Mechanochemical synthesis of crystalline and amorphous digold(i) helicates exhibiting anion- and phase-switchable luminescence properties

For the first time, mechanochemical synthesis has been used for the preparation of crystalline and amorphous dinuclear gold(i) helicates, [Au2L2](X)2 (L = xantphos; X = CF3SO3, SCN, BF4 and PF6), that show anion- and phase-switchable luminescence properties. This solid-state approach provides strategies for developing switchable luminescent materials

The dynamics of cultivation and floods in arable lands of Central Argentina

Although floods in watersheds have been associated with land-use change since ancient times, the dynamics of flooding is still incompletely understood. In this paper we explored the relations between rainfall, groundwater level, and cultivation to explain the dynamics of floods in the extremely flat and valuable arable lands of the Quinto river watershed, in central Argentina. The analysis involved an area of 12.4 million hectare during a 26-year period (1978–2003), which comprised two extensive flooding episodes in 1983–1988 and 1996–2003. Supported by information from surveys as well as field and remote sensing measurements, we explored the correlation among precipitation, groundwater levels, flooded area and land use. Flood extension was associated to the dynamics of groundwater level. While no correlation with rainfall was recorded in lowlands, a significant correlation (<i>P</i><0.01) between groundwater and rainfall in highlands was found when estimations comprise a time lag of one year. Correlations between groundwater level and flood extension were positive in all cases, but while highly significant relations (<i>P</i><0.01) were found in highlands, non significant relations (<i>P</i>>0.05) predominate in lowlands. Our analysis supports the existence of a cyclic mechanism driven by the reciprocal influence between cultivation and groundwater in highlands. This cycle would involve the following stages: (a) cultivation boosts the elevation of groundwater levels through decreased evapotranspiration; (b) as groundwater level rises, floods spread causing a decline of land cultivation; (c) flooding propitiates higher evapotranspiration favouring its own retraction; (d) cultivation expands again following the retreat of floods. Thus, cultivation would trigger a destabilizing feedback self affecting future cultivation in the highlands. It is unlikely that such sequence can work in lowlands. The results suggest that rather than responding directly and solely to the same mechanism, floods in lowlands may be the combined result of various factors like local rainfall, groundwater level fluctuations, surface and subsurface lateral flow, and water-body interlinking. Although the hypothetical mechanisms proposed here require additional understanding efforts, they suggest a promising avenue of environmental management in which cultivation could be steered in the region to smooth the undesirable impacts of floods

The Missing Link in the Magnetism of Hybrid Cobalt Layered Hydroxides: The Odd-Even Effect of the Organic Spacer

A dramatic change in the magnetic behaviour, which solely depends on the parity of the organic linker molecules, has been found in a family of layered Co-II hydroxides covalently functionalized with dicarboxylic molecules. These layered hybrid materials have been synthesized at room temperature using a one-pot procedure through the epoxide route. While hybrids connected by odd alkyl chains exhibit coercive fields (H-c) below ca. 3500 Oe and show spontaneous magnetization at temperatures (T-M) below 20 K, hybrids functionalized with even alkyl chains behave as hard magnets with H(c)5500 Oe and display a T-M higher than 55 K. This intriguing behaviour was studied by density functional theory with the incorporation of a Hubbard term (DFT+U) calculations, unveiling the structural subtleties underlying this observation. Indeed, the different molecular orientation exhibited by the even/odd alkyl chains, and the orientation of the covalently linked carboxylic groups modify the intensity of the magnetic coupling of both octahedral and tetrahedral in-plane sublattices, thus strongly affecting the magnetic properties of the hybrid. These findings offer an outstanding level of tuning in the molecular design of hybrid magnetic materials based on layered hydroxides

Room temperature synthesis of lanthanum phosphates with controlled nanotexture as host for Ln(III) through the Epoxide Route

Herein, the Epoxide Route, a one-pot room temperature alkalinization method based on the reaction between a nucleophile and an epoxide, has been employed to synthesize LaPO4 in the form of a Rhabdophane phase. The intrinsic features of this synthetic approach allow the reaction to be followed by pH monitoring, making possible the identification of the different precipitation steps involved in the formation of the solid. Once demonstrated the effectiveness of this chemical methodology, the size and shape of the LaPO4 particles were controlled by varying the identity and proportion of the organic co-solvents employed to perform the reaction. By these means, crystalline particles with dumbbell, urchin and needle shapes were obtained, with sizes that ranged from less than 200 nm to more than 5 μm. Finally, luminescent materials in the form of a LnPO4 Rhabdophane structure were easily obtained by the incorporation of EuIII along the whole composition range. Additionally, photophysical characterization of selected samples was performed, with a promising outcome. The results presented in this work pave the way to obtaining a wide variety of luminescent materials with sizes and morphologies adjustable on demand, by using a simple and reliable synthetic approach

Hydrological and productive impacts of recent land-use and land-cover changes in the semiarid Chaco: Understanding novel water excess in water scarce farmlands

Over the last decades, the rapid replacement of native forests by crops and pastures in the Argentinean semiarid Chaco plains has triggered unprecedented groundwater level raises resulting from deep drainage increases, leading to the first massive waterlogging event on records (~25,000 Ha flooded in 2015 near Bandera, one of the most cultivated clusters of the Chaco). In this paper, we link this episode to the ongoing deforestation and cropping scheme shifts through the combined analysis of remote sensing data, agricultural surveys, local farmer information and hydrologic modelling. From 2000 to 2015, the agricultural area of Bandera increased from 21% to 50%, mostly at the expense of dry forests. In this period, agriculture migrated from more intensive (i.e., double-cropping) to more water-conservative (i.e., late-summer single crops) schemes as a general strategy to reduce drought risks. These changes reduced regional evapotranspiration and increased the intensity of deep drainage in wet years. Contrasting cropping schemes displayed significant evapotranspiration differences, but all of them experienced substantial drainage losses (~100–200 mm) during the wettest year (2014/2015), suggesting that cropping adjustments have a limited capacity to halt the generation of water excesses. Nearly 50% of the cropped area in Bandera could not be sown or harvested following the groundwater recharge event of 2014/2015. In the ongoing context of shallow and rising water tables, the introduction of novel cropping schemes that include deep-rooted perennials, to promote transpirative groundwater discharge, seems crucial to avoid the recurrence of water excesses and their associated dryland salinity risk in the region.Fil: Giménez, Raúl. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Matemática Aplicada de San Luis "Prof. Ezio Marchi". Universidad Nacional de San Luis. Facultad de Ciencias Físico, Matemáticas y Naturales. Instituto de Matemática Aplicada de San Luis "Prof. Ezio Marchi"; ArgentinaFil: Mercau, Jorge Luis. Instituto Nacional de Tecnología Agropecuaria. Centro Regional La Pampa-San Luis. Estación Experimental Agropecuaria San Luis. Agencia de Extensión Rural San Luis; ArgentinaFil: Bert, Federico Esteban. Universidad de Buenos Aires; Argentina. Universidad de Buenos Aires. Facultad de Agronomía; ArgentinaFil: Kuppel, Sylvain. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Centre National de la Recherche Scientifique; Francia. University of Aberdeen; Reino UnidoFil: Baldi, Germán. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Matemática Aplicada de San Luis "Prof. Ezio Marchi". Universidad Nacional de San Luis. Facultad de Ciencias Físico, Matemáticas y Naturales. Instituto de Matemática Aplicada de San Luis "Prof. Ezio Marchi"; Argentina. Universidad Nacional de San Luis. Facultad de Ciencias Físico Matemáticas y Naturales. Departamento de Geología; ArgentinaFil: Houspanossian, Javier. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Matemática Aplicada de San Luis "Prof. Ezio Marchi". Universidad Nacional de San Luis. Facultad de Ciencias Físico, Matemáticas y Naturales. Instituto de Matemática Aplicada de San Luis "Prof. Ezio Marchi"; Argentina. Universidad Nacional de San Luis. Facultad de Ciencias Físico Matemáticas y Naturales. Departamento de Geología; ArgentinaFil: Magliano, Patricio Nicolás. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Matemática Aplicada de San Luis "Prof. Ezio Marchi". Universidad Nacional de San Luis. Facultad de Ciencias Físico, Matemáticas y Naturales. Instituto de Matemática Aplicada de San Luis "Prof. Ezio Marchi"; Argentina. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Departamento de Bioquímica y Ciencias Biológicas; ArgentinaFil: Jobbagy Gampel, Esteban Gabriel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Matemática Aplicada de San Luis "Prof. Ezio Marchi". Universidad Nacional de San Luis. Facultad de Ciencias Físico, Matemáticas y Naturales. Instituto de Matemática Aplicada de San Luis "Prof. Ezio Marchi"; Argentin

Contrasting CO2 and water vapour fluxes in dry forest and pasture sites of central Argentina

The dry forests of South America are a key player of the global carbon cycle and the regional water cycle, but they are being intensively deforested. We used eddy covariance measurements to compare the temporal patterns of CO2 and water vapour fluxes and their relationships with environmental variables in dry forest and pastures sites of central Argentina. Ecosystem fluxes showed clear contrasts in magnitude, timing and response to environmental controls between ecosystems. The dry forest displayed higher daily gross primary productivity (GPP, 10.6 vs. 7.8 g CO2 m−2 d−1) and ecosystem respiration (Reco, 9.1 vs. 7.0 g CO2 m−2 d−1) and lower net ecosystem exchange (NEE, −1.5 vs. −0.7 g CO2 m−2 d−1) than the pasture. These differences were explained by a lower tolerance of the pasture to cool temperatures and drought. The lowest NEE rates were observed between 26°C and 34°C in the pasture, but below this range, NEE increased sharply, switching to a carbon source with temperatures <20°C. By contrast, the dry forest remained as a strong carbon sink down to 18°C. The pasture also showed a stronger drop of GPP with drought compared with the dry forest, becoming a carbon source with soil wetness <25% of soil available water. Rainfall was strongly coupled with GPP in both ecosystems, but the dry forest responded to longer rainfall integration periods. This study helps to understand how ecosystems can respond to climate change, improve global scale modelling and increase the productivity and resilience of rangelands.Fil: Nosetto, Marcelo Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Matemática Aplicada de San Luis "Prof. Ezio Marchi". Universidad Nacional de San Luis. Facultad de Ciencias Físico, Matemáticas y Naturales. Instituto de Matemática Aplicada de San Luis "Prof. Ezio Marchi"; ArgentinaFil: Luna Toledo, Emanuel Santiago. Instituto Nacional de Tecnología Agropecuaria; Argentina. Universidad Nacional de Chilecito; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Magliano, Patricio Nicolás. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Matemática Aplicada de San Luis "Prof. Ezio Marchi". Universidad Nacional de San Luis. Facultad de Ciencias Físico, Matemáticas y Naturales. Instituto de Matemática Aplicada de San Luis "Prof. Ezio Marchi"; ArgentinaFil: Figuerola, Patricia Irene. Universidad Nacional de Chilecito; ArgentinaFil: Blanco, Lisandro Javier. Instituto Nacional de Tecnología Agropecuaria; ArgentinaFil: Jobbagy Gampel, Esteban Gabriel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Matemática Aplicada de San Luis "Prof. Ezio Marchi". Universidad Nacional de San Luis. Facultad de Ciencias Físico, Matemáticas y Naturales. Instituto de Matemática Aplicada de San Luis "Prof. Ezio Marchi"; Argentin

Sequía e inundación en la hiperllanura pampeana : una mirada desde el lote al municipio

71-77En la Región Pampeana la lluvia, y su elevada variabilidad, es la principal determinante de la producción agropecuaria (Hall et al., 1992)que motoriza la economía de muchos municipios. En los sistemas de producción pampeanos, en los que el riego es aún una práctica poco común, la escasez de lluvias resiente a la producción y propaga sus efectos en el tiempo y en la comunidad a partir de los daños económicos que genera. En el otro extremo, las lluvias excesivas desencadenan procesos de anegamiento e inundación capaces de generar daños de magnitud similar a los de la sequía. En paisajes extremadamente planos o de 'hiperllanura' (Jobbágy et al., 2008), como son los de la Pampa Deprimida e Interior, el escurrimiento lento y dificultoso lleva a que los excesos hídricos se almacenen localmente, elevando los niveles freáticos e incrementando el área ocupada por agua en las zonas más bajas del paisaje. Las inundaciones resultantes son de avance gradual y sostenido y pueden durar muchos meses, generando pérdidas productivas y daños en la infraestructura de áreas rurales y urbanas. En el Oeste Pampeano y en gran parte de la cuenca del Río Salado las fluctuaciones del nivel de la napa freática están estrechamente conectadas al balance hídrico local y con los cuerpos superficiales de agua (Aragón et al., 2010; Badano, 2010). Los excesos hídricos son almacenados localmente en lagunas o en la napa freática, que lentamente sube de nivel. Las napas cercanas a la superficie aumentan fuertemente el rendimiento de los cultivos, especialmente en años secos (Nosetto et al., 2009), representando una vía de transferencia de agua de años de exceso a años de déficit (Jobbagy et al., 2008). Sin embargo, una vez que la napa supera un umbral de cercanía a la superficie el rendimiento cae abruptamente (Nosetto et al., 2009)y, a nivel de paisaje, el área ocupada por cuerpos de agua se expande con mucha rapidez, las lagunas comienzan a coalecer y en casos extremos se disparan inundaciones regionales (Aragón et al., 2010). Como el drenaje superficial natural y/o artificial de los excedentes tiene un alcance limitado en la región (Badano, 2010), cobra gran importancia el control de la recarga para evitar llegar a ese umbral crítico en el que aumenta el riesgo de inundación. Existen evidencias de que el reemplazo de pasturas perennes por cultivos ha aumentado la recarga (Nosetto et al., 2012), especialmente cuando luego de algunos años secos se siembran campos bajos que luego, en años húmedos, quedan sin sembrar o pierden sus cultivos tempranamente. Al margen del riesgo de inundación, los productores también se beneficiarían si lograran disminuir los excedentes hídricos. Aumentar la transpiración vegetal es una de las avenidas más potentes para lograr mayor productividad del agua limitando otras vías de pérdidas del sistema (Passioura, 2006), como el drenaje profundo o la evaporación desde grandes cuerpos de agua durante una inundación. Por eso, aunque pueden existir conflictos entre distintos usos de la tierra y los intereses de los municipios, también es claro que puede haber oportunidades para un beneficio mutuo. Lograr un uso más inteligente y justo del territorio requiere del conocimiento de los beneficios y riesgos que enfrentan sus múltiples usuarios y las alternativas disponibles. Frente al rol dual del agua en la Hiperllanura Pampeana, es valioso adaptar las estrategias de uso de la tierra para minimizar riesgos y daños maximizando la producción y el desarrollo económico. Para dar este paso surge una necesidad previa que es la de comprender la percepción que distintos actores del territorio tienen respecto a estas fluctuaciones ecohidrológicas. Con ese objetivo, realizamos un taller de discusión en la localidad de América, guiados por las siguientes preguntas: ¿en qué medida difieren los efectos, productivos y económicos, de la sequía y la inundación? ¿Cómo afectan estas perturbaciones aperturbaciones a distintos productores y a todo un municipio? ¿Cuáles son sus opciones y respuestas más comunes? Este trabajo presenta los hallazgos más sobresalientes

CO2 and CH4 exchanges between land ecosystems and the atmosphere in northern high latitudes over the 21st century

Author Posting. © American Geophysical Union, 2006. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geophysical Research Letters 33 (2006): L17403, doi:10.1029/2006GL026972.Terrestrial ecosystems of the northern high latitudes (above 50oN) exchange large amounts of CO2 and CH4 with the atmosphere each year. Here we use a process-based model to estimate the budget of CO2 and CH4 of the region for current climate conditions and for future scenarios by considering effects of permafrost dynamics, CO2 fertilization of photosynthesis and fire. We find that currently the region is a net source of carbon to the atmosphere at 276 Tg C yr-1. We project that throughout the 21st century, the region will most likely continue as a net source of carbon and the source will increase by up to 473 Tg C yr-1 by the end of the century compared to the current emissions. However our coupled carbon and climate model simulations show that these emissions will exert relatively small radiative forcing on global climate system compared to large amounts of anthropogenic emissions.This study was supported by a NSF Biocomplexity (ATM-0120468) and ARCSS programs; the NASA Land Cover and Land Use Change and EOS Interdisciplinary Science (NNG04GJ80G) programs; and by funding from MIT Joint Program on the Science and Policy of Global Change, which is supported by a consortium of government, industry and foundation sponsors