Using the Expectation Maximization Algorithm with Heterogeneous Mixture Components for the Analysis of Spectrometry Data

Coupling a multi-capillary column (MCC) with an ion mobility (IM) spectrometer (IMS) opened a multitude of new application areas for gas analysis, especially in a medical context, as volatile organic compounds (VOCs) in exhaled breath can hint at a person's state of health. To obtain a potential diagnosis from a raw MCC/IMS measurement, several computational steps are necessary, which so far have required manual interaction, e.g., human evaluation of discovered peaks. We have recently proposed an automated pipeline for this task that does not require human intervention during the analysis. Nevertheless, there is a need for improved methods for each computational step. In comparison to gas chromatography / mass spectrometry (GC/MS) data, MCC/IMS data is easier and less expensive to obtain, but peaks are more diffuse and there is a higher noise level. MCC/IMS measurements can be described as samples of mixture models (i.e., of convex combinations) of two-dimensional probability distributions. So we use the expectation-maximization (EM) algorithm to deconvolute mixtures in order to develop methods that improve data processing in three computational steps: denoising, baseline correction and peak clustering. A common theme of these methods is that mixture components within one model are not homogeneous (e.g., all Gaussian), but of different types. Evaluation shows that the novel methods outperform the existing ones. We provide Python software implementing all three methods and make our evaluation data available at http://www.rahmannlab.de/research/ims

Treatment of bimodality in proficiency test of pH in bioethanol matrix

The pH value in bioethanol is a quality control parameter related to its acidity and to the corrosiveness of vehicle engines when it is used as fuel. In order to verify the comparability and reliability of the measurement of pH in bioethanol matrix among some experienced chemical laboratories, reference material (RM) of bioethanol developed by Inmetro - the Brazilian National Metrology Institute - was used in a proficiency testing (PT) scheme. There was a difference of more than one unit in the value of the pH measured due to the type of internal filling electrolytic solutions (potassium chloride, KCl or lithium chloride, LiCl) from the commercial pH combination electrodes used by the participant laboratories. Therefore, bimodal distribution has occurred from the data of this PT scheme. This work aims to present the possibilities that a PT scheme provider can use to overcome the bimodality problem. Data from the PT of pH in bioethanol were treated by two different statistical approaches: kernel density model and the mixture of distributions. Application of these statistical treatments improved the initial diagnoses of PT provider, by solving bimodality problem and contributing for a better performance evaluation in measuring pH of bioethanol.Comment: 20 pages, 6 figures, Accepted for publication in Accreditation and Quality Assurance (ACQUAL

Optimizing gravitational-wave searches for a population of coalescing binaries: Intrinsic parameters

We revisit the problem of searching for gravitational waves from inspiralling compact binaries in Gaussian coloured noise. For binaries with quasicircular orbits and non-precessing component spins, considering dominant mode emission only, if the intrinsic parameters of the binary are known then the optimal statistic for a single detector is the well-known two-phase matched filter. However, the matched filter signal-to-noise ratio is /not/ in general an optimal statistic for an astrophysical population of signals, since their distribution over the intrinsic parameters will almost certainly not mirror that of noise events, which is determined by the (Fisher) information metric. Instead, the optimal statistic for a given astrophysical distribution will be the Bayes factor, which we approximate using the output of a standard template matched filter search. We then quantify the possible improvement in number of signals detected for various populations of non-spinning binaries: for a distribution of signals uniformly distributed in volume and with component masses distributed uniformly over the range $1\leq m_{1,2}/M_\odot\leq 24$, $(m_1+m_2) /M_\odot\leq 25$ at fixed expected SNR, we find $\gtrsim 20\%$ more signals at a false alarm threshold of $10^{-6}\,$Hz in a single detector. The method may easily be generalized to binaries with non-precessing spins.Comment: Version accepted by Phys. Rev.

Common Arc Method for Diffraction Pattern Orientation

Very short pulses of x-ray free-electron lasers opened the way to obtain diffraction signal from single particles beyond the radiation dose limit. For 3D structure reconstruction many patterns are recorded in the object's unknown orientation. We describe a method for orientation of continuous diffraction patterns of non-periodic objects, utilizing intensity correlations in the curved intersections of the corresponding Ewald spheres, hence named Common Arc orientation. Present implementation of the algorithm optionally takes into account the Friedel law, handles missing data and is capable to determine the point group of symmetric objects. Its performance is demonstrated on simulated diffraction datasets and verification of the results indicates high orientation accuracy even at low signal levels. The Common Arc method fills a gap in the wide palette of the orientation methods.Comment: 16 pages, 10 figure