δ34S for tracing the origin of cheese and detecting its authenticity

Casein δ³⁴S of 725 samples of cheese from all over the world were measured using IRMS. δ³⁴S alone made it possible to establish characteristic ranges of values for two types of Italian cheese (Grana Padano PDO and Parmigiano Reggiano PDO) and for the different regions and provinces of both the Grana Padano PDO and the Parmigiano Reggiano PDO zones. Moreover, δ³⁴S of PDO Italian samples were compared to both Italian (not PDO) and foreign competitive cheese samples. In all the cases, sulfur isotopic ratio analysis was a powerful tool to fix characteristic ranges of values for cheeses coming from different countries and to improve the information given by other isotopic parameters.     

Sulphur isotopes in animal hair track distance to sea

Stable sulphur isotope ratios (³⁴S/³²S) in animal tissues have been suggested as a tracer of coastal residency of terrestrial animals, but data are lacking that quantify the inland range of the sulphur coastal signal and the effects of seasonality. Here, we present δ³⁴S measurements of sheep wool collected seasonally on eight farms across Ireland and wool samples collected opportunistically along the west and east coasts. We observed large (>10‰) δ³⁴S differences across the island and we show that wool δ³⁴S values were negatively correlated with distance to the west coast. We propose that this is due to the predominantly (south‐)westerly airflow, possibly combined with the influence of anthropogenic sulphur deposited from the east. While essentially all the sulphur contained in west‐coast wool is of marine origin, relatively high δ³⁴S values were still measured >100 km inland, suggesting that marine sulphur can be carried over long distances. Seasonal variations are small at the individual level for sedentary grazing animals. We conclude that sulphur isotopes ratios measured in archival keratinous tissues can be used to describe regional δ³⁴S isoscapes primarily defined by distance to coasts and thus provide a tool to detect short‐term movements of domestic, feral and wild animals within such isoscapes. Copyright © 2011 John Wiley & Sons, Ltd.     

Does natural weathering change the stable isotope composition (2H, 13C, 15N, 18O and 34S) of cattle hair?

Stable isotope analysis of hair has found applications in many fields of science because it provides a temporally resolved, fairly stable isotopic archive of mammalian individuals. We investigated whether this hair archive is modified by natural weathering while attached to a living animal. We analyzed the tail switch hairs of one suckler cow, sampled seven times over a period of four annual summer pasture–winter stall feeding cycles. We compared relative isotope ratios (δ²H, δ¹³C, δ¹⁵N, δ¹⁸O and δ³⁴S) of sections of hair that grew simultaneously but were exposed to natural weathering conditions over different periods of time. Natural wear caused a loss of mass of approx. 0.13% day^–1, with no apparent effect of environmental conditions. Changes in δ²H, δ¹³C, δ¹⁵N and δ¹⁸O were below the detection limit, indicating that hair is a reliable archive for the isotopes of these elements. In contrast, δ³⁴S values increased during the grazing period by about 1 ‰, with exposure to UV radiation appearing to have a major influence on this result. The δ³⁴S values decreased during the subsequent stall period, probably due to abrasion. Seasonal variation in δ³⁴S may indicate alternating environments that differ in their weathering conditions. Copyright © 2011 John Wiley & Sons, Ltd.     

Penicillin biosynthesis the immediate origin of the sulphur atom

A mixture of tripeptide isotopomers δ-(L-α-aminoadipyl)-L-cystelnyl-D [2-²H]-valine and δ-(L-α-aminoadipyl)-L-(³⁴S-cysteinyl)-D-valine were converted by the enzyme isopenicillin-N-synthetase into isopenicillin N. The distribution of the ²H and ³⁴S in this product, determined by mass spectrometry, showed there was no transfer of the sulphur between the precursor molecules during conversion to penicillin.     

Measurement of sulfur isotope composition (δ34S) by multiple‐collector thermal ionization mass spectrometry using a 33S‐36S double spike

A new analytical technique is described for the determination of δ³⁴S that is comparable to or better than modern gas source mass spectrometry in precision and accuracy, but requires about a factor of 10 less sample. The technique is based on the production of singularly charged arsenic sulfide molecular ions (AsS⁺) by thermal ionization using silica gel as an emitter and combines multiple‐collector thermal ionization mass spectrometry (MC‐TIMS) with a ³³S‐³⁶S double spike to correct instrumental fractionation. Three international sulfur standards (IAEA‐S‐1, IAEA‐S‐2, and IAEA‐S‐3) were measured to evaluate the precision and accuracy of the new technique and to evaluate the consensus values for these standards. Two different double spike preparations were used. The δ³⁴S values (reported relative to Vienna Canyon Diablo Troilite (VCDT), (δ³⁴S (‰) = ([((³⁴S/³²S)_sample/(³⁴S/³²S)_VCDT ? 1) × 1000]), ³⁴S/³²S_VCDT = 0.0441626) determined were ?0.32 ± 0.04‰ (1σ, n = 4) and ?0.31 ± 0.13‰ (1σ, n = 8) for IAEA‐S‐1, 22.65 ± 0.04‰ (1σ, n = 7) and 22.60 ± 0.06‰ (1σ, n = 5) for IAEA‐S‐2, and ?32.47 ± 0.07‰ (1σ, n = 8) for IAEA‐S‐3. The amount of natural sample used for these analyses ranged from 0.40 to 2.35 µmol. Replicate determinations of each standard showed less than 0.5‰ variability (IAEA‐S‐1 <0.4‰, IAEA‐S‐2 <0.2‰, and IAEA‐S‐3 <0.2‰). Because the technique is based on thermal ionization of AsS⁺, and As is mononuclidic, corrections for interferences or for scale contraction/expansion are not required. The availability of MC‐TIMS instruments in laboratories around the world makes this technique immediately available to a much larger scientific community who require highly accurate and precise measurements of sulfur. Published in 2005 by John Wiley & Sons, Ltd.     

Contribution a l'etude du dosage par radioactivation du sourfre et du phosphore en tres faibles concentrations dans les metaux de tres haute purete (Aluminium,magnesium, cuivre,fer, nickel)

The chemical separation of sulphur and phosphorus from pure iron and nickel, is described. Sulphur has been determined first by irradiation in fast neutrons, then by irradiation in mixed fast and thermal neutrons. The two methods gave two different results; so, we were led to point out the same phenomenon asJ. Le Hericy had already pointed out for the determination of sulphur in copper. We found that the abnormal amounts of sulphur came from external contamination with chlorine since sulphur is then produced by the³⁵Cl(n, p)³⁵S reaction. The diffusion of³⁵S atoms (produced on the edge of the samples) explains that the concentration of sulphur decreases from the edge to the middle of the sample. We prepared samples of iron and nickel, artificially covered with ammonium chloride, and we studied the apparent concentration of sulphur as a function of the depth in these samples. Our experiences pointed out that the contamination in sulphur yielded by the (n, p) reaction, reaches very quickly the middle of the samples. This phenomenon limits the determination of sulphur by the³⁴S(n, γ)³⁵S reaction, in nickel and iron.      

A suite of sensitive chemical methods to determine the δ15N of ammonium, nitrate and total dissolved N in soil extracts

Natural ¹⁵N abundances (δ¹⁵N values) of different soil nitrogen pools deliver crucial information on the soil N cycle for the analysis of biogeochemical processes. Here we report on a complete suite of methods for sensitive δ¹⁵N analysis in soil extracts. A combined chemical reaction of vanadium(III) chloride (VCl₃) and sodium azide under acidic conditions is used to convert nitrate into N₂O, which is subsequently analyzed by purge‐and‐trap isotope ratio mass spectrometry (PTIRMS) with a cryo‐focusing unit. Coupled with preparation steps (microdiffusion for collection of ammonium, alkaline persulfate oxidation to convert total dissolved N (TDN) or ammonium into nitrate) this allows the determination of the δ¹⁵N values of nitrate, ammonium and total dissolved N (dissolved organic N, microbial biomass N) in soil extracts with the same basic protocol. The limits of quantification for δ¹⁵N analysis with a precision of 0.5‰ were 12.4 µM for ammonium, 23.7 µM for TDN, 16.5 µM for nitrate and 22.7 µM for nitrite. Copyright © 2010 John Wiley & Sons, Ltd.     

A new sensitive and selective fluorescence method for determination of chlorine dioxide in water using rhodamine S

A new simple, selective and sensitive method for the determination of trace chlorine dioxide in water has been developed, based on the oxidation by chlorine dioxide to reduction the fluorescence of rhodamine dyes in ammonia-ammonium chloride buffer solution. Four rhodamine dyes systems such as rhodamine S, rhodamine G, rhodamine B and butyl-rhodamine B were tested. The rhodamine S system is the best, with a linear range of 0.0060-0.450 μg mL⁻¹ and a detection limit of 0.0030 μg mL⁻¹ ClO₂. It was applied to the determination of chlorine dioxide in synthetic samples and real samples, with satisfactory results. This method has good selectivity, especially, other chlorine species such as chlorine, hypochlorite, chlorite and chlorate do not interfere the determination. The mechanism of fluorescence reduction was also considered.     

Determination of Alizarin Red S using a novel B-Z oscillation system catalyzed by a tetraazamacrocyclic complex

A new and convenient method for the determination of Alizarin Red S by the perturbations caused by different amounts of Alizarin Red S on a novel B-Z oscillating system is proposed. This new type Belousov-Zhabotinskii involves a macrocyclic copper(II) complex [CuL](ClO₄)₂ as catalyst and malic acid as the substrate. The ligand L in the complex is 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene. It is found that the relationship between the change in the oscillation amplitude and the logarithm of the Alizarin Red S concentration in the range of 1.5 × 10⁻⁷ to 1 × 10⁻³ M fits a polynomial model: ΔA = 659 + 184.2 log [Alizarin Red S]+ 12.9 log² [Alizarin Red S]. The RSD obtained with ten samples is 4.4%. The probable mechanism involving the perturbation of Alizarin Red S on the oscillating chemical system is also discussed.      

Sedimentary characteristics of Mg-rich carbonate formations and minerogenic fluids of magnesite and talc occurrences in early proterozoic in eastern liaoning province,China

There are large to superlarge magnesite and talc deposits occurring in Mg-rich carbonate formations distributed in the early Proterozoic Dashiqiao Formation in eastern Liaoning Province, China. The discovery of the sedimentary gypsum, isotopic geochemistry of δ¹⁸O_smow, δ¹³C_PDB, δ³⁴S_VCDT and Sr/Ba ratio of carbonate, talc, quartz and gypsums with field investigation and sample analysis in laboratory demonstrate that the formation of magnesite and talc deposits is closely related to marine evaporates, which then underwent reworking of regional metamorphism and hydrothermal metasomatism. Metasomatic fluids originating from the paleoseawater played a controlling role in the formation of talc deposits.

     

Sedimentary characteristics of Mg-rich carbonate formations and minerogenic fluids of magnesite and talc occurrences in early proterozoic in eastern liaoning province,China

There are large to superlarge magnesite and talc deposits occurring in Mg-rich carbonate formations distributed in the early Proterozoic Dashiqiao Formation in eastern Liaoning Province, China. The discovery of the sedimentary gypsum, isotopic geochemistry of δ¹⁸O_smow, δ¹³C_PDB, δ³⁴S_VCDT and Sr/Ba ratio of carbonate, talc, quartz and gypsums with field investigation and sample analysis in laboratory demonstrate that the formation of magnesite and talc deposits is closely related to marine evaporates, which then underwent reworking of regional metamorphism and hydrothermal metasomatism. Metasomatic fluids originating from the paleoseawater played a controlling role in the formation of talc deposits.

     

Micro‐scale (1.5 µm) sulphur isotope analysis of contemporary and early Archean pyrite

We present a method for in situ sulphur (S) isotopic analysis of significantly small areas (1.5 µm in diameter) in pyrite using secondary ion mass spectrometry (NanoSIMS) to interpret microbial sulphur metabolism in the early earth. We evaluated the precision and accuracy of S isotopic ratios obtained by this method using hydrothermal pyrite samples with homogeneous S isotopic ratios. The internal precision of the δ³⁴S value was 1.5‰ at the level of 1 sigma of standard error (named 1SE) for a single spot, while the external reproducibility was estimated to be 1.6‰ at the level of 1 sigma of standard deviation (named 1SD, n = 25). For each separate sample, the average δ³⁴S value was comparable with that measured by a conventional method, and the accuracy was better than 2.3‰. Consequently, the in situ method is sufficiently accurate and precise to detect the S isotopic variations of small sample of the pyrite (less than 20 µm) that occurs ubiquitously in ancient sedimentary rocks. This method was applied to measure the S isotopic distribution of pyrite within black chert fragments in early Archean sandstone. The pyrite had isotopic zoning with a ³⁴S‐depleted core and ³⁴S‐enriched rim, suggesting isotopic evolution of the source H₂S from ?15 to ?5‰. Production of H₂S by microbial sulphate reduction (MSR) in a closed system provides a possible explanation for both the ³⁴S‐depleted initial H₂S and the progressive increase in the δ³⁴S_H2S value. Although more extensive data are necessary to strengthen the explanation for the origin of the MSR, the results show that the S isotopic distribution within pyrite crystals may be a key tracer for MSR activity in the early earth. Copyright © 2010 John Wiley & Sons, Ltd.     

Measurement of the δ34S value in methionine by double spike multi‐collector thermal ionization mass spectrometry using Carius tube digestion

Methionine is an essential amino acid and is the primary source of sulfur for humans. Using the double spike (³³S‐³⁶S) multi‐collector thermal ionization mass spectrometry (MC‐TIMS) technique, three sample bottles of a methionine material obtained from the Institute for Reference Materials and Measurements have been measured for δ³⁴S and sulfur concentration. The mean δ³⁴S value, relative to Vienna Canyon Diablo Troilite (VCDT), determined was 10.34 ± 0.11‰ (n = 9) with the uncertainty reported as expanded uncertainties (U). These δ³⁴S measurements include a correction for blank which has been previously ignored in studies of sulfur isotopic composition. The sulfur concentrations for the three bottles range from 56 to 88 µg/g. The isotope composition and concentration results demonstrate the high accuracy and precision of the DS‐MC‐TIMS technique for measuring sulfur in methionine. Published in 2010 by John Wiley & Sons, Ltd.     

Determination of (34)S:(32)S ratios by FTIR spectroscopy

A new method for determining (34)S:(32)S ratios using Fourier transform infrared spectroscopy has been developed. The four sulphur-containing gases SCO, H(2)S, SF(6) and SO(2) are assessed as possible compounds for the spectroscopic measurements, from which, after a consideration of available lines showing a clear isotopic shift and also of possible synthetic routes to the gas starting from a range of natural sample types, SO(2) was selected for further development of the instrumental method for the isotopic ratio determination. Sulphur in the samples present as the element, as metal sulphides or as organosulphur compounds, is converted by heating with V(2)O(5) into gaseous SO(2), and a part of the 518 cm(-1) band is recorded in the absorbance mode. The optimisation of instrumental parameters and of the chemical reaction conditions is described, and the results from the application of the method to the measurement of the level of enrichment of (34)S in a soil fungus are presented. The agreement between results at the natural abundances of 4.2% was better than 0.04% absolute for a sample size of 1.5 mg of sulphur.     

Determination of inorganic sulphur in aqueous solutions. An application for cyanide extracts of gold ore and plating solutions

Summary The method described for the determination of total sulphur in aqueous solutions known to contain no organic sulphur is based on quantitative conversion of sulphur species to sulphate by hydrogen peroxide at room temperature. The oxidation is first carried out under basic conditions for 1 h and then under acidic conditions for a further hour. The conversion of S^2–, S₂O ₅ ^2– , S²O ₃ ^2– , S₂O ₈ ^2– , SCN^– and SO ₃ ^2– to sulphate is quantitative. The sulphate is then determined turbidimetrically. The method is suitable for a wide range of inorganic solutions containing greater than 2 ppm sulphur. It was applied to determine the total sulphur content in several cyanide extracts of gold ore and plating solutions of zinc and nickel.

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Bestimmung von anorganischem Schwefel in wäßrigen Lösungen. Anwendung auf Cyanideextrakte von Golderzen und galvanische Bäder

     

Source identification of nitrate by means of stable nitrogen isotopes in the river Daugava and loads of nitrogen to the Gulf of Riga

Nitrogen isotope ratio of nitrate provides a powerful tool to investigate nitrate sources and cycling mechanisms. Although the use of an isotope ratio method for ¹⁵N/¹⁴N allows identifying the nitrate sources in rivers by estimating a seasonal variation of N-NO₃ concentration, however, there are some restrictions. Nitrification, the conversion of NH₄⁺ to NO₃-, can proceed with significant nitrogen isotope fractionation, preferentially accumulating ¹⁴N in the produced NO₃-, and can make it difficult to identify the nitrate source with a high proportion of the isotope δ¹⁵N. However, the uptake and assimilation of NH₄⁺ and NO₃- have the capability of affecting isotopic compositions of riverine nitrogen compounds, and this may hinder the determination of whether the impact of the nitrate source with a high proportion of the isotope δ¹⁵N reduces. In addition, this study demonstrates that nitrate nitrogen concentration may correlate with δ¹⁵N_NO3 values both positively and negatively. Such correlations are the result of isotope effects during nitrogen transformation processes (e.g. nitrification and assimilation) and isotopic variability in the various nitrate sources. A comparison of NO₃- concentration and δ¹⁵N_NO3 can be used to further distinguish mixing from biological processing. However, in order to get a more precise answer regarding the nitrate sources, it would be useful to take both the data of nitrogen isotopes and data of oxygen isotopes present in nitrates.     

Synthese und Struktur von S{NAs(tBu)2[Os3(CO)11]}2 Das erste Schwefeldiimid mit trans,trans-Konfiguration im Festkörper

Synthesis and Structure of S{NAs(^tBu)₂[Os₃(CO)₁₁]}₂. The First Sulphur Diimide with trans,trans Configuration in the Solid State In the reaction of bis(di-tert-butylarsino) sulphur diimide, S(NAs^tBu₂)₂, with the cluster Os₃(CO)₁₁(NCCH₃) either one or two [Os₃(CO)₁₁] units can be added to the sulphur diimide — according to the molar ratio — yielding Os₃(CO)₁₁As(^tBu)₂NSNAs^tBu₂ ( 1 ) or S{NAs(^tBu)₂[Os₃(CO)₁₁]}₂ ( 2 ), respectively. The title compound μ-[(trans,trans)-bis(di-tert-butyl-arsino)sulphur diimide-As,As]-bis(undecacarbonyl-triangulo-triosmium) ( 2 ) is also obtained upon thermolysis of 1 in refluxing octane; its structure was elucidated by X-ray crystallography. Complex 2 is the first sulphur diimide with a trans,trans configuration in solid state. The trans,trans configuration is forced by the bulky substituents. 2 crystallises with deuterochloroform (1:1) in the monoclinic space group C2/c: a = 25.887(3), b = 8.684(1), c = 26.357(4) Å, β = 103.34(1)°, Z = 4. Due to special positions the SN₂ moiety (inversion center) and the chloroform molecule (twofold axis) are disordered statistically. The S?N bond lengths amount 1.50(2) Å on the average, the angle at, sulphur (111(2)°) is smaller in comparison with open-chained sulphur diimides with the cis, trans and cis,cis configuration. The angles a t the K atoms are enlarged (131(2) and 135(2)°), respectively. With exception of small torsions around the S?N bonds the principle of coplanarity for sulphur diimides is also fulfilled for t,he trans, trans form. The amino residues occupy equatorial positions in the triosmium clusters. I n the triosmium triangle two bonds are almost equal in length (2.891(1) and 2.884(1) Å, respectively), the third Os? Os bond is somewhat enlarged (2.939(1) Å).     

Precise isotope-ratio determination by CGC hyphenated to ICP– MCMS for speciation of trace amounts of gaseous sulfur,with SF<Subscript>6</Subscript> as example compound

Capillary gas chromatography coupled to an inductively coupled plasma mass spectrometer with multiple-collector detection (GC–ICP–MCMS) has been used to assess the precision and instrumental mass bias in sulfur isotope-ratio determination for the gaseous sulfur species SF₆. The isotopic composition of the compound was certified by the institute for reference materials and measurements (IRMM, Belgium) and is available as PIGS 2010. Integration of the peaks (peak half-width 1.4 s) was performed using a special peak-integration method based on definition of the integration area by assessment of a uniform isotope-ratio area within the chromatographic peak. Instrumental mass bias was determined to be approximately 12% per mass unit and proved to be stable in the concentration range measured. Replicate injections of 2, 10, 20, and 30 ng (as S) SF₆ diluted in argon gave precision for the ³²S/³⁴S ratio from 0.6% RSD for 2-ng injections to 0.03% RSD for 30-ng injections. The ³²S/³³S and ³³S/³⁴S isotope-ratio precision was better than 0.4% RSD for injections of 10 ng (as S) and higher. Detection limits were in the absolute pg range for all measured sulfur isotopes.     

Colorimetry of sulphur anions

Summary The colorimetric method for the determination and evaluation of polythionates above trithionate has been adapted for use in conjunction with sulphur sols. This has been achieved simply by increasing the period of cyanolysis. The method gives good results for the concentration of sulphur. The n values in the formula S _n O ₆ ^2– , which also represents sulphur sols, are not very accurate, but the accuracy might be increased by high precision colorimetry. However, they do serve to distinguish between polythionates and colloidal sulphur.Part III.: Urban, P. J.: Z. analyt. Chem. 180, 110 (1961).