Precise Measurement of Isotope Ratios with a Double-Focusing Magnetic Sector ICP Mass Spectrometer

The potential of a commercially available double-focusing magnetic sector ICP mass spectrometer (Element, Finnigan MAT, Bremen, Germany) for precise isotope ratio measurement at the low-resolution setting (R = 300) was evaluated. Optimization of scanning conditions led to a relative standard deviation for a set of 10 consecutive 2 min measurements of ～0.1% ((206)Pb(+)/(207)Pb(+)) at signal intensities of ～200?000 counts/s (peak height). This compares favorably with the best values ever reported for quadrupole ICPMS and barely exceeds the theoretical value (counting statistics). Increasing the signal intensity to values ≥500?000 counts/s (peak height) resulted in a further reduction of the RSDs obtained (for both (25)Mg(+)/(26)Mg(+) and (206)Pb(+)/(207)Pb(+)) to typically 0.04%. These figures are remarkably better than those reported for commercially available quadrupole ICPMS systems. This improvement significantly reduces the difference between isotope ratio precision of ICPMS on one hand and those of thermal ionization mass spectrometry and plasma source multiple collector mass spectrometry on the other.     

Highly discriminative statistical features for email classification

This paper reports on email classification and filtering, more specifically on spam versus ham and phishing versus spam classification, based on content features. We test the validity of several novel statistical feature extraction methods. The methods rely on dimensionality reduction in order to retain the most informative and discriminative features. We successfully test our methods under two schemas. The first one is a classic classification scenario using a 10-fold cross-validation technique for several corpora, including four ground truth standard corpora: Ling-Spam, SpamAssassin, PU1, and a subset of the TREC 2007 spam corpus, and one proprietary corpus. In the second schema, we test the anticipatory properties of our extracted features and classification models with two proprietary datasets, formed by phishing and spam emails sorted by date, and with the public TREC 2007 spam corpus. The contributions of our work are an exhaustive comparison of several feature selection and extraction methods in the frame of email classification on different benchmarking corpora, and the evidence that especially the technique of biased discriminant analysis offers better discriminative features for the classification, gives stable classification results notwithstanding the amount of features chosen, and robustly retains their discriminative value over time and data setups. These findings are especially useful in a commercial setting, where short profile rules are built based on a limited number of features for filtering emails.     

Statistical Evaluation of Real-Time PCR Protocols Applied to Quantify Genetically Modified Maize

Real-time PCR (RTi-PCR) is the technique of choice for event-specific quantification of genetically modified organisms (GMOs) by determining the amount of event with respect to a species-specific reference gene. Reference genes can be amplified from the genome extracted from Certified Reference Materials (CRMs) or from ad hoc designed plasmids. In the present study, we statistically evaluate the performance of RTi-PCR protocols for GM maize MON810 event by using both genomic DNA from conventional CRMs and a plasmid containing sequences representative of four maize species-specific reference genes. The significance of simple and interaction effects of several variables included in the experimental design on DNA quantification methods and RTi-PCR were evaluated and discussed. Statistically significant differences on Ct values may have an impact on the GMOs quantification and consequently on the compliance of GM quantification-established legal thresholds. Our results confirm the reliability of the plasmid as alternative calibrant for the calculation of GMOs copy number.     

Influence of composition of MgAl2O4 supported NiCeO2ZrO2 catalysts on coke formation and catalyst stability for dry reforming of methane

Dry reforming of methane was studied over Ni catalysts supported on γAl₂O₃, CeO₂, ZrO₂ and MgAl₂O₄ (670 °C, 1.5 bar, 16–20 l CH₄ ml_catalyst⁻¹ h⁻¹). It is shown that MgAl₂O₄ supported Ni catalysts promoted with both CeO₂ and ZrO₂ are promising catalysts for dry reforming of methane with carbon dioxide. Within a certain composition range, the simultaneous promotion with CeO₂ and ZrO₂ has great influence on the amount of coke and the catalyst service time. XRD analyses indicate that formation of crystalline Ce_xZr_1−xO₂ mixed oxide phases occurs on double promotion. In particular, incorporation of low amounts of Zr in the CeO₂ fluorite structure provides stable dry reforming catalysis. As shown with TPR, promotion leads to a higher reduced state of Ni. SEM, XRD and TPR analyses demonstrate that highly dispersed, doubly promoted Ni catalysts with a strong metal-support interaction are essential for stable dry reforming and suppression of the formation of carbon filaments.     

A Multi-Disciplinary Contribution to the Provenance Determination of Ancient Greek and Roman Marble Artifacts

The problem of determining the provenance of the white marble used for antique artifacts has been tackled in different ways. During the past decade it became clear that a multimethod approach is required to solve the problem. In addition, reliable reference material, i.e., samples collected at the ancient quarry sites in an archaeologically and geologically justified manner, turned out to be a prerequisite for reliable provenance determination. A multimethod approach based on petrography, stable isotope analysis of O and C, and trace element analysis yields complementary information. These methods were applied to the same set of 225 quarry samples. When processed with powerful statistical methods, the data thus obtained allowed all major types of marble used in antiquity to be distinguished. Thus, most problems concerning the provenance of artifacts can be solved. This approach was successfully applied to the provenance determination of about 75 artifacts from different museums in Europe and the USA.     

New method for threshold voltage extraction of high-voltage MOSFETs based on gate-to-drain capacitance measurement

This letter reports on the extraction of the threshold voltage of laterally diffused MOS transistors. A clear analysis of the device physics is performed, highlighting the correlation between the change of the electron charge distribution along the channel and the device capacitance variations when the gate voltage is swept. Using numerical simulations, it is shown that the peak of the gate-to-drain capacitance is related to the transition of the surface from weak to moderate inversion in the intrinsic MOS transistor at the location of the maximum doping concentration, which corresponds to the threshold voltage of the device according to the MOS theory. Comparison between conventional I/sub D///spl radic/g/sub m/ extraction and the new proposed capacitance peak method is performed on both technology computer-aided design simulations and measurements in order to confirm the new experimental technique and related theory.     

Validation of the performance of a GMO multiplex screening assay based on microarray detection

A new screening method for the detection and identification of GMO, based on the use of multiplex PCR followed by microarray, has been developed and is presented. The technology is based on the identification of quite ubiquitous GMO genetic target elements first amplified by PCR, followed by direct hybridisation of the amplicons on a predefined microarray (DualChip^® GMO, Eppendorf, Germany). The validation was performed within the framework of a European project (Co-Extra, contract no 007158) and in collaboration with 12 laboratories specialised in GMO detection. The present study reports the strategy and the results of an ISO complying validation of the method carried out through an inter-laboratory study. Sets of blind samples were provided consisting of DNA reference materials covering all the elements detectable by specific probes present on the array. The GMO concentrations varied from 1% down to 0.045%. In addition, a mixture of two GMO events (0.1% RRS diluted in 100% TOPAS19/2) was incorporated in the study to test the robustness of the assay in extreme conditions. Data were processed according to ISO 5725 standard. The method was evaluated with predefined performance criteria with respect to the EC CRL method acceptance criteria. The overall method performance met the acceptance criteria; in particular, the results showed that the method is suitable for the detection of the different target elements at 0.1% concentration of GMO with a 95% accuracy rate. This collaborative trial showed that the method can be considered as fit for the purpose of screening with respect to its intra- and inter-laboratory accuracy. The results demonstrated the validity of combining multiplex PCR with array detection as provided by the DualChip^® GMO (Eppendorf, Germany) for the screening of GMO. The results showed that the technology is robust, practical and suitable as a screening tool.     

Determination of platinum and rhodium in environmental matrixes by solid sampling-electrothermal vaporization-inductively coupled plasma mass spectrometry

Electrothermal vaporization from a graphite furnace was used in combination with inductively coupled plasma mass spectrometry (ICPMS) for the determination of Pt and Rh in environmental matrixes. Solid samples of tunnel dust, grass, and atmospheric aerosol collected on a cellulose filter could be analyzed directly, such that sample dissolution-which is not self-evident for the determination of platinum group metals-could be avoided. By heating the graphite furnace according to a multistep temperature program, spectral interferences were avoided, since a "dry" plasma was obtained, while "parent" ions such as Cu, Zn, and Pb, giving origin to interfering molecular ions, were vaporized during the thermal pretreatment step. For tunnel dust, the most demanding sample matrix, a mixture of HCl and HF was used as a modifier to stimulate the vaporization of matrix components during the thermal pretreatment step and, hence, to alleviate matrix-induced analyte signal suppression during the actual vaporization step. Calibration was accomplished by means of single standard addition with an aqueous standard solution. The results obtained agreed within the experimental uncertainty with the corresponding reference values (certified values or results obtained using pneumatic nebulization ICPMS), while relative standard deviations of < or = 15% were typical for both Pt and Rh. In all samples, a Pt/Rh ratio of approximately 6-8 was established. For a typical sample mass of 2 mg, limits of detection were 0.35 ng/g for Pt and 0.05 ng/g for Rh.