Isoprene and monoterpene fluxes from central amazonian rainforest inferred from tower-based and airborne measurements, and implications on the atmospheric chemistry and the local carbon budget

We estimated the isoprene and monoterpene source strengths of a pristine tropical forest north of Manaus in the central Amazon Basin using three different micrometeorological flux measurement approaches. During the early dry season campaign of the Cooperative LBA Airborne Regional Experiment (LBA-CLAIRE-2001), a tower-based surface layer gradient (SLG) technique was applied simultaneously with a relaxed eddy accumulation (REA) system. Airborne measurements of vertical profiles within and above the convective boundary layer (CBL) were used to estimate fluxes on a landscape scale by application of the mixed layer gradient (MLG) technique. The mean daytime fluxes of organic carbon measured by REA were 2.1 mg C m^−2 h^−1 for isoprene, 0.20 mg C m^−2 h^−1 for α-pinene, and 0.39 mg C m^−2 h^−1 for the sum of monoterpenes. These values are in reasonable agreement with fluxes determined with the SLG approach, which exhibited a higher scatter, as expected for the complex terrain investigated. The observed VOC fluxes are in good agreement with simulations using a single-column chemistry and climate model (SCM).\ud \ud In contrast, the model-derived mixing ratios of VOCs were by far higher than observed, indicating that chemical processes may not be adequately represented in the model. The observed vertical gradients of isoprene and its primary degradation products methyl vinyl ketone (MVK) and methacrolein (MACR) suggest that the oxidation capacity in the tropical CBL is much higher than previously assumed. A simple chemical kinetics model was used to infer OH radical concentrations from the vertical gradients of (MVK+MACR)/isoprene. The estimated range of OH concentrations during the daytime was 3–8×10^6 molecules cm^−3, i.e., an order of magnitude higher than is estimated for the tropical CBL by current state-of-the-art atmospheric chemistry and transport models. The remarkably high OH concentrations were also supported by results of a simple budget analysis, based on the flux-to-lifetime relationship of isoprene within the CBL. Furthermore, VOC fluxes determined with the airborne MLG approach were only in reasonable agreement with those of the tower-based REA and SLG approaches after correction for chemical decay by OH radicals, applying a best estimate OH concentration of 5.5×10^6 molecules cm^−3. The SCM model calculations support relatively high OH concentration estimates after specifically being constrained by the mixing ratios of chemical constituents observed during the campaign.\ud \ud The relevance of the VOC fluxes for the local carbon budget of the tropical rainforest site during the measurements campaign was assessed by comparison with the concurrent CO2 fluxes, estimated by three different methods (eddy correlation, Lagrangian dispersion, and mass budget approach). Depending on the CO2 flux estimate, 1–6% or more of the carbon gained by net ecosystem productivity appeared to be re-emitted through VOC emissions

La geología de Misiones según el informe inédito de CARTA

The Misiones province, Argentina, is part of the Paraná basin and its most conspicuous geological features find their best correlate in the bordering countries, Paraguay and Brazil. Regarding the region, especially Brazil, the knowledge of the geology of this argentine province has had a relatively minor historical development, reaching, until a few decades ago, a rather general character in many aspects. However, at different times in its history, there were various kinds of efforts to explore, describe, understand and map the geology of Misiones province. One of these initiatives occurred in the early 1960s, when the government of the recently created Misiones province (1953) hired the Argentine Topographic and Aerophotogrammetric Survey Company (CARTA), to carry out a survey of the provincial territory (29,801 km2), together with the evaluation of its natural resources (geology, soils and forestry). The decision to invest resources, mainly provincial, in a project of this magnitude, was based on the need to have basic information for planning the economic development of Misiones. This contribution presents an overview of the geological studies carried out at the time, which, for a long time, were an important reference at the provincial level.La provincia de Misiones forma parte de la cuenca del Paraná y sus rasgos geológicos más conspicuos encuentran su mejor correlato en los países limítrofes, Paraguay y Brasil. Con respecto a la región, especialmente Brasil, el conocimiento de la geología de esta provincia argentina ha tenido un desarrollo histórico relativamente menor, alcanzando, hasta hace pocas décadas atrás, un carácter más bien general en muchos aspectos. Sin embargo, en distintos momentos de su historia, existieron esfuerzos de diversa índole por explorar, describir, comprender y cartografiar la geología misionera. Una de estas iniciativas ocurrió a principios de 1960, cuando el gobierno de la recientemente creada Provincia de Misiones (1953), contrató a la Compañía Argentina de Relevamientos Topográficos y Aerofotogramétricos (CARTA), para realizar un relevamiento de todo el territorio provincial (29.801 km2), junto con la evaluación de sus recursos naturales (geología, suelos y forestación). La decisión de invertir recursos, principalmente provinciales, en un proyecto de esta envergadura, se fundó en la necesidad de contar con información de base para la planificación del desarrollo económico de Misiones. En esta contribución se presenta una reseña de los estudios geológicos realizados entonces, los cuales, durante mucho tiempo, fueron una referencia importante a nivel provincial

The Dissociation Energy of the New Diatomic Molecules SiPb and GePb

The diatomic molecules SiPb and GePb were for the first time identified by producing high temperature vapors of the constituent pure elements in a double-oven-like molecular-effusion assembly. The partial pressures of the atomic, heteronuclear, and homonuclear gaseous species observed in the vapor, namely, Si, Ge, Pb, SiPb, GePb, Pb2, Gen, and Sin (n=2-3), were mass-spectrometrically measured in the overall temperature ranges 1753-1961 K (Ge-Pb) and 1992-2314 K (Si-Pb). The dissociation energies of the new species were determined by second- and third-law analyses of both the direct dissociation reactions and isomolecular exchange reactions involving homonuclear molecules. The selected values of the dissociation energies at 0 K (D0 degrees) are 165.1+/-7.3 and 141.6+/-6.9 kJ/mol, respectively, for SiPb and GePb, and the corresponding enthalpies of formation (DeltafH0 degrees) are 476.4+/-7.3 and 419.3+/-6.9 kJ/mol. The ionization efficiency curves of the two species were measured, giving the following values for the first ionization energies: 7.0+/-0.2 eV (SiPb) and 7.1+/-0.2 eV (GePb). A computational study of the species SiPb and GePb was also carried out at the CCSD(T) level of theory using the relativistic electron core potential approach. Molecular parameters, adiabatic ionization energies, adiabatic electron affinities, and dissociation energies of the title species were calculated, as well as the enthalpy changes of the exchange reactions involving the other Pb-containing diatomics of group 14. Finally, a comparison between the experimental and theoretical results is presented, and from a semiempirical correlation the unknown dissociation energies of the SiSn and PbC molecules are predicted as 234+/-7 and 185+/-11 kJ/mol, respectively

Influence of Environmental Factors and Air Composition on the Emission of [alpha]-Pinene from Quercus ilex Leaves

We studied the emission of [alpha]-pinene from Quercus ilex leaves. Only the abaxial side of the hypostomatous Q. ilex leaf emits [alpha]-pinene. Light induced photosynthesis and [alpha]-pinene emission. However, the response of photosynthesis to dark-to-light transitions was faster than that of [alpha]-pinene, suggesting that ATP controls the emission. The emission was higher at 30 than at 20[deg]C, whereas photosynthesis did not change. Therefore, the relationship between photosynthesis and [alpha]-pinene emission does not always hold. When CO2 was removed from the air, transpiration was stimulated but photosynthesis and [alpha]-pinene emission were inhibited. [alpha]-Pinene inhibition was more rapid under low O2. When CO2 in the air was increased, photosynthesis was stimulated and transpiration was reduced, but [alpha]-pinene emission was unaffected. Therefore, the emission depends on the availability of photosynthetic carbon, is not saturated at ambient CO2, and is not dependent on stomatal opening. The pattern of [alpha]-pinene emission from Q. ilex is different from that of plants having specialized structures for storage and emission of terpenes. We suggest that [alpha]-pinene emitted by Q. ilex leaves is synthesized in the chloroplasts and shares the same biochemical pathway with isoprene emitted by isoprene-emitting oak species

The Dissociation Energy of the New Diatomic Molecules SiPb and GePb

The diatomic molecules SiPb and GePb were for the first time identified by producing high temperature vapors of the constituent pure elements in a double-oven-like molecular-effusion assembly. The partial pressures of the atomic, heteronuclear, and homonuclear gaseous species observed in the vapor, namely, Si, Ge, Pb, SiPb, GePb, Pb2, Gen, and Sin (n=2-3), were mass-spectrometrically measured in the overall temperature ranges 1753-1961 K (Ge-Pb) and 1992-2314 K (Si-Pb). The dissociation energies of the new species were determined by second- and third-law analyses of both the direct dissociation reactions and isomolecular exchange reactions involving homonuclear molecules. The selected values of the dissociation energies at 0 K (D0 degrees) are 165.1+/-7.3 and 141.6+/-6.9 kJ/mol, respectively, for SiPb and GePb, and the corresponding enthalpies of formation (DeltafH0 degrees) are 476.4+/-7.3 and 419.3+/-6.9 kJ/mol. The ionization efficiency curves of the two species were measured, giving the following values for the first ionization energies: 7.0+/-0.2 eV (SiPb) and 7.1+/-0.2 eV (GePb). A computational study of the species SiPb and GePb was also carried out at the CCSD(T) level of theory using the relativistic electron core potential approach. Molecular parameters, adiabatic ionization energies, adiabatic electron affinities, and dissociation energies of the title species were calculated, as well as the enthalpy changes of the exchange reactions involving the other Pb-containing diatomics of group 14. Finally, a comparison between the experimental and theoretical results is presented, and from a semiempirical correlation the unknown dissociation energies of the SiSn and PbC molecules are predicted as 234+/-7 and 185+/-11 kJ/mol, respectively

Evaporation/decomposition behavior of 1-Butyl-3-Methylimidazolium Chloride (BMImCL) investigated through effusion and thermal analysis techniques

The evaporation/decomposition behavior of the ionic liquid 1-butyl-3-methylimidazolium chloride (BMImCl) was studied with various techniques, such as thermogravimetry (TG), Knudsen effusion mass loss (KEML), and Knudsen effusion mass spectrometry (KEMS), in order to investigate the competition between the simple evaporation of the liquid as gaseous ion pairs (NIP: neutral ion pair) and the thermal decomposition releasing volatile species. TG/DSC experiments were carried out from 293 to 823 K under both He and N2 flowing atmospheres on BMImCl as well as on BMImNTf2 (NTf2: bis(trifluoromethylsulfonyl)imide). Both ionic liquids were found undergoing a single step of mass loss in the temperature range investigated. However, while the BMImNTf2 mass loss was found to occur in different temperature ranges, depending on the inert gas used, the TG curves of BMImCl under helium and nitrogen flow were practically superimposable, thus suggesting the occurrence of thermal decomposition. Furthermore, KEML experiments on BMImCl (in the range between 398 and 481 K) indicated a clear dependence of the unit area mass loss rate on the effusion hole diameter, an effect not observed for the ILs with NTf2 anion. Finally, KEMS measurements in the 416–474 K range allowed us to identify the most abundant species in the vapor phase, which resulted in methyl chloride, butylimidazole, butyl chloride, and methylimidazole, which most probably formed from the decomposition of the liquid

Surgical site infection after gastrointestinal surgery in high-income, middle-income, and low-income countries: a prospective, international, multicentre cohort study

Background: Surgical site infection (SSI) is one of the most common infections associated with health care, but its importance as a global health priority is not fully understood. We quantified the burden of SSI after gastrointestinal surgery in countries in all parts of the world. Methods: This international, prospective, multicentre cohort study included consecutive patients undergoing elective or emergency gastrointestinal resection within 2-week time periods at any health-care facility in any country. Countries with participating centres were stratified into high-income, middle-income, and low-income groups according to the UN's Human Development Index (HDI). Data variables from the GlobalSurg 1 study and other studies that have been found to affect the likelihood of SSI were entered into risk adjustment models. The primary outcome measure was the 30-day SSI incidence (defined by US Centers for Disease Control and Prevention criteria for superficial and deep incisional SSI). Relationships with explanatory variables were examined using Bayesian multilevel logistic regression models. This trial is registered with ClinicalTrials.gov, number NCT02662231. Findings: Between Jan 4, 2016, and July 31, 2016, 13 265 records were submitted for analysis. 12 539 patients from 343 hospitals in 66 countries were included. 7339 (58·5%) patient were from high-HDI countries (193 hospitals in 30 countries), 3918 (31·2%) patients were from middle-HDI countries (82 hospitals in 18 countries), and 1282 (10·2%) patients were from low-HDI countries (68 hospitals in 18 countries). In total, 1538 (12·3%) patients had SSI within 30 days of surgery. The incidence of SSI varied between countries with high (691 [9·4%] of 7339 patients), middle (549 [14·0%] of 3918 patients), and low (298 [23·2%] of 1282) HDI (p < 0·001). The highest SSI incidence in each HDI group was after dirty surgery (102 [17·8%] of 574 patients in high-HDI countries; 74 [31·4%] of 236 patients in middle-HDI countries; 72 [39·8%] of 181 patients in low-HDI countries). Following risk factor adjustment, patients in low-HDI countries were at greatest risk of SSI (adjusted odds ratio 1·60, 95% credible interval 1·05–2·37; p=0·030). 132 (21·6%) of 610 patients with an SSI and a microbiology culture result had an infection that was resistant to the prophylactic antibiotic used. Resistant infections were detected in 49 (16·6%) of 295 patients in high-HDI countries, in 37 (19·8%) of 187 patients in middle-HDI countries, and in 46 (35·9%) of 128 patients in low-HDI countries (p < 0·001). Interpretation: Countries with a low HDI carry a disproportionately greater burden of SSI than countries with a middle or high HDI and might have higher rates of antibiotic resistance. In view of WHO recommendations on SSI prevention that highlight the absence of high-quality interventional research, urgent, pragmatic, randomised trials based in LMICs are needed to assess measures aiming to reduce this preventable complication

PAK4 Kinase Activity Plays a Crucial Role in the Podosome Ring of Myeloid Cells

p21-Activated kinase 4 (PAK4), a serine/threonine kinase, is purported to localize to podosomes: transient adhesive structures that degrade the extracellular matrix to facilitate rapid myeloid cell migration. We find that treatment of transforming growth factor β (TGF-β)-differentiated monocytic (THP-1) cells with a PAK4-targeted inhibitor significantly reduces podosome formation and induces the formation of focal adhesions. This switch in adhesions confers a diminution of matrix degradation and reduced cell migration. Furthermore, reduced PAK4 expression causes a significant reduction in podosome number that cannot be rescued by kinase-dead PAK4, supporting a kinase-dependent role. Concomitant with PAK4 depletion, phosphorylation of Akt is perturbed, whereas a specific phospho-Akt signal is detected within the podosomes. Using superresolution analysis, we find that PAK4 specifically localizes in the podosome ring, nearer to the actin core than other ring proteins. We propose PAK4 kinase activity intersects with the Akt pathway at the podosome ring:core interface to drive regulation of macrophage podosome turnover

Paleoenvironments and age of the Talampaya Formation: The Permo-Triassic boundary in northwestern Argentina

© 2015 Elsevier Ltd. The Talampaya Formation is the basal unit of the Ischigualasto-Villa Unión rift system and has been traditionally assigned to the Triassic based on stratigraphic relationships. A median U-Pb age of 252.38 (+0.09/-0.22) Ma was obtained from volcanic zircons collected from a tuff bed close to the top of this unit at the Bordo Atravesado locality in the Cuesta de Miranda area (La Rioja, Argentina). This radiometric age is very close to the accepted Permian-Triassic boundary indicating that, at least in this locality, sedimentation occurred during the Late Permian but may have extended into the earliest Triassic. This new evidence indicates that the onset of the extensional event that gave rise to the rift basins in western Argentina started during the Permian. Detailed sedimentological studies of the 260 m thick Talampaya Formation allowed subdividing the succession into seven facies associations grouped into three evolutionary stages indicating that sedimentary environments initially evolved from alluvial fans to a braided river system. Subsequent intrabasinal volcanism associated with sediment deposition by low-to moderate-sinuosity rivers is recorded in the lower third of the column. The middle and upper part of the unit captures the evolution from ephemeral fluvial systems with an eolian interval to an ephemeral clastic lake with intermittent volcanic ash deposits. These changes indicate a progressive lowering of the landscape and a transition towards arid or semiarid conditions