Determination of perfluorinated alkyl acid concentrations in biological standard reference materials

Standard reference materials (SRMs) are homogeneous, well-characterized materials used to validate measurements and improve the quality of analytical data. The National Institute of Standards and Technology (NIST) has a wide range of SRMs that have mass fraction values assigned for legacy pollutants. These SRMs can also serve as test materials for method development, method validation, and measurement for contaminants of emerging concern. Because inter-laboratory comparison studies have revealed substantial variability of measurements of perfluoroalkyl acids (PFAAs), future analytical measurements will benefit from determination of consensus values for PFAAs in SRMs to provide a means to demonstrate method-specific performance. To that end, NIST, in collaboration with other groups, has been measuring concentrations of PFAAs in a variety of SRMs. Here we report levels of PFAAs and perfluorooctane sulfonamide (PFOSA) determined in four biological SRMs: fish tissue (SRM 1946 Lake Superior Fish Tissue, SRM 1947 Lake Michigan Fish Tissue), bovine liver (SRM 1577c), and mussel tissue (SRM 2974a). We also report concentrations for three in-house quality-control materials: beluga whale liver, pygmy sperm whale liver, and white-sided dolphin liver. Measurements in SRMs show an array of PFAAs, with perfluorooctane sulfonate (PFOS) being the most frequently detected. Reference and information values are reported for PFAAs measured in these biological SRMs.

Magnetoconductivity tensor analysis of anomalous transport effects in neutron irradiated HgCdTe epilayers

Hg_1−xCd_xTe(x0.22) samples grown by LPE on CdZnTe(111B)-oriented substrates were exposed to various doses of thermal neutrons (1.0×10¹⁶−1.7×10¹⁶ n/cm²) and subsequently annealed for 24 h in Hg overpressure to remove damage and reduce the presence of Hg vacancies. Extensive magnetotransport measurements were performed on these samples as part of an investigation into the use of elemental transmutation for efficient p-type doping of this material. The data were analyzed using a multi-carrier approach which incorporates various scattering mechanisms and the presence of two conduction channels of differing alloy content to describe the changes in the transport properties due to neutron irradiation.     

Reevaluation of neutron flux characterization parameters for NIST RT-2 facility

It has been difficult to characterize the thermal to epithermal neutron flux ratio (f) and the measure of the nonideal epithermal neutron flux distribution (α) for the RT-2 pneumatic rabbit facility at the NIST National Bureau of Standards Reactor (NBSR). In a previous paper, only cadmium-covered irradiations yielded physically reasonable parameters. New measurements were performed using chromium, manganese, cobalt, zinc, zirconium, molybdenum, antimony, gadolinium, lutetium, and gold. The neutron temperature (T _n ) in RT-2 measured using bare lutetium and gold foils gave unphysical values. The bare foil methods for measuring f and α gave inconsistent results. The underlying reasons are demonstrated via MCNP simulation results for cumulative reaction rates of selected isotopes. To determine expected intervals for f, α and T, parametric methods were explored. Measured reaction rate probability per target atom (R _p ) values for the listed elements were fitted to a modified Westcott curve using an iterative least-squares method to verify consistency of measurements and nuclear data. An advanced parametric approach using a detailed MCNP model of the NBSR was used to calculate neutron flux characterization parameters.     

THE EFFECT OF EMULSION COMPOSITION OF ASA ON SIZING PERFORMANCE IN THE PAPER WEB

Effects of emulsifying chemicals and emulsion aging on the sizing performance of alkenyl succinic anhydride (ASA) were investigated. The emulsifying chemicals were nonionic and anionic surfactants and cationic starches. Image analysis in emulsion quality control was applied. It was found that the use of surfactants may deteoriate remarkably the sizing efficiency if the surfactant and its dosage is not carefully chosen. The need for surfactants in emulsification was affected by the properties of ASA and the mixing energy available. The act of cationic starch both as an effective stabilizer and as a retention agent in ASA-sizing systems was established.     

Compton scattering artifacts in electron excited X-ray spectra measured with a silicon drift detector

Artifacts are the nemesis of trace element analysis in electron-excited energy dispersive X-ray spectrometry. Peaks that result from nonideal behavior in the detector or sample can fool even an experienced microanalyst into believing that they have trace amounts of an element that is not present. Many artifacts, such as the Si escape peak, absorption edges, and coincidence peaks, can be traced to the detector. Others, such as secondary fluorescence peaks and scatter peaks, can be traced to the sample. We have identified a new sample-dependent artifact that we attribute to Compton scattering of energetic X-rays generated in a small feature and subsequently scattered from a low atomic number matrix. It seems likely that this artifact has not previously been reported because it only occurs under specific conditions and represents a relatively small signal. However, with the advent of silicon drift detectors and their utility for trace element analysis, we anticipate that more people will observe it and possibly misidentify it. Though small, the artifact is not inconsequential. Under some conditions, it is possible to mistakenly identify the Compton scatter artifact as approximately 1% of an element that is not present.     

Penalized Estimation of Free-Knot Splines

Abstract

Polynomial splines are often used in statistical regression models for smooth response functions. When the number and location of the knots are optimized, the approximating power of the spline is improved and the model is nonparametric with locally determined smoothness. However, finding the optimal knot locations is an historically difficult problem. We present a new estimation approach that improves computational properties by penalizing coalescing knots. The resulting estimator is easier to compute than the unpenalized estimates of knot positions, eliminates unnecessary “corners” in the fitted curve, and in simulation studies, shows no increase in the loss. A number of GCV and AIC type criteria for choosing the number of knots are evaluated via simulation.     

Deprotonation and regioselective addition of 2H-pyrazolo[3,4-c]quinolines to electrophiles

The deprotonation and regioselective reaction of 2H-pyrazolo[3,4-c]quinolines with a variety of electrophiles is described. Electrophiles include benzaldehyde, DMF, carbon dioxide, and iodine. This method provides a direct route to a class of pharmacologically interesting compounds.     

Functional Kernel Density Estimation: Point and Fourier Approaches to Time Series Anomaly Detection

We present an unsupervised method to detect anomalous time series among a collection of time series. To do so, we extend traditional Kernel Density Estimation for estimating probability distributions in Euclidean space to Hilbert spaces. The estimated probability densities we derive can be obtained formally through treating each series as a point in a Hilbert space, placing a kernel at those points, and summing the kernels (a “point approach”), or through using Kernel Density Estimation to approximate the distributions of Fourier mode coefficients to infer a probability density (a “Fourier approach”). We refer to these approaches as Functional Kernel Density Estimation for Anomaly Detection as they both yield functionals that can score a time series for how anomalous it is. Both methods naturally handle missing data and apply to a variety of settings, performing well when compared with an outlyingness score derived from a boxplot method for functional data, with a Principal Component Analysis approach for functional data, and with the Functional Isolation Forest method. We illustrate the use of the proposed methods with aviation safety report data from the International Air Transport Association (IATA).