging applications of ion-beam-synthesised buried SiC layers and microstructures in electronic, optical and micromechanical devices and as large-area SiC pseudosubstrates. Received: 11 November 2002 / Accepted: 12 November 2002 / Published online: 4 April 2003 RID="*" ID="*"Corresponding author. Fax: +49-821/598-3425, E-mail: lindner@physik.uni-augsburg.de     

Study of deposition patterns of plating layers in SiC/Cu composites by electro-brush plating

SiC reinforced copper composite coatings were prepared by electro-brush plating with micron-size silicon carbide (SiC) ranging from 1 to 5 μm on pure copper sheet in this paper. The micro-structural characterizations of SiC/Cu composite coatings were performed by optical microscope and Scanning Electron Microscope (SEM) coupled with spectrometer, to study co-deposition mechanism of SiC/Cu. It was found that there were three different patterns of SiC deposition in plating layers during electro-brush plating process, i.e. the particles could deposit inside copper grains, in grain boundaries, or in holes of the surface. To investigate deposition mechanism of each pattern, size of SiC and copper grains was compared. By comparison of size of copper grains and hard particles, SiC were either wrapped in copper grains or deposited in grain boundaries. Moreover, electro-brush plating layers at different brush velocities and current densities were obtained respectively, to analyze the microstructure evolution of the composite coatings. The hardness of plating layers was measured. The results indicated at the current density of 3 A/dm², the SiC/Cu coating was compact with SiC content at a high level and the hardness reached a maximum.     

Ultra-large lateral grain growth by double laser recrystallization of a-Si films

A new double laser recrystallization technique that can produce ultra-large direction- and location-controlled lateral grains is presented. An excimer laser is combined with a pulse-modulated Ar⁺ laser to yield grains of tens of micrometers in size. The effect of different parameters on lateral grain growth is investigated. These parameters include the time delay between the two lasers, the excimer-laser fluence, the Ar⁺-laser power and the pulse duration. The process has a wide process window and is insensitive to both the excimer-laser fluence and the Ar⁺-laser power fluctuations. Preheating of the a-Si film with the Ar⁺ laser before firing the excimer laser is necessary for inducing lateral grain growth. The transient excimer-laser irradiation is believed to generate nucleation sites for initiating the subsequent lateral grain growth. The surface roughness of the recrystallized poly-Si is measured by atomic force microscopy. Received: 14 September 2000 / Accepted: 24 February 2001 / Published online: 27 June 2001