Multi-residue analysis of pharmaceuticals in Belgian surface water : a novel screening-to-quantification approach using large-volume injection liquid chromatography coupled to high-resolution mass spectrometry

The ever growing number of emerging micropollutants such as pharmaceuticals requests rapid and sensitive full-spectrum analytical techniques. Time-of-flight highresolution mass spectrometry (TOF-HRMS) is a promising alternative for the state-ofthe- art MS/MS instruments because of its ability to simultaneously screen towards a virtually unlimited list of suspect compounds and to perform target quantification. The challenge for such suspect screening is to develop a strategy which minimizes the false negative rate without restraining numerous false positives. At the same time, omitting laborious sample enrichment through large-volume injection ultraperformance liquid chromatography (LVI-UPLC) is advantageous avoiding selective preconcentration. A novel suspect screening strategy was developed using LVI-UPLC-TOF-MS aiming the detection of 69 multi-class pharmaceuticals in surface water without the a priori availability of analytical standards. As a novel approach, the screening takes into account the signal intensity-dependent accurate mass error, hereby assuring the detection of 95% of pharmaceuticals present in surface water. Subsequently, the validation and applicability of the full-spectrum method for target quantification of the 69 pharmaceuticals in surface water is discussed. Analysis of five Belgian river water samples revealed the occurrence of 17 pharmaceuticals in a concentration range of 17 ng L-1 up to 3.1 μg L-1

Chain ladder method: Bayesian bootstrap versus classical bootstrap

The intention of this paper is to estimate a Bayesian distribution-free chain ladder (DFCL) model using approximate Bayesian computation (ABC) methodology. We demonstrate how to estimate quantities of interest in claims reserving and compare the estimates to those obtained from classical and credibility approaches. In this context, a novel numerical procedure utilising Markov chain Monte Carlo (MCMC), ABC and a Bayesian bootstrap procedure was developed in a truly distribution-free setting. The ABC methodology arises because we work in a distribution-free setting in which we make no parametric assumptions, meaning we can not evaluate the likelihood point-wise or in this case simulate directly from the likelihood model. The use of a bootstrap procedure allows us to generate samples from the intractable likelihood without the requirement of distributional assumptions, this is crucial to the ABC framework. The developed methodology is used to obtain the empirical distribution of the DFCL model parameters and the predictive distribution of the outstanding loss liabilities conditional on the observed claims. We then estimate predictive Bayesian capital estimates, the Value at Risk (VaR) and the mean square error of prediction (MSEP). The latter is compared with the classical bootstrap and credibility methods

Optimal modelling and experimentation for the improved sustainability of microfluidic chemical technology design

Optimization of the dynamics and control of chemical processes holds the promise of improved sustainability for chemical technology by minimizing resource wastage. Anecdotally, chemical plant may be substantially over designed, say by 35-50%, due to designers taking account of uncertainties by providing greater flexibility. Once the plant is commissioned, techniques of nonlinear dynamics analysis can be used by process systems engineers to recoup some of this overdesign by optimization of the plant operation through tighter control. At the design stage, coupling the experimentation with data assimilation into the model, whilst using the partially informed, semi-empirical model to predict from parametric sensitivity studies which experiments to run should optimally improve the model. This approach has been demonstrated for optimal experimentation, but limited to a differential algebraic model of the process. Typically, such models for online monitoring have been limited to low dimensions. Recently it has been demonstrated that inverse methods such as data assimilation can be applied to PDE systems with algebraic constraints, a substantially more complicated parameter estimation using finite element multiphysics modelling. Parametric sensitivity can be used from such semi-empirical models to predict the optimum placement of sensors to be used to collect data that optimally informs the model for a microfluidic sensor system. This coupled optimum modelling and experiment procedure is ambitious in the scale of the modelling problem, as well as in the scale of the application - a microfluidic device. In general, microfluidic devices are sufficiently easy to fabricate, control, and monitor that they form an ideal platform for developing high dimensional spatio-temporal models for simultaneously coupling with experimentation. As chemical microreactors already promise low raw materials wastage through tight control of reagent contacting, improved design techniques should be able to augment optimal control systems to achieve very low resource wastage. In this paper, we discuss how the paradigm for optimal modelling and experimentation should be developed and foreshadow the exploitation of this methodology for the development of chemical microreactors and microfluidic sensors for online monitoring of chemical processes. Improvement in both of these areas bodes to improve the sustainability of chemical processes through innovative technology. (C) 2008 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved

Assessing quality of experience of IPTV and video on demand services in real-life environments

The ever growing bandwidth in access networks, in combination with IPTV and video on demand (VoD) offerings, opens up unlimited possibilities to the users. The operators can no longer compete solely on the number of channels or content and increasingly make high definition channels and quality of experience (QoE) a service differentiator. Currently, the most reliable way of assessing and measuring QoE is conducting subjective experiments, where human observers evaluate a series of short video sequences, using one of the international standardized subjective quality assessment methodologies. Unfortunately, since these subjective experiments need to be conducted in controlled environments and pose limitations on the sequences and overall experiment duration they cannot be used for real-life QoE assessment of IPTV and VoD services. In this article, we propose a novel subjective quality assessment methodology based on full-length movies. Our methodology enables audiovisual quality assessment in the same environments and under the same conditions users typically watch television. Using our new methodology we conducted subjective experiments and compared the outcome with the results from a subjective test conducted using a standardized method. Our findings indicate significant differences in terms of impairment visibility and tolerance and highlight the importance of real-life QoE assessment