Chemical modeling for pH prediction of acidified musts with gypsum and tartaric acid in warm regions

Winemaking of musts acidified with up to 3 g/L of gypsum (CaSO4 2H2O) and tartaric acid, both individually and in combination, as well as a chemical modeling have been carried out to study the behaviour of these compounds as acidifiers. Prior to fermentation gypsum and tartaric acid reduce the pH by 0.12 and 0.17 pH units/g/L, respectively, but while gypsum does not increase the total acidity and reduces buffering power, tartaric acid shows the opposite behaviour. When these compounds were used in combination, the doses of tartaric acid necessary to reach a suitable pH were reduced. Calcium concentrations increase considerably in gypsum-acidified must, although they fell markedly after fermentation over time. Sulfate concentrations also increased, although with doses of 2 g/L they were lower than the maximum permitted level (2.5 g/L). Chemical modeling gave good results and the errors in pH predictions were less than 5% in almost all case

Nighttime atmospheric chemistry of iodine

Little attention has so far been paid to the nighttime atmospheric chemistry of iodine species. Current atmospheric models predict a buildup of HOI and I₂ during the night that leads to a spike of IO at sunrise, which is not observed by measurements. In this work, electronic structure calculations are used to survey possible reactions that HOI and I₂ could undergo at night in the lower troposphere, and hence reduce their nighttime accumulation. The new reaction NO₃+ HOI  →  IO + HNO₃ is proposed, with a rate coefficient calculated from statistical rate theory over the temperature range 260–300 K and at a pressure of 1000 hPa to be k(T)  =  2.7  ×  10¯¹² (300 K/T)²·⁶⁶ cm³ molecule¯¹ s¯¹. This reaction is included in two atmospheric models, along with the known reaction between I₂ and NO₃, to explore a new nocturnal iodine radical activation mechanism. The results show that this iodine scheme leads to a considerable reduction of nighttime HOI and I₂, which results in the enhancement of more than 25 % of nighttime ocean emissions of HOI +I₂ and the removal of the anomalous spike of IO at sunrise. We suggest that active nighttime iodine can also have a considerable, so far unrecognized, impact on the reduction of the NO₃ radical levels in the marine boundary layer (MBL) and hence upon the nocturnal oxidizing capacity of the marine atmosphere. The effect of this is exemplified by the indirect effect on dimethyl sulfide (DMS) oxidation

Chemistry on hot astrochemical dust surfaces: Sulfur in AGB outflows

Astrochemical models treat dust surfaces as ice covered. We investigate the effects of implementing increased bare dust binding energies of CO and S-bearing species on the chemistry in the outflows of asymptotic giant branch (AGB) stars. We demonstrate the potential for improving agreement with observations in the outflow of IK Tau. Increasing the binding energies to measured and computationally derived values in high mass-loss AGB outflows increased the production of daughter species. Switching from a high binding energy on bare dust to weaker binding to ice, the gas phase abundance increased at a radius in agreement with observations of IK Tau, suggesting that displacement of bound species could contribute to this observational puzzle. Using a strong binding to bare dust, a gas phase increase was not observed, however parent species concentrations had to be increased by around a factor of four to explain observed concentrations

Débat sur les perspectives économiques à court terme d’octobre 2019

Xavier Ragot : Le ralentissement du commerce mondial s'explique-t-il uniquement par la guerre commerciale ? Quel sera l'ampleur du ralentissement américain ? Jusqu'où ira le ralentissement de l'économie chinoise ? Les banques centrales peuvent-elles reprendre le contrôle de l'inflation ? Faut-il s'inquiéter de l'endettement des entreprises ? [Premier paragraphe

Iodine chemistry after dark

Little attention has so far been paid to the nighttime atmospheric chemistry of iodine species. Current atmospheric models predict a buildup of HOI and I₂ during the night that leads to a spike of IO at sunrise, which is not observed by measurements. In this work, electronic structure calculations are used to survey possible reactions that HOI and I₂ could undergo at night in the lower troposphere, and hence reduce their nighttime accumulation. The new reaction NO₃ + HOI → IO + HNO₃ is proposed, with a rate coefficient calculated from statistical rate theory over the temperature range 260 - 300 K and at a pressure of 1000 hPa to be k(T) = 2.7 x 10-¹² (300 K / T ) ².⁶⁶ cm³ molecule-¹ s-¹ . This reaction is included in two atmospheric models, along with the known reaction between I₂ and NO₃, to explore a new nocturnal iodine radical activation mechanism. The results show that this iodine scheme leads to a considerable reduction of nighttime HOI and I₂, which results in the enhancement of more than 25% of nighttime ocean emissions of HOI + I₂ and the removal of the anomalous spike of IO at sunrise. We suggest that active nighttime iodine can also have a considerable, so far unrecognized, impact on the reduction of the NO₃ radical levels in the MBL and hence upon the nocturnal oxidizing capacity of the marine atmosphere. The effect of this is exemplified by the indirect effect on dimethyl sulfide (DMS) oxidation

Low temperature studies of the removal reactions of¹CH<inf>2</inf>with particular relevance to the atmosphere of Titan

Methylene, CH 2 , is one of the major photolysis products of methane by Lyman-α radiation and is involved in the photochemistry of the atmospheres of Titan and the giant planets. The kinetics of the reactions of the first excited state of methylene, 1 CH 2 , with He, N 2 , O 2 , H 2 and CH 4 have been measured over the temperature range 43–160 K by pulsed laser photolysis, monitoring 1 CH 2 removal by laser induced fluorescence. Low temperatures were obtained with either a pulsed Laval expansion (43–134 K) or a, slow flow reaction cell (160 K). The rate coefficients for the reactions with N 2 , O 2 , H 2 and CH 4 all showed a strong negative temperature dependence. In combination with other literature data, the rate coefficients can be parameterised as: k He (43 < T/K < 800) = (1.90 ± 0.23) × 10 −12 × (T/298) 1.74±0.16 × exp ((88±23)/ T ) k N 2 (43 < T/K < 800) = (2.29 ± 1.12) × 10 −12 × (T/298) −2.15±1.38 × exp ((-74±96)/ T ) + (3.91 ± 0.78) × 10 −11 × exp ((-469±114)/ T ) k O 2 (43 < T/K < 300) = (6.16 ± 1.09) × 10 −11 × (T/298) −0.65±0.14 k H 2 (43 < T/K < 800) = (1.10 ± 0.04) × 10 −10 × (T/298) −0.40±0.06 × exp ((11.1±6.9)/ T ) k CH 4 (43 < T/K < 475) = (8.20 ± 0.46) × 10 −11 × (T/298) −0.93±0.10 × exp ((-20.5±12.8)/ T ) For the reactions of 1 CH 2 with H 2 and CH 4 , the branching ratio for quenching to ground state, 3 CH 2 , vs chemical reaction was also determined at 160 and 73 K. The values measured (H 2 : 0.39 ± 0.10 at 160 K, 0.78 ± 0.15 at 73 K; CH 4 : 0.49 ± 0.09 at 160 K, 0.64 ± 0.19 at 73 K) confirm trends of an increased proportion of reactive loss with increasing temperature determined at higher temperatures. The impacts of the new measurements for Titan's atmosphere have been ascertained using a 1D chemistry and transport model. A significant decrease (∼40%) in the mixing ratio of ethane between 800 and 1550 km is calculated due to the decrease contribution of methyl production from the reaction of 1 CH 2 with CH 4 , with smaller increases in the concentrations of ethene and acetylene. Ethene production is enhanced by more methylene being converted to methylidene, CH, and the subsequent reaction of CH with CH 4 to generate ethene. Photolysis of ethene is the major route to acetylene formation

Surface ocean-lower atmosphere study: Scientific synthesis and contribution to Earth system science

The domain of the surface ocean and lower atmosphere is a complex, highly dynamic component of the Earth system. Better understanding of the physics and biogeochemistry of the air-sea interface and the processes that control the exchange of mass and energy across that boundary define the scope of the Surface Ocean-Lower Atmosphere Study (SOLAS) project. The scientific questions driving SOLAS research, as laid out in the SOLAS Science Plan and Implementation Strategy for the period 2004-2014, are highly challenging, inherently multidisciplinary and broad. During that decade, SOLAS has significantly advanced our knowledge. Discoveries related to the physics of exchange, global trace gas budgets and atmospheric chemistry, the CLAW hypothesis (named after its authors, Charlson, Lovelock, Andreae and Warren), and the influence of nutrients and ocean productivity on important biogeochemical cycles, have substantially changed our views of how the Earth system works and revealed knowledge gaps in our understanding. As such SOLAS has been instrumental in contributing to the International Geosphere Biosphere Programme (IGBP) mission of identification and assessment of risks posed to society and ecosystems by major changes in the Earth́s biological, chemical and physical cycles and processes during the Anthropocene epoch. SOLAS is a bottom-up organization, whose scientific priorities evolve in response to scientific developments and community needs, which has led to the launch of a new 10-year phase. SOLAS (2015–2025) will focus on five core science themes that will provide a scientific basis for understanding and projecting future environmental change and for developing tools to inform societal decision-making

(Sub)stellar companions shape the winds of evolved stars

Binary interactions dominate the evolution of massive stars, but their role is less clear for low- and intermediate-mass stars. The evolution of a spherical wind from an asymptotic giant branch (AGB) star into a nonspherical planetary nebula (PN) could be due to binary interactions. We observed a sample of AGB stars with the Atacama Large Millimeter/submillimeter Array (ALMA) and found that their winds exhibit distinct nonspherical geometries with morphological similarities to planetary nebulae (PNe). We infer that the same physics shapes both AGB winds and PNe; additionally, the morphology and AGB mass-loss rate are correlated. These characteristics can be explained by binary interaction. We propose an evolutionary scenario for AGB morphologies that is consistent with observed phenomena in AGB stars and PNe