Consistency of arsenic speciation in global tobacco products with implications for health and regulation

Background: Tobacco smoke is a major risk to the health of its users and arsenic is among the components of smoke present at concentrations of toxicological concern. There are significant variations in human toxicity between inorganic and organic arsenic species and the aim of this study was to determine whether there are predictable relationships among major arsenic species in tobacco that could be useful for risk assessment.

Methods: 14 samples of tobacco were studied spanning a wide range of concentrations in samples from different geographical regions, including certified reference materials and cigarette products. Inorganic and major organic arsenic species were extracted from powdered tobacco samples by nitric acid using microwave digestion. Concentrations of arsenic species in these extracts were determined using HPLC-ICPMS.

Results: The concentrations of total inorganic arsenic species range from 144 to 3914 mu g kg(-1), while organic species dimethylarsinic acid (DMA) ranges from 21 to 176 mu g As kg(-1), and monomethylarsonic acid (MA) ranges from 30 to 116 mu g kg(-1). The percentage of species eluted compared to the total arsenic extracted ranges from 11.1 to 36.8% suggesting that some As species (possibly macro-molecules, strongly complexed or in organic forms) do not elute from the column. This low percentage of column-speciated arsenic is indicative that more complex forms of arsenic exist in the tobacco. All the analysed species correlate positively with total arsenic concentration over the whole compositional range and regression analysis indicates a consistent ratio of about 4:1 in favour of inorganic arsenic compared with MA + DMA.

Conclusions: The dominance of inorganic arsenic species among those components analysed is a marked feature of the diverse range of tobaccos selected for study. Such consistency is important in the context of a WHO expert panel recommendation to regulate tobacco crops and products using total arsenic concentration. If implemented more research would be required to develop models that accurately predict the smoker's exposure to reduced inorganic arsenic species on the basis of leaf or product concentration and product design features.

Detection Limits of Organic Compounds Achievable with Intense, Short-Pulse Lasers

Many organic molecules have strong absorption bands which can be accessed by ultraviolet short pulse lasers to produce efficient ionization. This resonant multiphoton ionization scheme has already been exploited as an ionization source in time-of-flight mass spectrometers used for environmental trace analysis. In the present work we quantify the ultimate potential of this technique by measuring absolute ion yields produced from the interaction of 267 nm femtosecond laser pulses with the organic molecules indole and toluene, and gases Xe, N2 and O2. Using multiphoton ionization cross sections extracted from these results, we show that the laser pulse parameters required for real-time detection of aromatic molecules at concentrations of one part per trillion in air and a limit of detection of a few attomoles are achievable with presently available commercial laser systems. The potential applications for the analysis of human breath, blood and tissue samples are discussed.

Application of factor analysis and geostatistics to identify processes controlling the distribution and bioaccessibility of trace elements in Northern Ireland soils

Geologic and environmental factors acting over varying spatial scales can control
trace element distribution and mobility in soils. In turn, the mobility of an element in soil will affect its oral bioaccessibility. Geostatistics, kriging and principal component analysis (PCA) were used to explore factors and spatial ranges of influence over a suite of 8 element oxides, soil organic carbon (SOC), pH, and the trace elements nickel (Ni), vanadium (V) and zinc (Zn). Bioaccessibility testing was carried out previously using the Unified BARGE Method on a sub-set of 91 soil samples from the Northern Ireland Tellus1 soil archive. Initial spatial mapping of total Ni, V and Zn concentrations shows their distributions are correlated spatially with local geologic formations, and prior correlation analyses showed that statistically significant controls were exerted over trace element bioaccessibility by the 8 oxides, SOC and pH. PCA applied to the geochemistry parameters of the bioaccessibility sample set yielded three principal components accounting for 77% of cumulative variance in the data
set. Geostatistical analysis of oxide, trace element, SOC and pH distributions using 6862 sample locations also identified distinct spatial ranges of influence for these variables, concluded to arise from geologic forming processes, weathering processes, and localised soil chemistry factors. Kriging was used to conduct a spatial PCA of Ni, V and Zn distributions which identified two factors comprising the majority of distribution variance. This was spatially accounted for firstly by basalt rock types, with the second component associated with sandstone and limestone in the region. The results suggest trace element bioaccessibility and distribution is controlled by chemical and geologic processes which occur over variable spatial ranges of influence.

Inexact-aware architecture design for ultra-low power bio-signal analysis

This study introduces an inexact, but ultra-low power, computing architecture devoted to the embedded analysis of bio-signals. The platform operates at extremely low voltage supply levels to minimise energy consumption. In this scenario, the reliability of static RAM (SRAM) memories cannot be guaranteed when using conventional 6-transistor implementations. While error correction codes and dedicated SRAM implementations can ensure correct operations in this near-threshold regime, they incur in significant area and energy overheads, and should therefore be employed judiciously. Herein, the authors propose a novel scheme to design inexact computing architectures that selectively protects memory regions based on their significance, i.e. their impact on the end-to-end quality of service, as dictated by the bio-signal application characteristics. The authors illustrate their scheme on an industrial benchmark application performing the power spectrum analysis of electrocardiograms. Experimental evidence showcases that a significance-based memory protection approach leads to a small degradation in the output quality with respect to an exact implementation, while resulting in substantial energy gains, both in the memory and the processing subsystem.

Heterogeneous error-resilient scheme for spectral analysis in ultra-low power wearable electrocardiogram devices

Wearable devices performing advanced bio-signal analysis algorithms are aimed to foster a revolution in healthcare provision of chronic cardiac diseases. In this context, energy efficiency is of paramount importance, as long-term monitoring must be ensured while relying on a tiny power source. Operating at a scaled supply voltage, just above the threshold voltage, effectively helps in saving substantial energy, but it makes circuits, and especially memories, more prone to errors, threatening the correct execution of algorithms. The use of error detection and correction codes may help to protect the entire memory content, however it incurs in large area and energy overheads which may not be compatible with the tight energy budgets of wearable systems. To cope with this challenge, in this paper we propose to limit the overhead of traditional schemes by selectively detecting and correcting errors only in data highly impacting the end-to-end quality of service of ultra-low power wearable electrocardiogram (ECG) devices. This partition adopts the protection of either significant words or significant bits of each data element, according to the application characteristics (statistical properties of the data in the application buffers), and its impact in determining the output. The proposed heterogeneous error protection scheme in real ECG signals allows substantial energy savings (11% in wearable devices) compared to state-of-the-art approaches, like ECC, in which the whole memory is protected against errors. At the same time, it also results in negligible output quality degradation in the evaluated power spectrum analysis application of ECG signals.

A method for carbon stable isotope analysis of methyl halides and chlorofluorocarbons at pptv concentrations

A pre-concentration system has been validated for use with a gas chromatography/mass spectrometry/isotope ratio mass spectrometer (GC/MS/IRMS) to determine ambient air 13C/12C ratios for methyl halides (MeCl and MeBr) and chlorofluorocarbons (CFCs). The isotopic composition of specific compounds can provide useful information on their atmospheric budgets and biogeochemistry that cannot be ascertained from abundance measurements alone. Although pre-concentration systems have been previously used with a GC/MS/IRMS for atmospheric trace gas analysis, this is the first study also to report system validation tests. Validation results indicate that the pre-concentration system and subsequent separation technologies do not significantly alter the stable isotopic ratios of the target methyl halides, CFC-12 (CCl2F2) and CFC-113 (C2Cl3F3). Significant, but consistent, isotopic shifts of -27.5 to -25.6 do occur within the system for CFC-11 (CCl3F), although the shift is correctible. The method presented has the capacity to separate these target halocarbons from more than 50 other compounds in ambient air samples. Separation allows for the determination of stable carbon isotope ratios of five of these six target trace atmospheric constituents within ambient air for large volume samples (10 L). Representative urban air analyses from Belfast City are also presented which give carbon isotope results similar to published values for 13C/12C analysis of MeCl (-39.1) and CFC-113 (-28.1). However, this is the first paper reporting stable carbon isotope signatures for CFC-11 (-29.4) and CFC-12 (-37.0).

Wavelet phase coherence analysis: Application to a quiet-sun magnetic element

A new application of wavelet analysis is presented that utilizes the inherent phase information residing within the complex Morlet transform. The technique is applied to a weak solar magnetic network region, and the temporal variation of phase difference between TRACE 1700 Angstrom and SOHO/SUMER C II 1037 Angstrom intensities is shown. We present, for the first time in an astrophysical setting, the application of wavelet phase coherence, including a comparison between two methods of testing real wavelet phase coherence against that of noise. The example highlights the advantage of wavelet analysis over more classical techniques, such as Fourier analysis, and the effectiveness of the former to identify wave packets of similar frequencies but with differing phase relations is emphasized. Using cotemporal, ground-based Advanced Stokes Polarimeter measurements, changes in the observed phase differences are shown to result from alterations in the magnetic topology.

Studies on the persistence of estradiol benzoate and nortestosterone decanoate in hair of cattle following treatment with growth promoters, determined by ultra-high-performance liquid chromatography-tandem mass spectrometry

Measurement of steroid esters in bovine hair samples, using sensitive liquid chromatography-tandem mass spectrometry (LC-MS/MS), provides a powerful tool for identifying animals treated illicitly with growth promoters. The successful application of such testing requires appropriate sampling of hair from treated animals. This paper describes the results of hair analysis by LC-MS/MS for two animal studies in which animals were treated with estradiol-3-benzoate and nortestosterone decanoate. The results from the first animal study indicate that animals treated with these anabolic steroids may not always be identified from analysis of hair samples; positive test results occur sporadically and only for some of the treated animals. The results from the second animal study identify conditions attaching to positive hair samples, such as, that concentrations of steroid esters in hair are related to distance of sampling from point of injection and to time post-treatment, that concentrations of steroid esters in hair are related to dose given to the animal but that this relationship may vary over time post-treatment, and that steroid esters may be measured in regrowth hair taken some weeks after treatment. Steroid esters are determined along the length of the hair, confirming that accumulation of steroid esters into hair occurs from various sources, including blood, sweat and sebum. The reported research provides some useful insights into the mechanisms governing the persistence of steroid esters in bovine hair following illicit treatment with growth promoters. (C) 2009 Elsevier B.V. All rights reserved.