Statistical variable selection: an alternative prioritization strategy during the nontarget analysis of LC-HR-MS data

Liquid chromatography coupled to high resolution mass spectrometry (LC-HR-MS) has been one of the main analytical tools for the analysis of small polar organic pollutants in the environment. LC-HR-MS typically produces a large amount of data for a single chromatogram. The analyst is therefore required to perform prioritization prior to nontarget structural elucidation. In the present study, we have combined the F-ratio statistical variable selection and the apex detection algorithms in order to perform prioritization in data sets produced via LC-HR-MS. The approach was validated through the use of semisynthetic data, which was a combination of real environmental data and the artificially added signal of 31 alkanes in that sample. We evaluated the performance of this method as a function of four false detection probabilities, namely: 0.01, 0.02, 0.05, and 0.1%. We generated 100 different semisynthetic data sets for each F-ratio and evaluated that data set using this method. This design of experiment created a population of 30 000 true positives and 32 000 true negatives for each F-ratio, which was considered sufficiently large enough in order to fully validate this method for analysis of LC-HR-MS data. The effect of both the F-ratio and signal-to-noise ratio (S/N) on the performance of the suggested approach were evaluated through normalized statistical tests. We also compared this method to the pixel-by-pixel as well as peak list approaches. More than 92% of features present in the final feature list via the F-ratio method were also present in the conventional peak list generated by MZmine. However, this method was the only approach successful in the classification of samples, and thus prioritization, when compared to the other evaluated approaches. The application potential and limitations of the suggested method are discussed.acceptedVersio

Incidence and survival for cancer in children and young adults in the North of England, 1968–1995: a report from the Northern Region Young Persons’ Malignant Disease Registry

The Northern Region Young Persons’ Malignant Disease Registry records information on young people under 25 years old diagnosed with cancer in the Northern Region of England. Incidence and survival rates were calculated for children and young adults diagnosed with cancer between 1968 and 1995. There were 2099 (M:F 1.28:1) children (age 0–14 years) and 2217 (M:F 1.23:1) young adults (15–24 years) diagnosed with a first cancer between 1968 and 1995. The age-standardized rate (ASR) for childhood cancer was 121 per million 0 to 14 year-olds per year. For young adults the ASR was 175 per million 15 to 24 year-olds, per year. Incidence of childhood cancer increased over time at a rate of 12 extra cases per million children, per decade (P< 0.001). In young adults incidence rates increased by 16 extra cases per million 15 to 24 year-olds, per decade (P< 0.001). For childhood cancer 5-year survival was 42% for those diagnosed 1968–1977, 57% for 1978–1987 and 71% (95% CI 67–75) for 1988–1995. Survival for young adults over the three periods was 45%, 62% and 73% (95% CI 70–78) respectively. The cumulative risk of developing cancer before the age of 25 is 1 in 285. Over the 28-year period there were significant improvements in survival and modest increases in incidence in both children and young adults. © 2000 Cancer Research Campaig

Challenges with Quantifying Tire Road Wear Particles: Recognizing the Need for Further Refinement of the ISO Technical Specification

Environmental monitoring data for tire road wear particles are vastly limited compared to those for other microplastics, primarily due to analytical challenges with quantification. Recently, two ISO technical specifications have been released using pyrolysis GC-MS for quantification. However, these methods have major assumptions, including that the content of natural and synthetic rubber in tire tread is constant across formulations and that the pyrolysis products chosen are selective. This study analyzed a wide range of commercially available tires from Australia and Norway, using pyrolysis GC-MS to test these assumptions. The percent mass of synthetic rubber in tires (n = 39) was highly variable, ranging from <0.05 to 28%, when using the ISO-recommended pyrolysis product 4-vinylcyclohexene. The content varied between brands and models, demonstrating that formulations are highly variable and unknown. The styrene butadiene dimer and trimer pyrolysis products were also assessed, and the calculated synthetic rubber content was higher, had an even greater variability, and had no correlation with concentrations calculated using 4-vinylcyclohexene. Using the ISO method has the potential to underreport environmental concentrations of TRWPs by a factor of at least 5, suggesting the specification requires further refinement, and there is an immediate need for large-scale analysis of commercial tire treads and assessments of suitable pyrolysis products.acceptedVersio

From Centroided to Profile Mode: Machine Learning for Prediction of Peak Width in HRMS Data

Centroiding is one of the major approaches used for size reduction of the data generated by high-resolution mass spectrometry. During centroiding, performed either during acquisition or as a pre-processing step, the mass profiles are represented by a single value (i.e., the centroid). While being effective in reducing the data size, centroiding also reduces the level of information density present in the mass peak profile. Moreover, each step of the centroiding process and their consequences on the final results may not be completely clear. Here, we present Cent2Prof, a package containing two algorithms that enables the conversion of the centroided data to mass peak profile data and vice versa. The centroiding algorithm uses the resolution-based mass peak width parameter as the first guess and self-adjusts to fit the data. In addition to the m/z values, the centroiding algorithm also generates the measured mass peak widths at half-height, which can be used during the feature detection and identification. The mass peak profile prediction algorithm employs a random-forest model for the prediction of mass peak widths, which is consequently used for mass profile reconstruction. The centroiding results were compared to the outputs of the MZmine-implemented centroiding algorithm. Our algorithm resulted in rates of false detection ≤5% while the MZmine algorithm resulted in 30% rate of false positive and 3% rate of false negative. The error in profile prediction was ≤56% independent of the mass, ionization mode, and intensity, which was 6 times more accurate than the resolution-based estimated values.publishedVersio

Atypical presentation of acute pancreatitis in a man with pancreatic insufficiency and cystic fibrosis: a case report

<p>Abstract</p> <p>Introduction</p> <p>Whether acute pancreatitis can occur in pancreatically insufficient individuals with cystic fibrosis remains a matter of debate.</p> <p>Case presentation</p> <p>We describe a case of acute pancreatitis occurring in a 52-year-old Caucasian Australian man with moderately severe cystic fibrosis lung disease and pancreatic insufficiency. An inflammatory mass within the head of his pancreas was confirmed using computed tomography, magnetic resonance imaging and pancreatic biopsy, but serum amylase and lipase remained normal throughout the acute phase of his illness. His symptoms and the pancreatic mass resolved following the insertion of a biliary stent and the introduction of ursodeoxycholic acid.</p> <p>Conclusion</p> <p>Our case report highlights the potential for acute pancreatitis to occur in patients with pancreatic insufficiency and cystic fibrosis. We further demonstrate that conventional biochemical markers that are normally assessed to confirm the diagnosis may not be of particular use. As patients with cystic fibrosis survive into their fourth and fifth decades of life, atypical presentations of acute pancreatitis may become more common.</p

Structural Controls on Shallow Cenozoic Fluid Flow in the Otago Schist, New Zealand

The Otago Schist in the South Island of New Zealand represents an exhumed Mesozoic accretionary prism. Two coastal areas (Akatore Creek and Bruce Rocks) south of Dunedin preserve structural and geochemical evidence for the development of postmetamorphic hydrothermal systems that involved widespread fluid-rock reaction at shallow crustal depths. The Jurassic to Triassic pumpellyite-actinolite (Akatore Creek) to upper greenschist facies (Bruce Rocks) metamorphic fabrics were crosscut by sets of regionally extensive Cretaceous exhumation joints. Many of the joints were subsequently reactivated to form networks of small-displacement (<metres) strike-slip faults containing cemented fault breccias and veins composed of hydrothermal calcite, siderite, and ankerite. Paleostress analysis performed on infrequent fault slickenlines indicates an overall strike-slip paleostress regime and a paleo-σ1 orientation (azimuth 094°) similar to the contemporary σ1 orientation in Otago and Canterbury (azimuth c. 110°-120°). High δ18O values in vein calcite (δ18OVPDB=21 to 28‰), together with the predominance of Type I calcite twins, suggest that vein formation occurred at low temperatures (<200°C) in the shallow crust and was associated with strongly channelized fluid flow along the joint and fault networks. Mass-balance calculations performed on samples from carbonate alteration zones show that significant mobilisation of elements occurred during fluid flow and fluid-rock reaction. Whole-rock and in situ carbonate 87Sr/86Sr data indicate varying degrees of interaction between the hydrothermal fluids and the host rock schists. Fluids were likely derived from the breakdown of metamorphic Ca-rich mineral phases with low 87Rb in the host schists (e.g., epidote or calcite), as well as more radiogenic components such as mica. Overall, the field and geochemical data suggest that shallow fluid flow in the field areas was channelized along foliation surfaces, exhumation joints, and networks of brittle faults, and that these structures controlled the distribution of fluid-rock reactions and hydrothermal veins. The brittle fault networks and associated hydrothermal systems are interpreted to have formed after the onset of Early Miocene compression in the South Island and may represent the manifestation of fracturing and fluid flow associated with reverse reactivation of regional-scale faults such as the nearby Akatore Fault

Assessing sample extraction efficiencies for the analysis of complex unresolved mixtures of organic pollutants: a comprehensive non-target approach

The comprehensive extraction recovery assessment of organic analytes from complex samples such as oil field produced water (PW) is a challenging task. A targeted approach is usually used for recovery and determination of compounds in these types of analysis. Here we suggest a more comprehensive and less biased approach for the extraction recovery assessment of complex samples. This method combines conventional targeted analysis with a non-targeted approach to evaluate the extraction recovery of complex mixtures. Three generic extraction methods: liquid-liquid extraction (Lq), and solid phase extraction using HLB cartridges (HLB), and the combination of ENV+ and C8 (ENV) cartridges, were selected for evaluation. PW was divided into three parts: non-spiked, spiked level 1, and spiked level 2 for analysis. The spiked samples were used for targeted evaluation of extraction recoveries of 65 added target analytes comprising alkanes, phenols, and polycyclic aromatic hydrocarbons, producing absolute recoveries. The non-spiked samples were used for the non-targeted approach, which used a combination of the F-ratio method and apex detection algorithm. Targeted analysis showed that the use of ENV cartridges and the Lq method performed better than use of HLB cartridges, producing absolute recoveries of 53.1 ± 15.2 for ENV and 46.8 ± 13.2 for Lq versus 19.7 ± 6.7 for HLB. These two methods appeared to produce statistically similar results for recoveries of analytes, whereas they were both different from the produced recoveries via the HLB method. The non-targeted approach captured unique features that were specific to each extraction method. This approach generated 26 unique features (mass spectral ions), which were significantly different between samples and were relevant in differentiating each extract from each method. Using a combination of these targeted and non-targeted methods we evaluated the extraction recoveries of the three extraction methods for analysis of PW

Comparisons of Aerosol Generation Across Different Musical Instruments and Loudness

Highlights•Aerosol number and mass concentrations measured during musical instrument playing.•A 1 dBA increase in sound pressure level yields ∼10% increase in number concentration.•Loudness of playing explains some but not all differences across instruments.•Musical instrument playing size distributions are consistent with those of breathing.•Simple songs sufficient to characterise aerosol emission during actual performance.AbstractRespiratory aerosols can serve as vectors for disease transmission, and aerosol emission is highly activity-dependent. COVID-19 severely impacted the performing arts due to concerns about disease spread by respiratory aerosols and droplets generated during singing and playing musical instruments. Aerosol generation from woodwind and brass performance is less understood compared to singing due to uncertainty about how the diverse range of musical instruments may impact respiratory aerosol concentrations and size distributions. Here, aerosol number and mass concentrations along with size distributions were measured for breathing, speaking, and playing four different woodwind and brass instruments by 23 professional instrumentalists. We find that a 1 dBA increase in sound pressure level corresponds to a ∼10% increase in aerosol number concentration. The aerosol size distribution is consistent with that of breathing. Differences in aerosol emission across musical instruments can be partly explained by the loudness of performance. Measuring aerosol generation from single notes or simple songs may be sufficient to characterise the aerosol emission range during actual performance, provided a range of loudnesses are accessed. These results provide insight into the factors contributing to aerosol emission during musical performance and facilitate risk assessments associated with infectious respiratory disease transmission in the performing arts