Harmonization and transferability of performance assessment: experience from four serum aluminum proficiency testing schemes

Proficiency testing schemes monitor laboratory performance and provide a stimulus for improvement in accuracy. Where several schemes operate in the same analytical sector, there are risks that assessments of performance may be in conflict. Performance assessment for the determination of trace elements such as aluminum in serum is particularly important due to the high risk of contamination and therefore erroneous results. The objectives of this work were (1) to compare several mathematical models to establish a predefined standard deviation for proficiency assessment and (2) to evaluate the influence of instrumental methods and proficiency testing scheme on the assessment of performance for serum aluminum measurements. For this purpose, three samples were sent to the participants of four proficiency testing schemes. Assigned values were calculated according to algorithm A according to ISO 13528 and standard deviation for proficiency assessment according to three methods based on individual variability, state of the art or previous proficiency testing results. The method based on individual variability produced a more stringent standard deviation compared to analytical imprecision based on the state of the art. The instrumental methods gave similar results, whereas significant differences were observed between the four proficiency testing schemes indicating that harmonization of the standard deviation for proficiency assessment fails to allow transferability from one proficiency testing scheme to another and that additional factor(s) contribute to variability in performance assessment.     

Parametric resonance and Hopf bifurcation analysis for a MEMS resonator

We study the response of a MEMS resonator, driven in an in-plane length-extensional mode of excitation. It is observed that the amplitude of the resulting vibration has an upper bound, i.e., the response shows saturation. We present a model for this phenomenon, incorporating interaction with a bending mode. We show that this model accurately describes the observed phenomena. The in-plane (“trivial”) mode is shown to be stable up to a critical value of the amplitude of the excitation. At this value, a new “bending” branch of solutions bifurcates. For appropriate values of the parameters, a subsequent Hopf bifurcation causes a beating phenomenon, in accordance with experimental observations.     

Strengthening the security of authenticated key exchange against bad randomness

Recent history has revealed that many random number generators (RNGs) used in cryptographic algorithms and protocols were not providing appropriate randomness, either by accident or on purpose. Subsequently, researchers have proposed new algorithms and protocols that are less dependent on the RNG. One exception is that all prominent authenticated key exchange (AKE) protocols are insecure given bad randomness, even when using good long-term keying material. We analyse the security of AKE protocols in the presence of adversaries that can perform attacks based on chosen randomness, i.e., attacks in which the adversary controls the randomness used in protocol sessions. We propose novel stateful protocols, which modify memory shared among a user’s sessions, and show in what sense they are secure against this worst case randomness failure. We develop a stronger security notion for AKE protocols that captures the security that we can achieve under such failures, and prove that our main protocol is correct in this model. Our protocols make substantially weaker assumptions on the RNG than existing protocols.     

Solubility of phosphonium ionic liquid in alcohols, benzene, and alkylbenzenes

The (solid + liquid) phase equilibria and (liquid + liquid) phase equilibria of binary mixtures containing quaternary phosphonium salt-tetrabutylphosphonium methanesulfonate and alcohols or alkylbenzenes were investigated. The systems {[(CH(3)CH(2)CH(2)CH(2))4P][CH(3)SO(3)] + 1-butanol, or 1-hexanol, 1-octanol, 1-decanol, or 1-dodecanol} and {[(CH(3)CH(2)CH(2)CH(2))4P][CH(3)SO(3)] + benzene, or toluene, ethylbenzene, or propylbenzene} have been measured by a dynamic method at a wide range of temperatures from 220 to 386 K. Solid-liquid equilibria with immiscibility in the liquid phase were detected with the aromatic hydrocarbons ethylbenzene and propylbenzene. The basic thermodynamic properties of pure ionic liquid--the melting point, enthalpy of fusion, enthalpy of solid-solid-phase transition, and glass transition--have been determined by differential scanning calorimetry. The experimental data of systems with alcohols were correlated by means of the UNIQUAC ASM and NRTL1 equations and of systems with alkylbenzenes with Wilson and NRTL equations utilizing parameters derived from the (solid + liquid) equilibrium. The root-mean-square deviations of the solubility temperatures for all calculated data are dependent upon the particular system and the particular equation used.     

Criteria to define the standard deviation for proficiency assessment for the determination of essential trace elements in serum: comparison of Z-scores based on the Horwitz function or on biological variability

A critical issue in the organisation of Proficiency Testing/External Quality Assessment Schemes is the definition of the criteria against which the performance of individual laboratories should be evaluated. Organisers of EQAS in Occupational and Environmental Laboratory Medicine (http://www.occupational-environmental-laboratory.com) collaborate to define common acceptable levels of performance. The aim of this study was to compare the Horwitz function to the Fraser’s approach. Sets of results obtained from the distribution of test materials in the Network schemes (for the measurands: copper, selenium or zinc in serum) were used to calculate Z-scores according to both approaches. Quality specifications derived from both approaches were also compared to the standard deviations obtained. Except for selenium, Horwitz criteria suggests a more stringent evaluation than Fraser criteria, the latter being very stringent as regard the participant analytical variability.     

Uncertainty calculation for calibrators of the IFCC HbA1c standardization network

Within the last decade, the IFCC HbA1c standardization network has established the metrologically highest reference measurement procedure for HbA1c testing. Based on this procedure, reference calibrators are produced which in turn provide the starting point for the standardization of the manufactures routine HbA1c assays. According to the IVD directive, the uncertainty of the reference calibrators must be calculated and reported together with their assigned values. Within this article, we elaborate the uncertainty calculation according to GUM (guide to the expression of uncertainty in measurement) in detail. Finally, the results are validated by a simulation study.     

Proficiency testing in analytical chemistry,microbiology and laboratory medicine – working group discussions on current status,problems and future directions

Working group (WG) discussions on proficiency testing and external quality assessment held at the Eurachem workshop, Portorož, Slovenia 26–27 Sept 2005 are summarised. The discussions focused on performance criteria (WG 1), different aspects of accreditation (WGs 2–3), the revised international harmonised protocol (WG 4), pre- and post-analytical schemes (WG 5), Internet applications (WG 6), experience from the CoEPT project (WG 7), and future aspects (WG 8). Current status, problems and future directions were identified. The WG contained a mix of participants with different expertise. This was done to promote cross-fertilisation of ideas between sectors. The WG issues reflected the content of the keynote lectures and some issues were covered from different perspectives by more than one WG.Presented at the Eurachem PT Workshop September 2005, Portorož, Slovenia.     

Measurements and calculations on the simple up-down adaptive procedure for speech-in-noise tests

The simple up-down adaptive procedure is a common method for measuring speech reception thresholds. It is used by the Dutch speech-in-noise telephone screening test [National Hearing test; Smits and Houtgast Ear Hear. 26, 89-95 (2005)]. The test uses digit triplets to measure the speech reception threshold in noise by telephone (SRTT(n)). About 66 000 people took this test within four months of its introduction and details were stored of all individual measurements. Analyses of this large volume of data have revealed that the standard deviation of SRTT(n) estimates increases with hearing loss. This paper presents a calculation model which--using an intelligibility function as input--can determine the standard deviation of SRTT(n) estimates and the bias for the simple up-down procedure. The effects of variations in the slope of the intelligibility function, the guess rate, the starting level, the heterogeneity of the speech material, and the possibilities of optimizing SRTT(n) measurements were all explored with this model. The predicted decrease in the standard deviation of SRTT(n) estimates as a result of optimizing the speech material was confirmed by measurements in 244 listeners. The paper concludes by discussing possibilities for optimizing the development of comparable tests.