Analysis of organic volatile residues in 9 mm spent cartridges

Determining the time since discharge of spent cartridges found on a crime scene may be very useful in firearm investigations. The potential of small calibre munitions was barely studied before and this work did therefore focus on that problematic. The first step was to optimize the detection potential of solidphase microextraction (SPME) followed by gas chromatography coupled to a mass spectrometry detector (GC/MS). This allowed determining the organic volatile composition of empty cartridges immediately after a gunshot. Identification of 32 detected compounds was confirmed by the analysis of reference substances. Preliminary aging studies over 32 hours were carried out on selected target compounds to evaluate their potential for the dating of shotguns.

Generation of polycyclic aromatic hydrocarbons (PAHs) during woodworking operations.

Occupational exposures to wood dust have been associated with an elevated risk of sinonasal cancer (SNC). Wood dust is recognized as a human carcinogen but the specific cancer causative agent remains unknown. One possible explanation is a co-exposure to; wood dust and polycyclic aromatic hydrocarbons (PAHs). PAHs could be generated during incomplete combustion of wood due to heat created by use of power tools. To determine if PAHs are generated from wood during common wood working operations, PAH concentrations in wood dust samples collected in an experimental chamber operated under controlled conditions were analyzed. In addition, personal air samples from workers exposed to wood dust (n = 30) were collected. Wood dust was generated using three different power tools: vibrating sander, belt sander, and saw; and six wood materials: fir, Medium Density Fiberboard (MDF), beech, mahogany, oak and wood melamine. Monitoring of wood workers was carried out by means of personal sampler device during wood working operations. We measured 21 PAH concentrations in wood dust samples by capillary gas chromatography-ion trap mass spectrometry (GC-MS). Total PAH concentrations in wood dust varied greatly (0.24-7.95 ppm) with the lowest being in MDF dust and the highest in wood melamine dust. Personal PAH exposures were between 37.5-119.8 ng m(-3) during wood working operations. Our results suggest that PAH exposures are present during woodworking operations and hence could play a role in the mechanism of cancer induction related to wood dust exposure.

Determination of 13C/12C ratios of endogenous urinary 5-amino-imidazole-4-carboxamide 1-D-ribofuranoside (AICAR)

RATIONALE: AICAR (5-aminoimidazole-4-carboxamide 1β-D-ribofuranoside) is prohibited in sport according to rules established by the World Anti-Doping Agency. Doping control laboratories identify samples where AICAR abuse is suspected by measuring its urinary concentration and comparing the observed level with naturally occurring concentrations. As the inter-individual variance of urinary AICAR concentrations is large, this approach requires a complementary method to unambiguously prove the exogenous origin of AICAR. Therefore, a method for the determination of carbon isotope ratios (CIRs) of urinary AICAR has been developed and validated. METHODS: Concentrated urine samples were fractionated by means of liquid chromatography for analyte cleanup. Derivatization of AICAR yielding the trimethylsilylated analog was necessary to enable CIR determinations by gas chromatography/combustion/isotope ratio mass spectrometry. The method was tested for its repeatability and stability over time and a linear mixing model was applied to test for possible isotopic discrimination. A reference population of n = 63 males and females was investigated to calculate appropriate reference limits to differentiate endogenous from exogenous urinary AICAR. These limits were tested by an AICAR elimination study. RESULTS: The developed method fulfills all the requirements for adequate sports drug testing and was found to be fit for purpose. The investigated reference population showed a larger variability in the CIR of AICAR than of the endogenous steroids. Nevertheless, the calculated thresholds for differences between AICAR and endogenous steroids can be applied straightforwardly to evaluate suspicious doping control samples with the same statistical confidence as established e.g. for testosterone misuse. These thresholds enabled the detection of a single oral AICAR administration for more than 40 h. CONCLUSIONS: Determination of thee CIRs is the method of choice to distinguish between an endogenous and an exogenous source of urinary AICAR. The developed method will enable investigations into doping control samples with elevated urinary concentrations of AICAR and clearly differentiate between naturally produced/elevated and illicitly administered AICAR.

Test methods: anabolics.

In the International Olympic Committee (IOC) accredited laboratories, specific methods have been developed to detect anabolic steroids in athletes' urine. The technique of choice to achieve this is gas-chromatography coupled with mass spectrometry (GC-MS). In order to improve the efficiency of anti-doping programmes, the laboratories have defined new analytical strategies. The final sensitivity of the analytical procedure can be improved by choosing new technologies for use in detection, such as tandem mass spectrometry (MS-MS) or high resolution mass spectrometry (HRMS). A better sample preparation using immuno-affinity chromatography (IAC) is also a good tool for improving sensitivity. These techniques are suitable for the detection of synthetic anabolic steroids whose structure is not found naturally in the human body. The more and more evident use, on a large scale, of substances chemically similar to the endogenous steroids obliges both the laboratory and the sports authorities to use the steroid profile of the athlete in comparison with reference ranges from a population or with intraindividual reference values.

Cuticular hydrocarbons of Chagas disease vectors in Mexico

Capillary gas-liquid chromatography was used to analyse the cuticular hydrocarbons of three triatomine species, Triatoma dimidiata, T. barberi and Dipetalogaster maxima, domestic vectors of Chagas disease in Mexico. Mixtures of saturated hydrocarbons of straight and methyl-branched chains were characteristic of the three species, but quantitatively different. Major methylbranched components mostly corresponded to different saturated isomers of monomethyl, dimethyl and trimethyl branched hydrocarbons ranging from 29 to 39 carbon backbones. Sex-dependant, quantitative differences in certain hydrocarbons were apparent in T. dimidiata.

Approaches to identifying and quantifying polycyclic aromatic hydrocarbons of molecular weight 302 in diesel particulates

Among the PAH class of compounds, high molecular weight PAH are now considered as relevant cancer inducers, but not all of them have the same biological activity. However, their analysis is difficult, mainly due to the presence of numerous isomers and due to their low volatility. Retention indices (Ri) for 13 dibenzopyrenes and homologues were determined by high-resolution capillary gas chromatography (GC) with four different stationary phases: a 5% phenyl-substituted methylpolysiloxane column (DB-5 ms), a 35% phenyl-substituted methylpolysiloxane column (BPX-35), a 50% phenyl-substituted methylpolysiloxane column (BPX-50), and a 35% trifluoropropylmethyl polysiloxane stationary phase (Rtx-200). Correlations for retention on each phase were investigated by using 8 independent molecular descriptors. Ri has been shown to be linearly correlated to PAH volume, polarisability alpha, Hückel-pi energy on the four examined columns. Ionisation potential Ip is a fourth variable which improves the regression model for DB-5ms, BPX-35, and BPX-50 column. Correlation coefficients ranging from r2 = 0.935 to r2 = 0.952 are then observed. Application of these indices to the identification and quantification of PAH with MW 302 in certified diesel particulate matter SRM 1650a is presented and discussed. [Authors]

Nonenzymatic oxidation of trienoic fatty acids contributes to reactive oxygen species management in Arabidopsis.

In higher plants such as Arabidopsis thaliana, omega-3 trienoic fatty acids (TFAs), represented mainly by alpha-linolenic acid, serve as precursors of jasmonic acid (JA), a potent lipid signal molecule essential for defense. The JA-independent roles of TFAs were investigated by comparing the TFA- and JA-deficient fatty acid desaturase triple mutant (fad3-2 fad7-2 fad8 (fad3 fad7 fad8)) with the aos (allene oxide synthase) mutant that contains TFAs but is JA-deficient. When challenged with the fungus Botrytis, resistance of the fad3 fad7 fad8 mutant was reduced when compared with the aos mutant, suggesting that TFAs play a role in cell survival independently of being the precursors of JA. An independent genetic approach using the lesion mimic mutant accelerated cell death2 (acd2-2) confirmed the importance of TFAs in containing lesion spread, which was increased in the lines in which the fad3 fad7 fad8 and acd2-2 mutations were combined when compared with the aos acd2-2 lines. Malondialdehyde, found to result from oxidative TFA fragmentation during lesion formation, was measured by gas chromatography-mass spectrometry. Its levels correlated with the survival of the tissue. Furthermore, plants lacking TFAs overproduced salicylic acid (SA), hydrogen peroxide, and transcripts encoding several SA-regulated and SA biosynthetic proteins. The data suggest a physiological role for TFAs as sinks for reactive oxygen species.

Indoor air quality in a public building following smoking bans

Introduction: Exposure to environmental tobacco smoke (ETS) is a major environmental risk factor. Indoor contaminants come from a variety of sources, which can include inadequate ventilation, volatile organic compounds (VOCs), biological agents, combustion products, and ETS. Because ETS is one of the most frequent causes of IAQ complaints as well as the high mortality of passive smoking, in June 2004 the University of Geneva made the decision to ban smoking inside the so called "Uni-Mail" building, the biggest Swiss University human science building of recent construction, and the ordinance was applied beginning in October 2004. This report presents the finding related to the IAQ of the "Uni-Mail" building before and after smoking bans using nicotine, suspended dust, condensate and PAHs level in air as tracers to perform an assessment of passive tobacco exposure for non-smokers inside the building. Methods: Respirable particles (RSP) A real time aerosol monitor (model DataRAM)was place at sampling post 1, level ground floor. Condensate It consists in extracting any organic matter taken on the glass fibre filters by MeOH, and then measuring the total absorbent of the MeOH extract to the UV wavelength of 447 nm. Nicotine Nicotine was taken by means of cartridges containing of XAD-4 to the fixed flow of 0.5 L/min. The analytical method used for the determination of nicotine is based on gas chromatography with Nitrogen selective detector GC-NPD. Results: Figure 1 shows the box plot density display of 3 parameters before and after smoking bans for all 7 sampling posts: dust, condensate and nicotine in air in μg/m3. Conclusion: Before the smoking ban, the level of the concentrations of respirable particles (RSP) is raised more, average of the day 320 μg/m3, with peaks of more than 1000 μg/m3, compared with the values of the surrounding air between 22 and 30 μg/m3. The nicotine level is definitely more important (average 5.53 μg/m3, field 1.5 to 17.9 μg/m3). Once the smoking bans inside the building were applied, one notes a clear improvement in terms of concentrations of pollutants. For dust, the concentration fell by 3 times (average: 130 μg/m3, range: 40 to 160 μg/m3) and that of nicotine by 10 times (average: 0.53 μg/m3, range: 0 to 1.69 μg/m3) compared to that found before smoking bans. The outdoor air RSP concentration was 22 μg/m3 or 10 times lower. Nicotine seems to be the best tracer for ETS free of interference, independent of location or season.

Activity of Brazilian and Bulgarian propolis against different species of Leishmania

Extracts of propolis samples collected in Brazil and Bulgaria were assayed against four Leishmania species - Leishmania amazonensis, L. braziliensis, L. chagasi from the New World, and L. major from the Old World - associated to different clinical forms of leishmaniasis. The composition of the extracts has been previously characterized by high temperature high resolution gas chromatography coupled to mass spectrometry. Considering the chemical differences among the extracts and the behavior of the parasites, it was observed significant differences in the leishmanicidal activities with IC50/1 day values in the range of 2.8 to 229.3 µg/ml . An overall analysis showed that for all the species evaluated, Bulgarian extracts were more active than the ethanol Brazilian extract. As the assayed propolis extracts have their chemical composition determined it merits further investigation the effect of individual components or their combinations on each Leishmania species.

ELOVL6 Genetic Variation Is Related to Insulin Sensitivity: A New Candidate Gene in Energy Metabolism

BACKGROUND: The elongase of long chain fatty acids family 6 (ELOVL6) is an enzyme that specifically catalyzes the elongation of saturated and monounsaturated fatty acids with 12, 14 and 16 carbons. ELOVL6 is expressed in lipogenic tissues and it is regulated by sterol regulatory element binding protein 1 (SREBP-1). OBJECTIVE: We investigated whether ELOVL6 genetic variation is associated with insulin sensitivity in a population from southern Spain. DESIGN: We undertook a prospective, population-based study collecting phenotypic, metabolic, nutritional and genetic information. Measurements were made of weight and height and the body mass index (BMI) was calculated. Insulin resistance was measured by homeostasis model assessment. The type of dietary fat was assessed from samples of cooking oil taken from the participants' kitchens and analyzed by gas chromatography. Five SNPs of the ELOVL6 gene were analyzed by SNPlex. RESULTS: Carriers of the minor alleles of the SNPs rs9997926 and rs6824447 had a lower risk of having high HOMA_IR, whereas carriers of the minor allele rs17041272 had a higher risk of being insulin resistant. An interaction was detected between the rs6824447 polymorphism and the intake of oil in relation with insulin resistance, such that carriers of this minor allele who consumed sunflower oil had lower HOMA_IR than those who did not have this allele (P = 0.001). CONCLUSIONS: Genetic variations in the ELOVL6 gene were associated with insulin sensitivity in this population-based study.

Chemistry, cytotoxicity and antileishmanial activity of the essential oil from Piper auritum

Leishmaniasis is one of the most important parasitic infections, but current treatments are unsatisfactory due to their toxicity, cost and resistance. Therefore, the development of new antileishmanial compounds is imperative. Many people who live in endemic areas use plants as an alternative to treat the disease. In this paper, we characterised the essential oil from Piper auritum, evaluated its cytotoxicity and determined its antileishmanial activity. The chromatogram obtained by gas chromatography revealed 60 peaks and we found that safrole was the most abundant compound, composing 87% of the oil. The oil was active against the promastigotes of Leishmania major, Leishmania mexicana, Leishmania braziliensis and Leishmania donovani with a favourable selectivity index against peritoneal macrophages from BALB/c mice. The Piper-oil inhibited the growing of intracellular amastigotes of L. donovani with an IC50 value of 22.3 ± 1.8 μg/mL. This study demonstrates the usefulness of the essential oils as a promising alternative to treat leishmaniasis.

New trends in the kitchen: propellants assessment of edible food aerosol sprays used on food.

New products available for food creations include a wide variety of "supposed" food grade aerosol sprays. However, the gas propellants used cannot be considered as safe. The different legislations available did not rule any maximum residue limits, even though these compounds have some limits when used for other food purposes. This study shows a preliminary monitoring of propane, butane and dimethyl ether residues, in cakes and chocolate after spraying, when these gases are used as propellants in food aerosol sprays. Release kinetics of propane, butane and dimethyl ether were measured over one day with sprayed food, left at room temperature or in the fridge after spraying. The alkanes and dimethyl ether analyses were performed by headspace-gas chromatography-mass spectrometry/thermal conductivity detection, using monodeuterated propane and butane generated in situ as internal standards. According to the obtained results and regardingthe extrapolations of the maximum residue limits existing for these substances, different delays should be respected according to the storage conditions and the gas propellant to consume safely the sprayed food.

Stable carbon isotope composition of perirenal adipose tissue fatty acids from Engadine sheep grazing either mountain or lowland pasture

To provide further insights into ruminant lipid digestion and metabolism, and into cis9, trans-11 18:2 synthesis, 12 growing Engadine lambs grazing either mountain pasture (2,250 m above sea level; n = 6) or lowland pasture (400 m above sea level; n = 6) were studied. Both pastures consisted exclusively of C-3 plants. Before the experiment, all animals grazed a common pasture for 6 wk. Grasses and perirenal adipose tissues of the sheep were analyzed for fatty acids by gas chromatography. Stable C-isotope ratios (delta C-13 values in % vs. the Vienna Pee Dee Belemnite standard) were determined in the composite samples by elemental analysis-isotope ratio mass spectrometry. The delta C-13 of the individual fatty acids were measured by gas chromatography-combustion-isotope ratio mass spectrometry. The delta C-13 value of the entire mountain pasture grass was -27.5% (SD 0.31), whereas that of the lowland pasture grass was -30.0% (SD 0.07). This difference was reflected in the perirenal adipose tissues of the corresponding sheep (P < 0.05), even though the delta C-13 values were less in the animals than in the grass. The delta C-13 values for cis-9 16:1 and cis-9 18:1 in perirenal fat differed between mountain and lowland lambs (P < 0.05). The 16:0 in the adipose tissue was enriched in C-13 by 5% compared with the dietary 16:0, likely as a result of partly endogenous synthesis. The d13C values of cis-9, trans-11 18:2 (cis-9, trans-11 CLA) in the adipose tissue were smaller than those of its dietary precursors, cis-9, cis-12 18:2 and cis-9, cis-12, cis-15 18:3; conversely, the delta C-13 values of trans-11 18:1 were not, suggesting that large proportions of perirenal cis-9, trans-11 18:2 were of endogenous origin and discrimination against C-13 occurred during Delta(9)-desaturation. The same discrimination was indicated by the isotopic shift between 16:0 and cis-9 16:1 in the mountain grazing group. Furthermore, the delta C-13 values of cis-9, trans-11 18:2 were smaller relative to the precursor fatty acids in the mountain lambs compared with the lowland group. This result suggests a reduced extent of biohydrogenation in lambs grazing on mountain grass in comparison with those grazing on lowland grass. This was supported by the smaller cis-9, trans-11 18:2 concentrations in total fatty acids found in the adipose tissues of the lowland lambs (P < 0.001). The results of this study demonstrate that natural differences between delta C-13 values of swards from different pastures and the adipose tissue fatty acids could be used as tracers in studies of lipid metabolism in ruminants.

The cuticular hydrocarbons of the Triatoma sordida species subcomplex (Hemiptera: Reduviidae)

The cuticular hydrocarbons of the Triatoma sordida subcomplex (Hemiptera: Reduviidae: Triatominae) were ana-lysed by gas chromatography and their structures identified by mass spectrometry. They comprised mostly n-alkanes and methyl-branched alkanes with one-four methyl substitutions. n-alkanes consisted of a homologous series from C21-C33 and represented 33-45% of the hydrocarbon fraction; n-C29 was the major component. Methyl-branched alkanes showed alkyl chains from C24-C43. High molecular weight dimethyl and trimethylalkanes (from C35-C39) represented most of the methyl-branched fraction. A few tetramethylalkanes were also detected, comprising mostly even-numbered chains. Several components such as odd-numbered 3-methylalkanes, dimethylalkanes and trimethylalkanes of C37 and C39 showed patterns of variation that allowed the differentiation of the species and populations studied. Triatoma guasayana and Triatoma patagonica showed the most distinct hydrocarbon patterns within the subcomplex. The T. sordida populations from Brazil and Argentina showed significantly different hydrocarbon profiles that posed concerns regarding the homogeneity of the species. Triatoma garciabesi had a more complex hydrocarbon pattern, but it shared some similarity with T. sordida. The quantitative and qualitative variations in the cuticular hydrocarbons may help to elucidate the relationships between species and populations of this insect group.

Plasma and urine profiles of Delta9-tetrahydrocannabinol and its metabolites 11-hydroxy-Delta9-tetrahydrocannabinol and 11-nor-9-carboxy-Delta9-tetrahydrocannabinol after cannabis smoking by male volunteers to estimate recent consumption by athletes.

Since 2004, cannabis has been prohibited by the World Anti-Doping Agency for all sports competitions. In the years since then, about half of all positive doping cases in Switzerland have been related to cannabis consumption. In doping urine analysis, the target analyte is 11-nor-9-carboxy-Delta(9)-tetrahydrocannabinol (THC-COOH), the cutoff being 15 ng/mL. However, the wide urinary detection window of the long-term metabolite of Delta(9)-tetrahydrocannabinol (THC) does not allow a conclusion to be drawn regarding the time of consumption or the impact on the physical performance. The purpose of the present study on light cannabis smokers was to evaluate target analytes with shorter urinary excretion times. Twelve male volunteers smoked a cannabis cigarette standardized to 70 mg THC per cigarette. Plasma and urine were collected up to 8 h and 11 days, respectively. Total THC, 11-hydroxy-Delta(9)-tetrahydrocannabinol (THC-OH), and THC-COOH were determined after hydrolysis followed by solid-phase extraction and gas chromatography/mass spectrometry. The limits of quantitation were 0.1-1.0 ng/mL. Eight puffs delivered a mean THC dose of 45 mg. Plasma levels of total THC, THC-OH, and THC-COOH were measured in the ranges 0.2-59.1, 0.1-3.9, and 0.4-16.4 ng/mL, respectively. Peak concentrations were observed at 5, 5-20, and 20-180 min. Urine levels were measured in the ranges 0.1-1.3, 0.1-14.4, and 0.5-38.2 ng/mL, peaking at 2, 2, and 6-24 h, respectively. The times of the last detectable levels were 2-8, 6-96, and 48-120 h. Besides high to very high THC-COOH levels (245 +/- 1,111 ng/mL), THC (3 +/- 8 ng/mL) and THC-OH (51 +/- 246 ng/mL) were found in 65 and 98% of cannabis-positive athletes' urine samples, respectively. In conclusion, in addition to THC-COOH, the pharmacologically active THC and THC-OH should be used as target analytes for doping urine analysis. In the case of light cannabis use, this may allow the estimation of more recent consumption, probably influencing performance during competitions. However, it is not possible to discriminate the intention of cannabis use, i.e., for recreational or doping purposes. Additionally, pharmacokinetic data of female volunteers are needed to interpret cannabis-positive doping cases of female athletes.