Estimation of comprehensive two-dimensional gas chromatographic response from one-dimensional gas chromatography data

Trabajo presentado a la XV Reunión Científica de la Sociedad Española de Cromatografía y Técnicas Afines (SECyTA) celebrada en Castellón de la Plana del 28 al 30 de octubre de 2015Optimization of a separation in comprehensive two-dimensional gas chromatography (GC×GC) requires the selection of an appropriate set column, and the optimisation of their respective dimensions, temperature programs and flow rates. Until not so long ago, a time consuming trial and error process was the only way to select the columns and chromatographic conditions for the two GC dimensions. During the last few years, several attempts have been proposed to estimate the chromatographic response in GC×GC [1-4]. Although most of these methods are helpful contributions, some of them focussed exclusively on the retention time estimation and do not consider the effect of peak width, also essential for a correct prediction of the chromatographic separation capability. Others are based on theoretical formulas not applicable to the extreme experimental conditions used in GC×GC, or are only valid for specific types of compounds or stationary phases: these models cannot be corrected for different separation problems. In this work, modelization of retention time and peak width has been carried out from experimental 1D GC data in order to estimate the response in GC×GC separation for different column sets operated under different flows and temperatures. Several theoretical and experimental models are proposed for estimation of 1D and 2D retention time and peak width; in experimental models, 1D GC data are required together with information on column characteristics and operation conditions. Models for hold-up time, retention factor and peak width were first validated in 1D GC from the fit between experimental and calculated data. Their validation in GC×GC was carried out by using n-alkanes and a mixture of disaccharides as their trimethylsilyl oxime derivatives. Comparison of experimental and estimated data showed good results for retention time in both first and second dimension. Peak widths presented, however, some errors, caused by the no consideration on estimation of the effect of the modulator or the rather unusual chromatographic conditions used. The developed programme is very versatile as it can be used for the calculation of the chromatographic response of compounds with different polarity and volatility, analysed under different pressures and temperature ramps, and with different sets of columns. [1] J.V. Seeley, E.M. Libby, K.A.H. Edwards, S.K. Seeley, J. Chromatogr. A 1216 (2009) 1650. [2] F.L. Dorman, P.D. Schettler, L.A. Vogt, J.W. Cochran, J. Chromatogr. A 1186 (2008) 196. [3] Y. Zhao, J. Zhang, B. Wang, S.H. Kim, A. Fang, B. Bogdanov, Z. Zhou, C. McClain, X. Zhang, J. Chromatogr. A 1218 (2011) 2577. [4] S. Zhu, S. He, D.R. Worton, A.H. Goldstein, J. Chromatogr. A 1233 (2012) 147. Acknowledgements: This work has been funded by Ministerio de Economía y Competitividad (project CTQ2012-32957), Comunidad Autónoma de Madrid (Spain) and European funding from FEDER program (AVANSECAL-CM S2013/ABI-3028) and Fundación Ramón Areces. ACS thanks Ministerio de Economía y Competitividad of Spain for a Ramón y Cajal contract.CTQ2012-32957Peer reviewe

Flood Hazard Management in Public Mountain Recreation Areas vs. Ungauged Fluvial Basins. Case Study of the Caldera de Taburiente National Park, Canary Islands (Spain)

Las Angustias River is an ungauged stream in the Caldera de Taburiente National Park (Spain), where frequent intense flash-flood events occur. The aim of this research is to analyze the flood hazard at the Playa de Taburiente. Based on the limited information available (short time-series of daily precipitation), a statistical frequency analysis of 24 h rainfall was completed and the precipitation results were transformed into surface runoff. To determine if the model underestimates the flows that are generated in the basin, the dendro-geomorphological information available was used to calibrate results. The results of the HMS model were significantly lower. At this point, both the rainfall data and the rainfall-runoff model were re-analyzed to maximize the rainfall intensity values and the runoff generated (increasing the CN value for the basin). For the 1997 flood event, a 1250 m3·s−1 flood minimizes the RMSE for the disturbed tree sample; this flow value also clearly exceeds any peak flow derived from the rainfall-runoff analysis. It is only when rainfall intensity and surface runoff are maximized that the peak flows obtained approximate those associated with dendro-geomorphological data. The results highlight the difficulties of flood hazard management in ungauged torrential basins in mountain recreational areas (such as National Parks). Thus, in the absence of flow records, when considering the maximum rainfall intensity scenario may be a useful and effective tool for flood risk management

Paleogeografía sísmica de zonas costeras en la Península Ibérica: su impacto en el análisis de terremotos antiguos e históricos en España

This paper presents three examples of ancient earthquakes occurring in coastal areas of the S and SE of the Iberian Peninsula (218 BC, AD 40-60 and AD 1048) with the aim of illustrating the use of geological and archaeological data in their macroseismic characterization. Historical information for ancient earthquakes that occurred in Spain prior to the 10th century is scarce or non-existent. This paper shows that the current state of knowledge on palaeoseismology and archaeoseismology on these ancient events clearly exceeds the existing historical information allowing the increase of macroseismic information points by using the ESI-07 scale (Environmental Seismic Intensity). Consequently, the geologic analyses of ancient earthquakes contribute to their understanding and parametric evaluations, and improve further advances in seismic hazard assessments. The most significant issue outlined in the present paper is the analysis of the ancient palaeogeography of the affected areas. The studied examples analysed were located in open estuarine areas that have been filled by fluvial sediments or anthropogenic fills over time. The effects of the 218 BC earthquake-tsunami event in the Gulf of Cadiz are analysed in estuarine areas, and especially in the ancient Roman Lagus Ligustinus (Guadalquivir Depression marshes); the effects of the earthquake in AD 40-60 is analysed in the old Roman city of Baelo Claudia located in the Bolonia Bay (Strait of Gibraltar); and the effects of the earthquake of AD 1048on the ancient Sinus Ilicitanus (Bajo Segura Depression) during Muslim times. Descriptions from Roman and Arabic geographers are cross-checked with existing palaeogeographic models based on geological data. This type of analysis results in ancient macroseismic scenarios for the interpretation of theoretical distributions of intensities and environmental effects supporting the concept of “seismic palaeogeography” proposed in this paperEl presente trabajo recoge tres ejemplos de terremotos antiguos (218 AC, 40-60 AD y 1048 AD) ocurridos en zonas litorales del S y SO de la Península Ibérica con la intención de ilustrar el uso de datos geológicos y ar¬queológicos en la caracterización macrosísmica de los mismos. En la mayor parte de los sísmos ocurridos con anterioridad al siglo X d.C. la información documental histórica que se posee es muy escasa o inexistente. El presente trabajo muestra que el actual estado de conocimiento en paleosismología y arqueosismologia sobre este tipo de terremotos sobrepasa con creces la información documental histórica, permitiendo la multiplica¬ción de los puntos de información macrosísmica mediante el uso de la escala ESI-07 (Environmental Seismic Intensity). Consecuentemente, el análisis geológico de los terremotos antiguos mejora su conocimiento y análisis paramétrico, permitiendo avanzar la evaluación de la peligrosidad sísmica de las zonas afectadas. El aspecto que se pone de especial relieve en este trabajo es el análisis de la paleogeografía existente en la antigüedad, ya que todas las zonas (afectadas) analizadas en este trabajo corresponden a zonas estuarinas abiertas que se han ido rellenado por aportes fluviales o de forma artificial con el tiempo. Se analizan los efectos del terremoto de 218 AC en las zonas estuarinas del Golfo de Cádiz y muy especialmente en el antiguo Lacus Ligustinus (marismas del Guadalquivir) durante época romana; los efectos del terremoto de 40-60 AD en la antigua Bahía de Baelo Claudia (Estrecho de Gibraltar); y los efectos del terremoto de 1048 AD en el antiguo Sinus ilicitanus (Depresión del Bajo Segura) durante época musulmana. Se han cotejado descripciones de geógrafos romanos y árabes con modelos basados en datos geológicos. Este tipo de análisis ha permitido generar antiguos escenarios macrosísmicos basados en la paleogeografía y reinterpretar las distribuciones teóricas de intensidades y los efectos ambientales de los terremotos estudiados que es a lo que se refiere el concepto de “paleogeografía sísmica” propuesto en este trabajoThis work has been funded by the Spanish-FEDER research projects CGL2012-37281 C02.01 (QTECTBETICA-USAL), CGL2012-33430 (CSIC) and CGL2013-42847-R (UNED

Análisis arqueosismológico del conjunto arqueológico romano de Mulva- Munigua (Sevilla, España). Resultados preliminares

El conjunto arqueológico romano de Mulva-Munigua (Sevilla, España) presenta daños en las edificaciones que pueden ser interpretadas como resultado de la ocurrencia de un evento sísmico (Efectos Arqueológicos de los Terremotos: EAEs) a finales del siglo III A.D., fecha coincidente con el inicio del periodo de declive económico de este asentamiento romano. Para intentar establecer el posible origen sísmico de las deformaciones, se ha procedido al inventario y análisis de las estructuras deformadas presentes en el yacimiento. No obstante, algunas de estas deformaciones también se pueden interpretar como resultado de procesos gravitaciones asociados a la ladera Este de la colina sobre la que se sitúa parte del yacimiento. Las direcciones de máxima deformación (ey) obtenidas del análisis de EAEs indica dos direcciones preferentes de la deformación (o movimiento preferente del terreno): NNO-SSE y ENEOSO. Aunque los datos presentan una dispersión importante, se puede establecer que la orientación principal NNO-SSE es compatible con un evento sísmico situado en el borde norte del Valle del Guadalquivir. La orientación ENE-OSO podría relacionarse con un evento posterior, o más seguramente con procesos de ladera de carácter cosísmico o no.The Roman archaeological site of Mulva-Munigua (Sevilla, Spain) displays building damage features suggesting a seismic origin (Earthquake Archaeological Effects: EAEs). The proposed seismic event could be tentatively dated in the late 3rd century AD, coinciding with the beginning of the economic fall of the Roman Empire at Iberia. However, some of the recorded EAEs can be also interpreted as a result of intervening slope movements in the eastern hillslope of this roman site. The inventory and analysis of the proposed EAEs make possible to discern between seismic oriented damage and other causes. In spite of the data show a significant dispersion, their analysis result in two different orientations of maximum deformation (ey) or preferential ground movement: NNW-SSE and ENE-WSW. The main ey orientation (NNW-SSE) can be tentatively related to a seismic event occurred in the environs of the northern border of the Guadalquivir Depression. The secondary orientation (ENE-WSW) can be interpreted as a consequence of latter slope movements triggered (or not) by other ancient earthquakes

65. Physical and clinical dosimetry by means of Monte Carlo using a process distribution tool

The choice of the most appropriate strategy in a Radiotherapy treatment is mainly based on the use of a planning system. With the introduction of new techniques (conformal and/or small fields, asymmetrical and non coplanar beams, true 3D calculations, IMRT) the trustworthiness of the algorithms is being questioned. An alternative verification procedure is every time more necessary to warranty a treatment delivery. The reliability of Monte Carlo is generally accepted. However, its clinical use has not been operative due to the high CPU times needed. During the last few years our objective has been focussed to reduce this time by means of new process distribution techniques. Tnis drop has made it feasible, not only the physical dosimetry under special conditions, but also a numerous variety of clinical cases: photon and electron conformal fields, Radiosurgery and IMRT. The carried out procedure is presented. Furthermore, experimental dosimetry data as well as conventional TPS calculations are compared with Monte Carlo simulations

Pre-Flight Calibration of the Mars 2020 Rover Mastcam Zoom (Mastcam-Z) Multispectral, Stereoscopic Imager

The NASA Perseverance rover Mast Camera Zoom (Mastcam-Z) system is a pair of zoomable, focusable, multi-spectral, and color charge-coupled device (CCD) cameras mounted on top of a 1.7 m Remote Sensing Mast, along with associated electronics and two calibration targets. The cameras contain identical optical assemblies that can range in focal length from 26 mm (25.5∘×19.1∘ FOV) to 110 mm (6.2∘×4.2∘ FOV) and will acquire data at pixel scales of 148-540 μm at a range of 2 m and 7.4-27 cm at 1 km. The cameras are mounted on the rover’s mast with a stereo baseline of 24.3±0.1 cm and a toe-in angle of 1.17±0.03∘ (per camera). Each camera uses a Kodak KAI-2020 CCD with 1600×1200 active pixels and an 8 position filter wheel that contains an IR-cutoff filter for color imaging through the detectors’ Bayer-pattern filters, a neutral density (ND) solar filter for imaging the sun, and 6 narrow-band geology filters (16 total filters). An associated Digital Electronics Assembly provides command data interfaces to the rover, 11-to-8 bit companding, and JPEG compression capabilities. Herein, we describe pre-flight calibration of the Mastcam-Z instrument and characterize its radiometric and geometric behavior. Between April 26thth and May 9thth, 2019, ∼45,000 images were acquired during stand-alone calibration at Malin Space Science Systems (MSSS) in San Diego, CA. Additional data were acquired during Assembly Test and Launch Operations (ATLO) at the Jet Propulsion Laboratory and Kennedy Space Center. Results of the radiometric calibration validate a 5% absolute radiometric accuracy when using camera state parameters investigated during testing. When observing using camera state parameters not interrogated during calibration (e.g., non-canonical zoom positions), we conservatively estimate the absolute uncertainty to be 0.2 design requirement. We discuss lessons learned from calibration and suggest tactical strategies that will optimize the quality of science data acquired during operation at Mars. While most results matched expectations, some surprises were discovered, such as a strong wavelength and temperature dependence on the radiometric coefficients and a scene-dependent dynamic component to the zero-exposure bias frames. Calibration results and derived accuracies were validated using a Geoboard target consisting of well-characterized geologic samples

Using surveillance data to estimate pandemic vaccine effectiveness against laboratory confirmed influenza A(H1N1)2009 infection : two case-control studies, Spain, season 2009-2010

Background: Physicians of the Spanish Influenza Sentinel Surveillance System report and systematically swab patients attended to their practices for influenza-like illness (ILI). Within the surveillance system, some Spanish regions also participated in an observational study aiming at estimating influenza vaccine effectiveness (cycEVA study). During the season 2009-2010, we estimated pandemic influenza vaccine effectiveness using both the influenza surveillance data and the cycEVA study. Methods: We conducted two case-control studies using the test-negative design, between weeks 48/2009 and 8/2010 of the pandemic season. The surveillance-based study included all swabbed patients in the sentinel surveillance system. The cycEVA study included swabbed patients from seven Spanish regions. Cases were laboratory-confirmed pandemic influenza A(H1N1)2009. Controls were ILI patients testing negative for any type of influenza. Variables collected in both studies included demographic data, vaccination status, laboratory results, chronic conditions, and pregnancy. Additionally, cycEVA questionnaire collected data on previous influenza vaccination, smoking, functional status, hospitalisations, visits to the general practitioners, and obesity. We used logistic regression to calculate adjusted odds ratios (OR), computing pandemic influenza vaccine effectiveness as (1-OR *100. Results: We included 331 cases and 995 controls in the surveillance-based study and 85 cases and 351 controls in the cycEVA study. We detected nine (2.7%) and two (2.4%) vaccine failures in the surveillance-based and cycEVA studies, respectively. Adjusting for variables collected in surveillance database and swabbing month, pandemic influenza vaccine effectiveness was 62% (95% confidence interval (CI): -5; 87). The cycEVA vaccine effectiveness was 64% (95%CI: -225; 96) when adjusting for common variables with the surveillance system and 75% (95%CI: -293; 98) adjusting for all variables collected. Conclusion: Point estimates of the pandemic influenza vaccine effectiveness suggested a protective effect of the pandemic vaccine against laboratory-confirmed influenza A(H1N1)2009 in the season 2009-2010. Both studies were limited by the low vaccine coverage and the late start of the vaccination campaign. Routine influenza surveillance provides reliable estimates and could be used for influenza vaccine effectiveness studies in future seasons taken into account the surveillance system limitations

The PanCam Instrument for the ExoMars Rover

The scientific objectives of the ExoMars rover are designed to answer several key questions in the search for life on Mars. In particular, the unique subsurface drill will address some of these, such as the possible existence and stability of subsurface organics. PanCam will establish the surface geological and morphological context for the mission, working in collaboration with other context instruments. Here, we describe the PanCam scientific objectives in geology, atmospheric science, and 3-D vision. We discuss the design of PanCam, which includes a stereo pair of Wide Angle Cameras (WACs), each of which has an 11-position filter wheel and a High Resolution Camera (HRC) for high-resolution investigations of rock texture at a distance. The cameras and electronics are housed in an optical bench that provides the mechanical interface to the rover mast and a planetary protection barrier. The electronic interface is via the PanCam Interface Unit (PIU), and power conditioning is via a DC-DC converter. PanCam also includes a calibration target mounted on the rover deck for radiometric calibration, fiducial markers for geometric calibration, and a rover inspection mirror.publishersversionPeer reviewe