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An alternative calibration procedure for use when performing carbon isotope ratio measurements by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) has been developed. This calibration procedure does not rely on the corrections in-built in the instrument software, as the carbon isotope ratios of a sample are calculated from the measured raw peak areas. The method was developed for the certification of a urine reference material for sports drug testing, as the estimation of measurement uncertainty is greatly simplified. To ensure that the method is free from bias arising from the choice of calibration material and instrument, the carbon isotope ratios of steroids in urine extracts were measured using two different instruments in different laboratories, and three different reference materials (CU/USADA steroid standards from Brenna Laboratory, Cornell University; NIST RM8539 mineral oil; methane calibrated against NIST RM8560 natural gas). The measurements were performed at LGC and the Australian National Measurement Institute (NMI). It was found that there was no significant difference in measurement results when different instruments and reference materials were used to measure the carbon isotope ratio of the major testosterone metabolites androsterone and etiocholanolone, or the endogenous reference compounds pregnanediol, 11- ketoetiocholanolone and 11ß-hydroxyandrosterone. Expanded measurement uncertainties at the 95% coverage probability ranged from 0.21‰ to 1.4‰, depending on analyte, instrument and reference material. The measurement results of this comparison were used to estimate a measurement uncertainty of δ(13)C for the certification of the urine reference material being performed on a single instrument using a single reference material at NMI.

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The potential of high-precision calcium and lead isotope ratio measurements using laser ablation coupled to multicollector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) to aid distinction between four genuine and five counterfeit pharmaceutical packaging samples and further classification of counterfeit packaging samples has been evaluated. We highlight the lack of reference materials for LA-MC-ICP-MS isotope ratio measurements in solids. In this case the problem is minimised by using National Institute of Standards and Technology Standard Reference Material (NIST SRM) 915a calcium carbonate (as solid pellets) and NIST SRM610 glass disc for sample bracketing external standardisation. In addition, a new reference material, NIST SRM915b calcium carbonate, has been characterised in-house for Ca isotope ratios and is used as a reference sample. Significant differences have been found between genuine and counterfeit samples; the method allows detection of counterfeits and aids further classification of packaging samples. Typical expanded uncertainties for measured-corrected Ca isotope ratio values ((43)Ca/(44)Ca and (42)Ca/(44)Ca) were found to be below 0.06% (k = 2, 95% confidence) and below 0.2% for measured-corrected Pb isotope ratios ((207)Pb/(206)Pb and (208)Pb/(206)Pb). This is the first time that Ca isotope ratios have been measured in packaging materials using LA coupled to a multicollector (MC)-ICP-MS instrument. The use of LA-MC-ICP-MS for direct measurement of Ca and Pb isotopic variations in cardboard/ink in packaging has definitive potential to aid counterfeit detection and classification.

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This article reviews recent developments in the use of multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) to provide high-precision carbon isotope ratio measurements. MC-ICP-MS could become an alternative method to isotope ratio mass spectrometry (IRMS) for rapid carbon isotope ratio determinations in organic compounds and characterisation and certification of isotopic reference materials. In this overview, the advantages, drawbacks and potential of the method for future applications are critically discussed. Furthermore, suggestions for future improvements in terms of precision and sensitivity are made. No doubt, this is an exciting analytical challenge and, as such, hurdles will need to be cleared.

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Isotope ratio mass spectrometry (IRMS) and multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) are highly important techniques that can provide forensic evidence that otherwise would not be available. MC-ICP-MS has proved to be a very powerful tool for measuring high precision and accuracy isotope amount ratios. In this work, the potential of combining isotope amount ratio measurements performed by MC-ICP-MS and IRMS for the detection of counterfeit pharmaceutical tablets has been investigated. An extensive study for the antiviral drug Heptodin has been performed for several isotopic ratios combining MC-ICP-MS and an elemental analyser EA-IRMS for stable isotope amount ratio measurements. The study has been carried out for 139 batches of the antiviral drug and analyses have been performed for C, S, N and Mg isotope ratios. Authenticity ranges have been obtained for each isotopic system and combined to generate a unique multi-isotopic pattern only present in the genuine tablets. Counterfeit tablets have then been identified as those tablets with an isotopic fingerprint outside the genuine isotopic range. The combination of those two techniques has therefore great potential for pharmaceutical counterfeit detection. A much greater power of discrimination is obtained when at least three isotopic systems are combined. The data from these studies could be presented as evidence in court and therefore methods need to be validated to support their credibility. It is also crucial to be able to produce uncertainty values associated to the isotope amount ratio measurements so that significant differences can be identified and the genuineness of a sample can be assessed.

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A new method for the measurement of longitudinal variations of sulfur isotope amount ratios in single hair strands using a laser ablation system coupled to a multicollector inductively coupled plasma mass spectrometer (LA-MC-ICP-MS) is reported here for the first time. Ablation parameters have been optimized for the measurement of sulfur isotope ratios in scalp human hair strands of 80-120-microm thickness and different washing procedures have been evaluated. The repeatability of the method has been tested and the ability to measure sulfur isotopic variations in 1,000-microm-long hair segments has been evaluated. A horse hair sample previously characterized for carbon and nitrogen isotope ratios in an interlaboratory study has been characterized by LA-MC-ICP-MS to be used as an in-house standard for the bracketing of human hair strands. (34)S/(32)S isotope amount ratios have been measured and corrected for instrumental mass bias adopting the external standardization approach using National Institute of Standards and Technology (NIST) RM8553 and full uncertainty budgets have been calculated using the Kragten approach. Results are reported as both (34)S/(32)S isotope amount ratios and deltaS(V-CDT) values (sulfur isotopic differences relative to a reference sample expressed in the Vienna Canyon Diablo Troilite (V-CDT) scale) calculated using NIST RM8553, NIST RM8554, and NIST RM8556 to anchor results to the V-CDT scale. The main advantage of the new method versus conventional gas source isotope ratio mass spectrometry measurements is that longitudinal variations in sulfur isotope amount ratios can be resolved. Proof of concept is shown with human scalp hair strands from three individuals, two UK residents and one traveler (long periods of time abroad). The method enables monitoring of longitudinal isotope ratio variations in single hair strands. Absolute ratios are reported and delta(34)S(V-CDT) values are plotted for comparison. Slight variations of <1.2 per thousand were detected in the hair strands from UK residents whereas the traveler presented a variation of >5 per thousand. Thus, the measurement of sulfur isotopic variations in hair samples has potential to be an indicator of geographical origin and recent movements and could be used in combination with isotope ratio measurements in water/foodstuffs from different geographical locations to provide important information in nutritional and geographical studies.

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A new method for the measurement of SI traceable carbon isotope amount ratios using a multicollector inductively coupled mass spectrometer (MC-ICPMS) is reported for the first time. Carbon (13)C/(12)C isotope amount ratios have been measured for four reference materials with carbon isotope amount ratios ranging from 0.010659 (delta(13)C(VPDB) = -46.6 per thousand) to 0.011601 (delta(13)C(VPDB) = +37 per thousand). Internal normalization by measuring boron (11)B/(10)B isotope amount ratios has been used to correct for the effects of instrumental mass bias. Absolute (13)C/(12)C ratios have been measured and corrected for instrumental mass bias and full uncertainty budgets have been calculated using the Kragten approach. Corrected (13)C/(12)C ratios for NIST RM8545 (Lithium Carbonate LSVEC), NIST RM8573 (L-Glutamic Acid USGS40), NIST RM8542 (IAEA-CH6 Sucrose) and NIST RM8574 (L-Glutamic Acid USGS41) differed from reference values by 0.06-0.20%. Excellent linear correlation (R = 0.9997) was obtained between corrected carbon isotope amount ratios and expected carbon isotope amount ratios of the four chosen NIST RMs. The method has proved to be linear within this range (from (13)C/(12)C = 0.010659 to (13)C/(12)C =0.011601), and therefore, it is suitable for the measurement of carbon isotope amount ratios within the natural range of variation of organic carbon compounds, carbonates, elemental carbon, carbon monoxide, and carbon dioxide. In addition, a CO2 gas sample previously characterized in-house by conventional dual inlet isotope ratio mass spectrometry has been analyzed and excellent agreement has been found between the carbon isotope amount ratio value measured by MC-ICPMS and the IRMS measurements. Absolute values for carbon isotope amount ratios traceable to the SI are given for each NIST RM, and the combined uncertainty budget (including instrumental error and each parameter contributing to Russell expression for mass bias correction) has been found to be < 0.1% for the four materials. The advantage of the method versus conventional gas source isotope ratio mass spectrometry measurements is that carbon isotope amount ratios are measured as C(+) instead of CO2(+), and therefore, an oxygen (17)O correction due to the presence of (12)C(17)O(16)O(+) is not required. Organic compounds in solution can be measured without previous derivatization, combustion steps, or both, thus making the process simple. The novel methodology opens new avenues for the measurement of absolute carbon isotope amount ratios in a wide range of samples.

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A systematic comparison of delta34S measurements by multicollector inductively coupled plasma mass spectrometry (MCICPMS) using two different standardisation approaches and two different reference materials as working standards is reported for the first time. Full uncertainty budgets have been calculated using the Kragten approach. Internal standardisation by measuring Si ratios and external standardisation by bracketing samples with either NIST RM8553 or NIST RM8554 have been compared to correct for the effects of mass bias. The delta34S value and the associated uncertainty ( per thousand) were found to be slightly different when using different approaches. Corrected 34S:32S ratios for NIST RM8553 and NIST RM8554 differed from those previously reported by 0.1 to 0.5% when using external standardisation. 34S:32S ratios for NIST RM8553 and NIST RM8554 differed from those previously reported by 0.06 to 0.15% when using Si internal standardisation. This indicated that in order to minimise deviation from true ratio values, Si internal standardisation would be a more appropriate option when using a Neptune MCICPMS instrument. delta(34)S values were obtained for four different methionine samples and expanded uncertainties (k = 2) expressed in delta34S ( per thousand) ranged from 0.7 per thousand to 1.6 per thousand. Regardless of the approach used for the mass bias correction, three parameters provided the major contributions to the standard uncertainty of the delta34S(V-CDT) value. These were the measured 34S:32S in the sample, the measured 34S:32S for the working standard and the known delta34S(V-CDT) value of the working standard. Results using both approaches are compared and the Si internal standardisation approach is used to provide results for an inter-laboratory comparison.

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A new method has been developed for measuring the D/H ratio of the nonexchangeable sites of citric acid by isotope ratio mass spectrometry (IRMS). Pure citric acid is transformed into its calcium salt and subsequently analyzed by pyrolysis-IRMS. The citric acid isolated from authentic fruit juices (citrus, pineapple, and red fruits) systematically shows higher D/H values than its nonfruit counterpart produced by fermentation of various sugar sources. The discrimination obtained with this simplified method is similar to that obtained previously by applying site specific isotopic fractionation-nuclear magnetic resonance (SNIF-NMR) to an ester derivative of citric acid. The combination of carbon 13 and deuterium measurements of extracted citric acid is proposed as a routine method for an optimum detection of exogenous citric acid in all kinds of fruit juices.

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The effect of humic acids on the sequential extraction of metals from various soils and sediments has been studied. A new multi-element extraction method optimised via experimental design has been employed. The method uses centrifugation to pass the extractant solution, at varying pH, through the sediment sample. The sequential leaches were collected and analysed by ICP-AES. Chemometric data processing was utilised to identify the composition of the physico-chemical components in order to characterise the sample. A sediment sample collected from Carnon River (Cornwall, UK) and a reference material (NIST 2711 agricultural soil) were spiked with humic acids and the sequential extraction scheme was used to monitor the changes in metal distribution. The method has proved a quick and reliable way to evaluate different sediment samples, and has potential as a new tool for environmental geochemistry analysis.

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The optimisation of a simple multielement extraction method employing an experimental design approach is described. The method uses centrifugation to pass one extractant solution at varying pH through a contaminated soil sample. The nature and concentration of the acid, rate of centrifugation and time, number of sequential leachates and the ratio of extractant volume: sample weight have been studied in order to obtain the optimum conditions for extraction. A fractional factorial experimental design was performed, and the results were used to identify significance which was then evaluated by carrying out a central composite experimental approach. Once optimum conditions had been obtained, sequential leaches were analysed by ICP-AES and chemometrics were employed to identify the composition of each component. Comparisons have been made with previous studies and tentative assignments, based on well defined separated fractions and percentage compositions for individual elements, used to identify the different physico-chemical components in the sample.

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