Transition Metals in Atmospheric Liquid Phases. Sources, Reactivity, and Sensitive Parameters

Deguillaume, Laurent; Leriche, Maud; Desboeufs, Karine; Mailhot, Gilles; George, Christian; Chaumerliac, Nadine

doi:10.1002/chin.200549218

Cited by 98 publications

(187 citation statements)

References 239 publications

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“…This in turn forms the basis for understanding their thermodynamic properties and reactivity, having implications for modeling and understanding phenomena ranging from water exchange reactions 3,4 to photochemical processes 5 and atmospheric liquid chemistry of 3d transition-metal ions in solution. 6 While the structure of 3d transition metal (TM) ions and their complexes in aqueous solution can be addressed experimentally with numerous scattering and spectroscopic methods, 7 bonding can be assessed with a limited set of spectroscopic tools among which, historically, UV−vis spectroscopy has played a dominant role. Complementing such experimental results and due to the strongly polarized character of the coordinate bond, ligand-field theory 8,9 can be successfully applied to hexaaqua complexes.…”

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confidence: 99%

“…We investigate electronic structure of the hexaaqua complex [Ni(H 2 O) 6 ] 2+ with measured and calculated Ni L-edge RIXS. We show how the X-ray spectroscopic results complement information from UV−vis spectroscopy.…”

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confidence: 99%

“…We have chosen Ni 2+ (aq) for several reasons. First, as the Ni 2+ −water interaction can be regarded as local and limited to only the first solvation sphere, 18 6 ] 2+ complex is thus ideally suited to address the interplay of local atomic and intermolecular interactions in hexaaqua complexes. We note that Ni 2+ compounds have been used before as a test case for XAS and RIXS spectroscopies.…”

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“…The ab initio RASPT2 calculations on [Ni(H 2 O) 6 ] 2+ were performed using the MOLCAS software package. 56 The geometry of the [Ni(H 2 O) 6 VTZP quality were used in the CASPT2/RASPT2 calculations. 57,58 Scalar relativistic effects were introduced via a spinfree Douglas−Kroll−Hess transformation.…”

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From Ligand Fields to Molecular Orbitals: Probing the Local Valence Electronic Structure of Ni²⁺ in Aqueous Solution with Resonant Inelastic X-ray Scattering

et al. 2013

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Bonding of the Ni 2+ (aq) complex is investigated with an unprecedented combination of resonant inelastic X-ray scattering (RIXS) measurements and ab initio calculations at the Ni L absorption edge. The spectra directly reflect the relative energies of the ligand-field and charge-transfer valence-excited states. They give element-specific access with atomic resolution to the ground-state electronic structure of the complex and allow quantification of ligand-field strength and 3d−3d electron correlation interactions in the Ni 2+ (aq) complex. The experimentally determined ligand-field strength is 10Dq = 1.1 eV. This and the Racah parameters characterizing 3d−3d Coulomb interactions B = 0.13 eV and C = 0.42 eV as readily derived from the measured energies match very well with the results from UV−vis spectroscopy. Our results demonstrate how L-edge RIXS can be used to complement existing spectroscopic tools for the investigation of bonding in 3d transition-metal coordination compounds in solution. The ab initio RASPT2 calculation is successfully used to simulate the L-edge RIXS spectra. ■ INTRODUCTION3d transition metals in aqueous solution are interesting from a fundamental point of view as their hexaaqua complexes [M(H 2 O) 6 ] n+ represent the archetype of Werner complexes with coordinative bonding in octahedral symmetry. 1 Considering hydrogen bonding between the various coordination spheres of water molecules, they could even be regarded as chelate complexes, 2 and new insight into their electronic structure could help understanding the interplay of bonding, structure, and dynamics in these complexes. This in turn forms the basis for understanding their thermodynamic properties and reactivity, having implications for modeling and understanding phenomena ranging from water exchange reactions 3,4 to photochemical processes 5 and atmospheric liquid chemistry of 3d transition-metal ions in solution. 6 While the structure of 3d transition metal (TM) ions and their complexes in aqueous solution can be addressed experimentally with numerous scattering and spectroscopic methods, 7 bonding can be assessed with a limited set of spectroscopic tools among which, historically, UV−vis spectroscopy has played a dominant role. Complementing such experimental results and due to the strongly polarized character of the coordinate bond, ligand-field theory 8,9 can be successfully applied to hexaaqua complexes. In particular, the dependence of the ligand-field (LF) state energies on ligand-field strength and 3d−3d Coulomb interactions for all 3d n complexes were first calculated by Tanabe and Sugano in their seminal work from 1954. 10,11 The low-energy electronic excited state spectrum of a typical TM coordination complex can thus be described by, with increasing photon energy, the LF excitations, followed by the charge-transfer (CT) and ligand-centered excitations. At present, the excitations to LF states of octahedral TM complexes are very well understood at the semiempirical level of ligand-field theory. Today, ab ini...

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confidence: 99%

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confidence: 99%

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confidence: 99%

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confidence: 99%

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From Ligand Fields to Molecular Orbitals: Probing the Local Valence Electronic Structure of Ni²⁺ in Aqueous Solution with Resonant Inelastic X-ray Scattering

et al. 2013

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Sources and atmospheric processes impacting oxalate at a suburban coastal site in Hong Kong: Insights inferred from 1 year hourly measurements

et al. 2015

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Oxalic acid is one of the most abundant dicarboxylic acids in the atmosphere, receiving a great deal of attention due to its potential influence on cloud condensation nucleus activities. In this work, we report 10 months of hourly oxalate measurements in particulate matter of less than 2.5 μm in aerodynamic diameter (PM 2.5 ) by a Monitor for Aerosols and Gases in ambient Air at a suburban coastal site in Hong Kong from April 2012 to February 2013. A total of more than 6000 sets of oxalate and inorganic ion data were obtained. The mean (±SD) oxalate concentration was 0.34 (±0.18) μg m À3 , accounting for 2.8% of the total ion mass and 1.5% of the PM 2.5 mass. Seasonal variation showed higher concentrations in fall and winter (0.54 and 0.36 μg m À3 , respectively) and lower concentrations in spring and summer (~0.26 μg m À3 ). Different from the inorganic ions, a shallow dip in the oxalate concentration consistently occurred in the morning after sunrise (around 9:00 A.M.) throughout all seasons. Our analysis suggests that this was likely due to photolysis of oxalate-Fe (III) complex under sunlight. In summer, a small daytime peak was discernable for oxalate and nitrate. This characteristic, together with a more evident diurnal variation of O 3 , indicates comparatively more active photochemical oxidation in summer than other seasons. High correlations were observed between oxalate and non-sea-salt SO 4 2À (NSS) (R 2 = 0.63) and O x (O 3 + NO 2 ) (R 2 = 0.48), indicating significant commonality in their secondary formation. Positive matrix factorization analysis of oxalate and other real-time gas and particle-phase component data estimates that secondary formation processes, including secondary gas or aqueous oxidation processes (49%), oxidation processes of biomass burning emissions (37%), accounted for the majority of PM 2.5 oxalate. A backward trajectories cluster analysis found that higher oxalate/NSS ratios were associated with low pollution samples under the influence of marine air masses while the ratios were lower in high pollution samples that were typically associated with continental air masses passing through areas of high anthropogenic emissions. Isolating the "low pollution marine" aerosols across the entire data set indicates that oxalate production increased in the summer compared to other seasons, suggesting either more active marine emissions of oxalate precursors or stronger photochemical processes in the summer.

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Evolution of trace elements in the planetary boundary layer in southern China: Effects of dust storms and aerosol‐cloud interactions

Wang

Zhou³

et al. 2017

JGR Atmospheres

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Aerosols and cloud water were analyzed at a mountaintop in the planetary boundary layer in southern China during March–May 2009, when two Asian dust storms occurred, to investigate the effects of aerosol‐cloud interactions (ACIs) on chemical evolution of atmospheric trace elements. Fe, Al, and Zn predominated in both coarse and fine aerosols, followed by high concentrations of toxic Pb, As, and Cd. Most of these aerosol trace elements, which were affected by dust storms, exhibited various increases in concentrations but consistent decreases in solubility. Zn, Fe, Al, and Pb were the most abundant trace elements in cloud water. The trace element concentrations exhibited logarithmic inverse relationships with the cloud liquid water content and were found highly pH dependent with minimum concentrations at the threshold of pH ~5.0. The calculation of Visual MINTEQ model showed that 80.7–96.3% of Fe(II), Zn(II), Pb(II), and Cu(II) existed in divalent free ions, while 71.7% of Fe(III) and 71.5% of Al(III) were complexed by oxalate and fluoride, respectively. ACIs could markedly change the speciation distributions of trace elements in cloud water by pH modification. The in‐cloud scavenging of aerosol trace elements likely reached a peak after the first 2–3 h of cloud processing, with scavenging ratios between 0.12 for Cr and 0.57 for Pb. The increases of the trace element solubility (4–33%) were determined in both in‐cloud aerosols and postcloud aerosols. These results indicated the significant importance of aerosol‐cloud interactions to the evolution of trace elements during the first several cloud condensation/evaporation cycles.

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Transition Metals in Atmospheric Liquid Phases. Sources, Reactivity, and Sensitive Parameters

Abstract: Sensitive Parameters -[368 refs.]. -(DEGUILLAUME*, L.; LERICHE, M.; DESBOEUFS, K.; MAILHOT, G.; GEORGE, C.; CHAUMERLIAC, N.; Chem. Rev. (Washington, D. C.) 105 (2005) 9, 3388-3431; Lab. Meteorol. Phys., Univ. Blaise Pascal, F-63177 Aubiere, Fr.; Eng.) -Schramke 49-218

Cited by 98 publications

References 239 publications

From Ligand Fields to Molecular Orbitals: Probing the Local Valence Electronic Structure of Ni²⁺ in Aqueous Solution with Resonant Inelastic X-ray Scattering

From Ligand Fields to Molecular Orbitals: Probing the Local Valence Electronic Structure of Ni²⁺ in Aqueous Solution with Resonant Inelastic X-ray Scattering

Sources and atmospheric processes impacting oxalate at a suburban coastal site in Hong Kong: Insights inferred from 1 year hourly measurements

Evolution of trace elements in the planetary boundary layer in southern China: Effects of dust storms and aerosol‐cloud interactions

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Transition Metals in Atmospheric Liquid Phases. Sources, Reactivity, and Sensitive Parameters

Abstract: Sensitive Parameters -[368 refs.]. -(DEGUILLAUME*, L.; LERICHE, M.; DESBOEUFS, K.; MAILHOT, G.; GEORGE, C.; CHAUMERLIAC, N.; Chem. Rev. (Washington, D. C.) 105 (2005) 9, 3388-3431; Lab. Meteorol. Phys., Univ. Blaise Pascal, F-63177 Aubiere, Fr.; Eng.) -Schramke 49-218

Cited by 98 publications

References 239 publications

From Ligand Fields to Molecular Orbitals: Probing the Local Valence Electronic Structure of Ni2+ in Aqueous Solution with Resonant Inelastic X-ray Scattering

From Ligand Fields to Molecular Orbitals: Probing the Local Valence Electronic Structure of Ni2+ in Aqueous Solution with Resonant Inelastic X-ray Scattering

Sources and atmospheric processes impacting oxalate at a suburban coastal site in Hong Kong: Insights inferred from 1 year hourly measurements

Evolution of trace elements in the planetary boundary layer in southern China: Effects of dust storms and aerosol‐cloud interactions

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From Ligand Fields to Molecular Orbitals: Probing the Local Valence Electronic Structure of Ni²⁺ in Aqueous Solution with Resonant Inelastic X-ray Scattering

From Ligand Fields to Molecular Orbitals: Probing the Local Valence Electronic Structure of Ni²⁺ in Aqueous Solution with Resonant Inelastic X-ray Scattering