Headspace analysis of smokeless powders: Development of mass calibration methods using microdrop printing for chromatographic and ion mobility spectrometric detection

Smokeless powder additives are usually detected by their extraction from post-blast residues or unburned powder particles followed by analysis using chromatographic techniques. This work presents the first comprehensive study of the detection of the volatile and semi-volatile additives of smokeless powders using solid phase microextraction (SPME) as a sampling and pre-concentration technique. Seventy smokeless powders were studied using laboratory based chromatography techniques and a field deployable ion mobility spectrometer (IMS). The detection of diphenylamine, ethyl and methyl centralite, 2,4-dinitrotoluene, diethyl and dibutyl phthalate by IMS to associate the presence of these compounds to smokeless powders is also reported for the first time. A previously reported SPME-IMS analytical approach facilitates rapid sub-nanogram detection of the vapor phase components of smokeless powders. A mass calibration procedure for the analytical techniques used in this study was developed. Precise and accurate mass delivery of analytes in picoliter volumes was achieved using a drop-on-demand inkjet printing method. Absolute mass detection limits determined using this method for the various analytes of interest ranged between 0.03–0.8 ng for the GC-MS and between 0.03–2 ng for the IMS. Mass response graphs generated for different detection techniques help in the determination of mass extracted from the headspace of each smokeless powder. The analyte mass present in the vapor phase was sufficient for a SPME fiber to extract most analytes at amounts above the detection limits of both chromatographic techniques and the ion mobility spectrometer. Analysis of the large number of smokeless powders revealed that diphenylamine was present in the headspace of 96% of the powders. Ethyl centralite was detected in 47% of the powders and 8% of the powders had methyl centralite available for detection from the headspace sampling of the powders by SPME. Nitroglycerin was the dominant peak present in the headspace of the double-based powders. 2,4-dinitrotoluene which is another important headspace component was detected in 44% of the powders. The powders therefore have more than one headspace component and the detection of a combination of these compounds is achievable by SPME-IMS leading to an association to the presence of smokeless powders.

Investigation of particle identification methods for the analysis of the photoproduction of neutral kaons on a liquid deuterium target

The Photoproduction of neutral kaons off a deuteron target has been investigated at the Tohoku University Laboratory of Nuclear Science. The PID methods investigated incorporated a combination of momentum, velocity (β=v/c), and energy deposition per unit length (dE/dx) measurements. The analysis demonstrates that energy deposition and time of flight are exceedingly useful. A higher signal to background ratio was achieved for hard cuts in combination. A probabilistic likelihood estimation approach (LE) as a method for PID was also explored. The probability of a particle being correctly identified by this LE method and the preliminary results denote the need for highly precise limitations on the distributions from which the parameters would be extracted. It was confirmed that these PID are applicable approaches to properly identify pions for the analysis of this experiment. However, the background evident in the mass spectra points to the need for a higher level of proton identification.

Headspace Analysis of Smokeless Powders: Development of Mass Calibration Methods using Microdrop Printing for Chromatographic and Ion Mobility Spectrometric Detection

Smokeless powder additives are usually detected by their extraction from post-blast residues or unburned powder particles followed by analysis using chromatographic techniques. This work presents the first comprehensive study of the detection of the volatile and semi-volatile additives of smokeless powders using solid phase microextraction (SPME) as a sampling and pre-concentration technique. Seventy smokeless powders were studied using laboratory based chromatography techniques and a field deployable ion mobility spectrometer (IMS). The detection of diphenylamine, ethyl and methyl centralite, 2,4-dinitrotoluene, diethyl and dibutyl phthalate by IMS to associate the presence of these compounds to smokeless powders is also reported for the first time. A previously reported SPME-IMS analytical approach facilitates rapid sub-nanogram detection of the vapor phase components of smokeless powders. A mass calibration procedure for the analytical techniques used in this study was developed. Precise and accurate mass delivery of analytes in picoliter volumes was achieved using a drop-on-demand inkjet printing method. Absolute mass detection limits determined using this method for the various analytes of interest ranged between 0.03 - 0.8 ng for the GC-MS and between 0.03 - 2 ng for the IMS. Mass response graphs generated for different detection techniques help in the determination of mass extracted from the headspace of each smokeless powder. The analyte mass present in the vapor phase was sufficient for a SPME fiber to extract most analytes at amounts above the detection limits of both chromatographic techniques and the ion mobility spectrometer. Analysis of the large number of smokeless powders revealed that diphenylamine was present in the headspace of 96% of the powders. Ethyl centralite was detected in 47% of the powders and 8% of the powders had methyl centralite available for detection from the headspace sampling of the powders by SPME. Nitroglycerin was the dominant peak present in the headspace of the double-based powders. 2,4-dinitrotoluene which is another important headspace component was detected in 44% of the powders. The powders therefore have more than one headspace component and the detection of a combination of these compounds is achievable by SPME-IMS leading to an association to the presence of smokeless powders.

Tooth wear in Irish teenagers: a laboratory and epidemiological study

Aim: To investigate the characteristics, development and determinants of toothwear among Irish schoolchildren. Methods: A cross-sectional (examination at 16-years-old) and longitudinal (examinations at 5-,12-,14-years) study were conducted. Two indices were used to measure toothwear, children/parents completed a demographic profile and questionnaire on oral hygiene and dietary practices, health, and lifestyle in both studies. Saliva was collected from consenting 16-year-olds. The explanatory variables for the cross-sectional and longitudinal study were derived from children/parents responses. Differences in salivary profiles were determined for subsets; the protein concentration was determined with Bradford protein assay and protein carbonyl concentration (a protein oxidation marker) was determined spectrophotometrically. Gel-electrophoresis and mass spectrometry determined proteins and ion chromatography inorganic ions. Statistical significance was accepted at p<0.05. Results: At 16-years-old the prevalence of toothwear with dentine visible was 44%. No difference in salivary flow rates existed. In unstimulated saliva a higher mean, protein carbonyl (p<0.0001) and total calcium concentration (p<0.002) existed for the group with moderate toothwear. In stimulated saliva the moderate toothwear group had a lower mean protein concentration(p<0.0001). The 2-DE protein spots prepared for a sub-group differed between those with toothwear and without. Mass spectrometry, identified one of the different proteins as IgA. For 16-year-olds, the self-reported factors indicated that brushing after breakfast was associated with lower toothwear scores(p<0.03). Nail-biting, being asthmatic or reporting a dry mouth were associated with higher toothwear scores(all p<0.05). Eating an apple daily or less was associated with less toothwear(p<0.002). In the longitudinal study toothwear into dentine at age five or 12-years was associated with more toothwear at age 14(all p<0.05). Discussion: The results illustrate the multifactorial aetiology of toothwear. The biochemical and physical correlates of saliva with toothwear requires further research. Conclusion: The impact of previous toothwear, salivary, dietary and personal factors on toothwear in the early permanent dentition is demonstrated.

Seawater carbonate chemistry and growth, calcification of Thoracosphaera heimii in a laboratory experiment

Ocean acidification is considered a major threat to marine ecosystems and may particularly affect calcifying organisms such as corals, foraminifera and coccolithophores. Here we investigate the impact of elevated pCO2 and lowered pH on growth and calcification in the common calcareous dinoflagellate Thoracosphaera heimii. We observe a substantial reduction in growth rate, calcification and cyst stability of T. heimii under elevated pCO2. Furthermore, transcriptomic analyses reveal CO2 sensitive regulation of many genes, particularly those being associated to inorganic carbon acquisition and calcification. Stable carbon isotope fractionation for organic carbon production increased with increasing pCO2 whereas it decreased for calcification, which suggests interdependence between both processes. We also found a strong effect of pCO2 on the stable oxygen isotopic composition of calcite, in line with earlier observations concerning another T. heimii strain. The observed changes in stable oxygen and carbon isotope composition of T. heimii cysts may provide an ideal tool for reconstructing past seawater carbonate chemistry, and ultimately past pCO2. Although the function of calcification in T. heimii remains unresolved, this trait likely plays an important role in the ecological and evolutionary success of this species. Acting on calcification as well as growth, ocean acidification may therefore impose a great threat for T. heimii.

Monitoring of Bridges using Computer Vision Methods

This paper is an overview of the development and application of Computer Vision for the Structural Health
Monitoring (SHM) of Bridges. A brief explanation of SHM is provided, followed by a breakdown of the stages of computer
vision techniques separated into laboratory and field trials. Qualitative evaluations and comparison of these methods have been
provided along with the proposal of guidelines for new vision-based SHM systems.

Inter-Laboratory Evaluation of a Next-Generation Sequencing Panel for Acute Myeloid Leukemia

INTRODUCTION: Acute myeloid leukemia (AML) is a heterogeneous clonal disorder often associated with dismal overall survival. The clinical diversity of AML is reflected in the range of recurrent somatic mutations in several genes, many of which have a prognostic and therapeutic value. Targeted next-generation sequencing (NGS) of these genes has the potential for translation into clinical practice. In order to assess this potential, an inter-laboratory evaluation of a commercially available AML gene panel across three diagnostic centres in the UK and Ireland was performed.

METHODS: DNA from six AML patient samples was distributed to each centre and processed using a standardised workflow, including a common sequencing platform, sequencing chips and bioinformatics pipeline. A duplicate sample in each centre was run to assess inter- and intra-laboratory performance.

RESULTS: An average sample read depth of 2725X (range 629-5600) was achieved using six samples per chip, with some variability observed in the depth of coverage generated for individual samples and between centres. A total of 16 somatic mutations were detected in the six AML samples, with a mean of 2.7 mutations per sample (range 1-4) representing nine genes on the panel. 15/16 mutations were identified by all three centres. Allelic frequencies of the mutations ranged from 5.6 to 53.3 % (median 44.4 %), with a high level of concordance of these frequencies between centres, for mutations detected.

CONCLUSION: In this inter-laboratory comparison, a high concordance, reproducibility and robustness was demonstrated using a commercially available NGS AML gene panel and platform.

A laboratory study of water ice erosion by low-energy ions

Water ice covers the surface of various objects in the outer Solar system.Within the heliopause, surface ice is constantly bombarded and sputtered by energetic particles from the solar wind and magnetospheres. We report a laboratory investigation of the sputtering yield of water ice when irradiated at 10 K by 4 keV singly (13C+, N+, O+, Ar+) and doubly charged ions (13C2+, N2+, O2+). The experimental values for the sputtering yields are in good agreement with the prediction of a theoretical model. There is no significant difference in the yield for singly and doubly charged ions. Using these yields, we estimate the rate of water ice erosion in the outer Solar system objects due to solar wind sputtering. Temperature-programmed desorption of the ice after irradiation with 13C+ and 13C2+ demonstrated the formation of 13CO and 13CO2, with 13CO being the dominant formed species.

Laboratory investigation of contactless displacement measurement using computer vision systems

Much of the bridge stock on major transport links in North America and Europe was constructed in the 1950’s and 1960’s and has since deteriorated or is carrying loads far in excess of the original design loads. Structural Health Monitoring Systems (SHM) can provide valuable information on the bridge capacity but the application of such systems is currently limited by access and system cost. This paper investigates the development of a low cost portable SHM system using commercially available cameras and computer vision techniques. A series of laboratory tests have been carried out to test the accuracy of displacement measurements using contactless methods. The results from each of the tests have been validated with established measurement methods, such as linear variable differential transformers (LVDTs). A video image of each test was processed using two different digital image correlation programs. The results obtained from the digital image correlation methods provided an accurate comparison with the validation measurements. The calculated displacements agree within 4% of the verified measurements LVDT measurements in most cases confirming the suitability full camera based SHM systems

Investigating Feasibility of Drive-by Bridge Monitoring by Laboratory Experiments

A potentially powerful drive-by bridge inspection approach was proposed to inspect bridge conditions utilizing the vibrations of a test vehicle while it passes over the target bridge. This approach suffers from the effect of roadway surface roughness and two solutions were proposed in previous studies: one is to subtract the responses of two vehicles (time-domain method) before spectral analysis and the other one is to subtract the spectrum of one vehicle from that of the other (frequency-domain method). Although the two methods were verified theoretically and numerically, their practical effectiveness is still an open question.Furthermore, whether the outcome spectra processed by those methods could be used to detect potential bridge damage is of our interests. In this study, a laboratory experiment was carried out with a test tractor-trailer system and a scaled bridge. It was observed that, first, for practical applications, it would be preferable to apply the frequency-domain method, avoiding the need to meet a strict requirement in synchronizing the responses of the two trailers in time domain; second, the statistical pattern of the processed spectra in a specific frequency band could be an effective anomaly indicator incorporated in drive-by inspection methods.

A comparison of in situ vs. ex situ filtration methods on the assessment of dissolved and particulate metals at hydrothermal vents

The objective of this study was to assess the impact of the filtration method (in situ vs. ex situ) on the dissolved/particulate partitioning of 12 elements in hydrothermal samples collected from the Lucky Strike vent field (Mid-Atlantic Ridge; MAR). To do so, dissolved ( <0.45 mu m) and particulate Mg, Li, Mn, U, V, As, Ba, Fe, Zn, Cd, Pb and Cu were measured using different techniques (HR-ICP-MS, ICP-AES and CCSA). Using in situ filtration as a baseline, we showed that ex situ filtration (on-board and on shore after freezing) resulted in an underestimation of the dissolved pool, which was counterbalanced by an overestimation of the particulate pool for almost all the elements studied. We also showed that on-board filtration was acceptable for the assessment of dissolved and particulate Mn, Mg, Li and U for which the measurement bias for the dissolved fraction did not exceed 3%. However, in situ filtration appeared necessary for the accurate assessment of the dissolved and particulate concentrations of V, As, Fe, Zn, Ba, Cd, Pb and Cu. In the case of Fe, on-board filtration underestimated the dissolved pool by up to 96%. Laboratory filtration (after freezing) resulted in a large bias in the dissolved and particulate concentrations, unambiguously discounting this filtration method for deep-sea chemical speciation studies. We discuss our results in light of the precipitation processes that can potentially affect the accuracy of ex situ filtration methods.

Semiology versus laboratory approaches: comparison between interarm blood preassure differences and APOB/APOA ratio

Nowadays complementary diagnostic methods are replacing clinical examination and semiology is loosing space in our clinical practice. One of our main concerns in clinical practice is to assess Cardiovascular risk (CVR). And previous studies reported an increased CVR with a divergence of 10mmhg or more measured between both arms-interarm blood pressure difference (IAD)

Comparative assessment of seller’s staining test (SST) and direct fluorescent antibody test for rapid and accurate laboratory diagnosis of rabies.

Background: Rabies causes 55, 000 annual human deaths globally and about 10,000 people are exposed annually in Nigeria. Diagnosis of animal rabies in most African countries has been by direct microscopic examination. In Nigeria, the Seller’s stain test (SST) was employed until 2009. Before then, both SST and dFAT were used concurrently until the dFAT became the only standard method. Objective: This study was designed to assess the sensitivity and specificity of the SST in relation to the ‘gold standard’ dFAT in diagnosis of rabies in Nigeria. Methods: A total of 88 animal specimens submitted to the Rabies National Reference Laboratory, Nigeria were routinely tested for rabies by SST and dFAT. Results: Overall, 65.9% of the specimens were positive for rabies by SST, while 81.8% were positive by dFAT. The sensitivity of SST in relation to the gold standard dFAT was 81.0% (95% CIs; 69.7% - 88.6%), while the specificity was 100% (95% CIs; 76% - 100%). Conclusion: The relatively low sensitivity of the SST observed in this study calls for its replacement with the dFAT for accurate diagnosis of rabies and timely decisions on administration of PEP to prevent untimely deaths of exposed humans.

Assessment of laboratory test utilization for HIV/AIDS care in urban ART clinics of Lilongwe, Malawi

Background The 2011 Malawi HIV guidelines promote CD4 monitoring for pre-ART assessment and considering HIVRNA monitoring for ART response assessment, while some clinics used CD4 for both. We assessed clinical ordering practices as compared to guidelines, and determined whether the samples were successfully and promptly processed. Methods We conducted a retrospective review of all patients seen in from August 2010 through July 2011,, in two urban HIV-care clinics that utilized 6-monthly CD4 monitoring regardless of ART status. We calculated the percentage of patients on whom clinicians ordered CD4 or HIVRNA analysis. For all samples sent, we determined rates of successful labprocessing, and mean time to returned results. Results Of 20581 patients seen, 8029 (39%) had at least one blood draw for CD4 count. Among pre-ART patients, 2668/2844 (93.8%) had CD4 counts performed for eligibility. Of all CD4 samples sent, 8082/9207 (89%) samples were successfully processed. Of those, mean time to processing was 1.6 days (s.d 1.5) but mean time to results being available to clinician was 9.3 days (s.d. 3.7). Regarding HIVRNA, 172 patients of 17737 on ART had a blood draw and only 118/213 (55%) samples were successfully processed. Mean processing time was 39.5 days (s.d. 21.7); mean time to results being available to clinician was 43.1 days (s.d. 25.1). During the one-year evaluated, there were multiple lapses in processing HIVRNA samples for up to 2 months. Conclusions Clinicians underutilize CD4 and HIVRNA as monitoring tools in HIV care. Laboratory processing failures and turnaround times are unacceptably high for viral load analysis. Alternative strategies need to be considered in order to meet laboratory monitoring needs.