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During the past five million yrs, benthic d18O records indicate a large range of climates, from warmer than today during the Pliocene Warm Period to considerably colder during glacials. Antarctic ice cores have revealed Pleistocene glacial-interglacial CO2 variability of 60-100 ppm, while sea level fluctuations of typically 125 m are documented by proxy data. However, in the pre-ice core period, CO2 and sea level proxy data are scarce and there is disagreement between different proxies and different records of the same proxy. This hampers comprehensive understanding of the long-term relations between CO2, sea level and climate. Here, we drive a coupled climate-ice sheet model over the past five million years, inversely forced by a stacked benthic d18O record. We obtain continuous simulations of benthic d18O, sea level and CO2 that are mutually consistent. Our model shows CO2 concentrations of 300 to 470 ppm during the Early Pliocene. Furthermore, we simulate strong CO2 variability during the Pliocene and Early Pleistocene. These features are broadly supported by existing and new d11B-based proxy CO2 data, but less by alkenone-based records. The simulated concentrations and variations therein are larger than expected from global mean temperature changes. Our findings thus suggest a smaller Earth System Sensitivity than previously thought. This is explained by a more restricted role of land ice variability in the Pliocene. The largest uncertainty in our simulation arises from the mass balance formulation of East Antarctica, which governs the variability in sea level, but only modestly affects the modeled CO2 concentrations.

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La respuesta higroscópica de la madera varía a lo largo de la dirección radial del árbol. El aumento de corta de ejemplares jóvenes y el uso de troncos de pequeños diámetros en la industria de los productos forestales, hacen preciso estudiar el comportamiento higroscópico tanto de la madera juvenil como de la madura. Su determinación proporciona información para comprender los mecanismos de sorción. Asimismo, la obtención de las propiedades termodinámicas de ambos tipos de madera facilita la modelización de procesos industriales como el secado o el encolado. En el presente trabajo, se ha comparado el comportamiento higroscópico y las propiedades termodinámicas de la madera juvenil y madura de Abies pinsapo Boissier, Abies alba Mill., Pinus canariensis C. Sm. ex DC., Pinus nigra Arnold, Pinus uncinata Mill. ex Mirb. y Pinus pinea L. Para este propósito se han utilizado las isotermas de sorción obtenidas mediante el método tradicional de sales saturadas descrito por COST Action E8 a 15, 35 y 50ºC en Abies pinsapo, Abies alba, Pinus nigra, Pinus uncinata y Pinus pinea, y a 35 y 50ºC en Pinus canariensis. Igualmente, se ha empleado el equipo dynamic vapor sorption (DVS) en la obtención de las isotermas de Pinus pinea a 35 y 50ºC. El ajuste de las curvas se ha realizado mediante el modelo Guggenheim, Anderson y de Boer-Dent (GAB), cumpliendo todas las muestras los criterios de aceptación establecidos. En el estudio de las isotermas se ha calculado el coeficiente y área de histéresis entre el proceso de adsorción y desorción para cada una de las muestras. Con el fin de comprender el comportamiento higroscópico experimentado por cada madera se ha determinado la composición química, espectros de infrarrojos (FTIR) y difractogramas de rayos X de cada una. Los parámetros termodinámicos - calor isostérico neto y total heat of wetting - se han obtenido a partir de las isotermas de sorción mediante el método de integración de la ecuación de Clausius-Clapeyron. Finalmente, se han comparado los datos obtenidos con el método tradicional de sales saturadas y con dynamic vapor sorption con el propósito de conocer la existencia de similitudes entre ambas metodologías. Los resultados mostraron que los puntos de equilibrio son, en la mayor parte de los casos, superiores en la madera madura frente a la juvenil, y por tanto las isotermas de la madera madura se encuentran siempre por encima de las de la juvenil, debido principalmente a la composición química. Respecto a las propiedades termodinámicas, se ha determinado que la energía involucrada en los procesos de sorción es superior en la madera madura que en la madera juvenil, siendo mayor en el proceso de desorción frente al de adsorción. En la comparación de las metodologías de sales saturadas y dynamic vapor sorption no se han detectado casi diferencias significativas en el proceso de adsorción, mientras que sí se han obtenido en el de desorción. ABSTRACT The hygroscopic response of wood varies throughout the radial direction of the tree. The longer cut of young trees and the use of small-diameter trunks in the forest product industry make it necessary to study the hygroscopic behaviour of both juvenile and mature wood. Determining this behaviour in both types of wood provides information for understanding the sorption mechanisms. Similarly, obtaining the thermodynamic properties of juvenile and mature wood facilitates modelling of industrial processes such as drying and bonding. In this study a comparison was made of the hygroscopic behaviour and thermodynamic properties of juvenile and mature wood of Abies pinsapo Boissier, Abies alba Mill., Pinus canariensis C. Sm. ex DC., Pinus nigra Arnold, Pinus uncinata Mill. ex Mirb. and Pinus pinea L. This was done by obtaining the sorption isotherms using the traditional saturated salt method described by COST Action E8 at 15, 35 and 50ºC in Abies pinsapo, Abies alba, Pinus nigra, Pinus uncinata and Pinus pinea, and at 35 and 50ºC in Pinus canariensis. In addition, dynamic vapour sorption (DVS) was used to obtain the isotherms of Pinus pinea at 35 and 50ºC. The curves were fitted using the Guggenheim, Anderson and de Boer- Dent (GAB) model and all samples met the established acceptance criteria. In the study of the isotherms, the hysteresis coefficient and area of the hysteresis loop between adsorption and desorption were calculated for each sample. To understand the hygroscopic behaviour of juvenile and mature wood, the chemical composition, infrared spectra (FTIR) and X-ray diffractograms of each type of wood were determined. The thermodynamic parameters - net isosteric heat and total heat of wetting - were obtained from the sorption isotherms by applying the integration method of the Clausius-Clapeyron equation. The data obtained using the traditional saturated salt method and with dynamic vapour sorption were compared to determine the similarities between the two methods. The results showed that the equilibrium points are greater in the mature wood than in the juvenile wood in most cases, and therefore the mature wood isotherms are always above the juvenile wood isotherms, mainly because of the chemical composition. As regards the thermodynamic properties, it was determined that the energy involved in the sorption processes is greater in the mature wood than in the juvenile wood, and is greater in the desorption process than in the adsorption process. On comparing the saturated salt and dynamic vapour sorption methods, almost no significant differences were detected in the adsorption process, but significant differences were obtained in the desorption process.