Coordination-driven self-assembly of a novel carbonato-bridged heteromolecular neutral nickel(II) triangle by atmospheric CO2 fixation

Formation of a quasi-symmetrical mu(3)-carbonato-bridged self-assembled heteromolecular triangle of Ni(II), [(mu(3)-CO3){Ni-2(salmeNH)(2)(NCS)(2)}[Ni(salmeNH(2))(2)]center dot Et2O center dot H2O (HsalmeNH = 2-[(3-methylamino-propylimino)-methyl]-phenol) involves atmospheric CO2 uptake in a neutral medium, by spontaneous self-reorganization of the starting mononuclear Ni(II)-Schiff-base complex, [Ni(salmeNH)(2)]. The environment around Ni(II) in two of the subunits is different from the third one. The starting complex, (Ni(salmeNH)(2)], and one of the possible intermediate species, [Ni(salmeNH(2))(2)(NCS)(2)], which has a very similar coordination environment to that in the third Ni(II) center, have been characterized structurally. A plausible mechanism for the formation of such a triangle has also been proposed. The compound shows a very strong antiferromagnetic coupling. Fit as a regular triangular arrangement gave J = -53.1, g = 2.24, and R = 1.5 x 10(-4).

Evaluation of data for atmospheric models: master equation/RRKM calculations on the combination reaction, BrO+NO2 -> BrONO2, a conundrum

Experimental data for the title reaction were modeled using master equation (ME)/RRKM methods based on the Multiwell suite of programs. The starting point for the exercise was the empirical fitting provided by the NASA (Sander, S. P.; Finlayson-Pitts, B. J.; Friedl, R. R.; Golden, D. M.; Huie, R. E.; Kolb, C. E.; Kurylo, M. J.; Molina, M. J.; Moortgat, G. K.; Orkin, V. L.; Ravishankara, A. R. Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation Number 15; Jet Propulsion Laboratory: Pasadena, California, 2006)(1) and IUPAC (Atkinson, R.; Baulch, D. L.; Cox, R. A.: R. F. Hampson, J.; Kerr, J. A.; Rossi, M. J.; Troe, J. J. Phys. Chem. Ref. Data. 2000, 29, 167) 2 data evaluation panels, which represents the data in the experimental pressure ranges rather well. Despite the availability of quite reliable parameters for these calculations (molecular vibrational frequencies (Parthiban, S.; Lee, T. J. J. Chem. Phys. 2000, 113, 145)3 and a. value (Orlando, J. J.; Tyndall, G. S. J. Phys. Chem. 1996, 100,. 19398)4 of the bond dissociation energy, D-298(BrO-NO2) = 118 kJ mol(-1), corresponding to Delta H-0(circle) = 114.3 kJ mol(-1) at 0 K) and the use of RRKM/ME methods, fitting calculations to the reported data or the empirical equations was anything but straightforward. Using these molecular parameters resulted in a discrepancy between the calculations and the database of rate constants of a factor of ca. 4 at, or close to, the low-pressure limit. Agreement between calculation and experiment could be achieved in two ways, either by increasing Delta H-0(circle) to an unrealistically high value (149.3 kJ mol(-1)) or by increasing , the average energy transferred in a downward collision, to an unusually large value (> 5000 cm(-1)). The discrepancy could also be reduced by making all overall rotations fully active. The system was relatively insensitive to changing the moments of inertia in the transition state to increase the centrifugal effect. The possibility of involvement of BrOONO was tested and cannot account for the difficulties of fitting the data.

Exploring NOy chemistry in levitated aqueous aerosol droplets

Chemistry of reactive nitrogen oxides, NOy, is crucial for our understanding of composition and properties of the Earth’s atmosphere. The proof-of-principle experiments demonstrated that we are able to study the atmospheric fate of nitrogen oxides that has significant impact on global climate and hydrological cycle, thus affecting the likelihood of local floods and acid rain.

Night-time tropospheric chemistry of the unsaturated alcohols (Z)-pent-2-en-1-ol and pent-1-en-3-ol: Kinetic studies of reactions of NO3 and N2O5 with stress-induced plant emissions

The night-time tropospheric chemistry of two stress-induced volatile organic compounds (VOCs), (Z)-pent-2-en-1-ol and pent-1-en-3-ol, has been studied at room temperature. Rate coefficients for reactions of the nitrate radical (NO3) with these pentenols were measured using the discharge-flow technique. Because of the relatively low volatility of these compounds, we employed off-axis continuous-wave cavity-enhanced absorption spectroscopy for detection of NO3 in order to be able to work in pseudo first-order conditions with the pentenols in large excess over NO3. The rate coefficients were determined to be (1.53 +/- 0.23) x 10(-13) and (1.39 +/- 0.19) x 10(-14) cm(3) molecule(-1) s(-1) for reactions of NO3 with (Z)-pent-2-en-1-ol and pent-1-en-3-ol. An attempt to study the kinetics of these reactions with a relative-rate technique, using N2O5 as source of NO3 resulted in significantly higher apparent rate coefficients. Performing relative-rate experiments in known excesses of NO2 allowed us to determine the rate coefficients for the N2O5 reactions to be (5.0 +/- 2.8) x 10(-19) cm(3) molecule(-1) s(-1) for (Z)-pent-2-en-1-ol, and (9.1 +/- 5.8) x 10(-19) cm(3) molecule(-1) s(-1) for pent-1-en-3-ol. We show that these relatively slow reactions can indeed interfere with rate determinations in conventional relative-rate experiments.

A study of the ethene-ozone reaction with photoelectron spectroscopy: measurement of product branching ratios and atmospheric implications

The ozone-ethene reaction has been investigated at low pressure in a flow-tube interfaced to a u.v. photoelectron spectrometer. Photoelectron spectra recorded as a function of reaction time have been used to estimate partial pressures of the reagents and products, using photoionization cross-sections for selected photoelectron bands of the reagents and products, which have been measured separately. Product yields compare favourably with results of other studies, and the production of oxygen and acetaldehyde have been measured as a function of time for the first time. A reaction scheme developed for the ozone-ethene reaction has been used to simulate the reagents and products as a function of time. The results obtained are in good agreement with the experimental measurements. For each of the observed products, the simulations allow the main reaction (or reactions) for production of that product to be established. The product yields have been used in a global model to estimate their global annual emissions in the atmosphere. Of particular interest are the calculated global annual emissions of formaldehyde (0.96 ± 0.10 Tg) and formic acid, (0.05 ± 0.01 Tg) which are estimated as 0.04% and 0.7% of the total annual emission respectively.

Physicochemical changes occuring in oil when atmospheric frying is combined with post-frying vacuum application

The aim of this study was to investigate the effect of atmospheric frying followed by drainage under vacuum on the stability of oil, compared to similar frying with drainage at atmospheric pressure. Changes in the oil were assessed by the free fatty acid (FFA) content, p-anisidine value (AnV), colour, viscosity, fatty acid profile and concentration of tocols. The rate of FFA formation in the case of vacuum drainage was found to be about half that of atmospheric drainage. Oil deterioration by oxidation and polymerisation was also reduced by the use of vacuum drainage. The AnV of the oil after vacuum drainage was lower by about 12%, the total colour difference was improved by 14% and viscosity was slightly reduced after 5 days of frying, compared to the values for oil that had been drained at atmospheric pressure. There was a reduction in the loss of polyunsaturated fatty acids in the case of vacuum drainage after 5 days of frying but differences in retention of tocols were only evident in the first two days of frying.

Latitudinal variation of the effect of aviation NOx emissions on atmospheric ozone and methane and related climate metrics

We evaluate the response to regional and latitudinal changes in aircraft NOx emissions using several climate metrics (radiative forcing (RF), Global Warming Potential (GWP), Global Temperature change Potential (GTP)). Global chemistry transport model integrations were performed with sustained perturbations in regional aircraft and aircraft-like NOx emissions. The RF due to the resulting ozone and methane changes is then calculated. We investigate the impact of emission changes for specific geographical regions (approximating to USA, Europe, India and China) and cruise altitude emission changes in discrete latitude bands covering both hemispheres. We find that lower latitude emission changes (per Tg N) cause ozone and methane RFs that are about a factor of 6 larger than those from higher latitude emission changes. The net RF is positive for all experiments. The meridional extent of the RF is larger for low latitude emissions. GWPs for all emission changes are positive, with tropical emissions having the largest values; the sign of the GTP depends on the choice of time horizon.

Ozonolysis of methyl oleate monolayers at the air–water interface: oxidation kinetics, reaction products and atmospheric implications

Ozonolysis of methyl oleate monolayers at the air–water interface results in surprisingly rapid loss of material through cleavage of the C[double bond, length as m-dash]C bond and evaporation/dissolution of reaction products. We determine using neutron reflectometry a rate coefficient of (5.7 ± 0.9) × 10−10 cm2 molecule−1 s−1 and an uptake coefficient of [similar]3 × 10−5 for the oxidation of a methyl ester monolayer: the atmospheric lifetime is [similar]10 min. We obtained direct experimental evidence that <2% of organic material remains at the surface on atmospheric timescales. Therefore known long atmospheric residence times of unsaturated fatty acids suggest that these molecules cannot be present at the interface throughout their ageing cycle, i.e. the reported atmospheric longevity is likely to be attributed to presence in the bulk and viscosity-limited reactive loss. Possible reaction products were characterized by ellipsometry and uncertainties in the atmospheric fate of organic surfactants such as oleic acid and its methyl ester are discussed. Our results suggest that a minor change to the structure of the molecule (fatty acid vs. its methyl ester) considerably impacts on reactivity and fate of the organic film.

The DACCIWA project: dynamics-aerosol-chemistry-cloud interactions in West Africa

Massive economic and population growth, and urbanization are expected to lead to a tripling of anthropogenic emissions in southern West Africa (SWA) between 2000 and 2030. However, the impacts of this on human health, ecosystems, food security, and the regional climate are largely unknown. An integrated assessment is challenging due to (a) a superposition of regional effects with global climate change, (b) a strong dependence on the variable West African monsoon, (c) incomplete scientific understanding of interactions between emissions, clouds, radiation, precipitation, and regional circulations, and (d) a lack of observations. This article provides an overview of the DACCIWA (Dynamics-Aerosol-Chemistry-Cloud Interactions in West Africa) project. DACCIWA will conduct extensive fieldwork in SWA to collect high-quality observations, spanning the entire process chain from surface-based natural and anthropogenic emissions to impacts on health, ecosystems, and climate. Combining the resulting benchmark dataset with a wide range of modeling activities will allow (a) assessment of relevant physical, chemical, and biological processes, (b) improvement of the monitoring of climate and atmospheric composition from space, and (c) development of the next generation of weather and climate models capable of representing coupled cloud-aerosol interactions. The latter will ultimately contribute to reduce uncertainties in climate predictions. DACCIWA collaborates closely with operational centers, international programs, policy-makers, and users to actively guide sustainable future planning for West Africa. It is hoped that some of DACCIWA’s scientific findings and technical developments will be applicable to other monsoon regions.

Complementarity of neutron reflectometry and ellipsometry for the study of atmospheric reactions at the air–water interface

The combined application of neutron reflectometry (NR) and ellipsometry to determine the oxidation kinetics of organic monolayers at the air–water interface is described for the first time. This advance was possible thanks to a new miniaturised reaction chamber that is compatible with the two techniques and has controlled gas delivery. The rate coefficient for the oxidation of methyl oleate monolayers by gas-phase O3 determined using NR is (5.4 ± 0.6) × 10−10 cm2 per molecule per s, which is consistent with the value reported in the literature but is now better constrained. This highlights the potential for the investigation of faster atmospheric reactions in future studies. The rate coefficient determined using ellipsometry is (5.0 ± 0.9) × 10−10 cm2 per molecule per s, which indicates the potential of this more economical, laboratory-based technique to be employed in parallel with NR. In this case, temporal fluctuations in the optical signal are attributed to the mobility of islands of reaction products. We outline how such information may provide critical missing information in the identification of transient reaction products in a range of atmospheric surface reactions in the future.