Chemical Mechanism Development: Laboratory Studies and Model Applications

Within the German Tropospheric Research Programme (TFS) numerous kinetic and mechanistic studies on the tropospheric reaction/degradation of the following reactants were carried out: oxygenated VOC, aromatic VOC, biogenic VOC, short-lived intermediates, such as alkoxy and alkylperoxy radicals.At the conception of the projects these selected groups were classes of VOC or intermediates for which the atmospheric oxidation mechanisms were either poorly characterised or totally unknown. The motivation for these studies was the attainment of significant improvements in our understanding of the atmospheric chemical oxidation processes of these compounds, particularly with respect to their involvement in photooxidant formation in the troposphere. In the present paper the types of experimental investigations performed and the results obtained within the various projects are briefly summarised. The major achievements are highlighted and discussed in terms of their contribution to improving our understanding of the chemical processes controlling photosmog formation in the troposphere.     

The Influence of Oxalate on Fe-Catalyzed S(IV) Oxidation by Oxygen in Aqueous Solution

This study demonstrates that oxalate has a strong inhibiting effect onFe-catalyzed S(IV) oxidation by oxygen in aqueous solution. While thepseudo-first order rate constant of S(IV) oxidation was determined to be1.6 × 10³ M^-1 s^-1 in experimentswithout oxalate, the oxidation of S(IV) was totally inhibited at a molarconcentration ratio of iron:oxalate = 1:5 at an oxalate concentration of 4M. Under these conditions, the Fe(II)/Fe(III) ratio remained nearlyconstant during the observed reaction time. The determined rate constants wereindependent of the initial oxidation state of iron. However, with increasingconcentrations of oxalate, a longer induction period is observed forexperiments with iron initially in the Fe(II) oxidation state.     

Semiannual and annual variations in the height of the ionospheric F2-peak

Ionosonde data from sixteen stations are used to study the semiannual and annual variations in the height of the ionospheric F2-peak, hmF2. The semiannual variation, which peaks shortly after equinox, has an amplitude of about 8 km at an average level of solar activity (10.7 cm flux = 140 units), both at noon and midnight. The annual variation has an amplitude of about 11 km at northern midlatitudes, peaking in early summer; and is larger at southern stations, where it peaks in late summer. Both annual and semiannual amplitudes increase with increasing solar activity by day, but not at night. The semiannual variation in hmF2 is unrelated to the semiannual variation of the peak electron density NmF2, and is not reproduced by the CTIP and TIME-GCM computational models of the quiet-day thermosphere and ionosphere. The semiannual variation in hmF2 is approximately isobaric, in that its amplitude corresponds quite well to the semiannual variation in the height of fixed pressure-levels in the thermosphere, as represented by the MSIS empirical model. The annual variation is not isobaric. The annual mean of hmF2 increases with solar 10.7 cm flux, both by night and by day, on average by about 0.45 km/flux unit, rather smaller than the corresponding increase of height of constant pressure-levels in the MSIS model. The discrepancy may be due to solar-cycle variations of thermospheric winds. Although geomagnetic activity, which affects thermospheric density and temperature and therefore hmF2 also, is greatest at the equinoxes, this seems to account for less than half the semiannual variation of hmF2. The rest may be due to a semiannual variation of tidal and wave energy transmitted to the thermosphere from lower levels in the atmosphere.     

The role of sodium bicarbonate in the nucleation of noctilucent clouds

It is proposed that a component of meteoric smoke, sodium bicarbonate (NaHCO₃), provides particularly effective condensation nuclei for noctilucent clouds. This assertion is based on three conditions being met. The first is that NaHCO₃ is present at sufficient concentration (10⁴ cm^–3) in the upper mesosphere between 80 and 90 km. It is demonstrated that there is strong evidence for this based on recent laboratory measurements coupled with atmospheric modelling. The second condition is that the thermodynamics of NaHCO₃(H₂O)_n cluster formation allow spontaneous nucleation to occur under mesospheric conditions at temperatures below 140 K. The Gibbs free energy changes for forming clusters with n = 1 and 2 were computed from quantum calculations using hybrid density functional/Hartree-Fock (B3LYP) theory and a large basis set with added polarization and diffuse functions. The results were then extrapolated to higher n using an established dependence of the free energy on cluster size and the free energy for the sublimation of H₂O to bulk ice. A 1-dimensional model of sodium chemistry was then employed to show that spontaneous nucleation to form ice particles (n > 100) should occur between 84 and 89 km in the high-latitude summer mesosphere. The third condition is that other metallic components of meteoric smoke are less effective condensation nuclei, so that the total number of potential nuclei is small relative to the amount of available H₂O. Quantum calculations indicate that this is probably the case for major constituents such as Fe(OH)₂, FeO₃ and MgCO₃.     

IMPACT: an implicit time integration scheme for chemical species and families

The implicit time integration scheme of Stott and Harwood (1993) was proposed as an efficient scheme for use in three-dimensional chemical models of the atmosphere. The scheme was designed for chemistry schemes using chemical families, in which species with short lifetimes are grouped into longer-lived families. Further study with more complex chemistry, more species and reactions showed the scheme to be non-convergent and unstable under certain conditions; particularly for the perturbed chemical scenarios of polar stratospheric winters. In this work the scheme has been improved by revising the treatment of families and the convergence properties of the scheme. The new scheme has been named IMPACT (IMPlicit Algorithm for Chemical Time-stepping). It remains easy to implement and produces simulations that compare well with integrations using more accurate higher order schemes.     

Fog and rain water chemistry at Mt. Fuji: A case study during the September 2002 campaign

Measurements of fog and rain water chemistry at the summit of Mt. Fuji, the highest peak in Japan, as well as at Tarobo, the ESE slope of Mt. Fuji in September 2002. The pH of fog and rain water sampled at Mt. Fuji varied over a range of 4.0–6.8. Acidic fogs (pH < 5.0) were observed at the summit when the air mass came from the industrial regions on the Asian continent. The ratio of [SO₄²⁻]/[NO₃⁻] in the fog water was lower at Tarobo than at the summit. High concentrations of Na⁺ and Cl⁻ were determined in the rain water sampled at the summit, possibly because of the long-range transport of sea-salt particles raised by a typhoon through the middle troposphere. The vertical transport of sea-salt particles would influence the cloud microphysical properties in the middle troposphere. Significant loss of Mg²⁺ was seen in the rain water at the summit. The concentrations of peroxides in the fog and rain water were relatively large (10–105 μM). The potential capacity for SO₂ oxidation seems to be strong from summer to early autumn at Mt. Fuji. The fog water peroxide concentrations displayed diurnal variability. The peroxide concentrations in the nighttime were significantly higher than those in the daytime.     

芙蓉锡矿田骑田岭花岗岩黑云母矿物化学组成及其对锡成矿的指示意义

芙蓉锡矿田骑田岭复式岩体主要由早阶段角闪石黑云母花岗岩和晚阶段黑云母花岗岩组成.电子探针分析结果表明角闪石黑云母花岗岩中的黑云母属于铁黑云母,黑云母花岗岩中的黑云母属于铁叶云母.相对于黑云母花岗岩,角闪石黑云母花岗岩中黑云母的MgO、TiO2含量偏高,Al2O3含量偏低.矿物化学研究结果显示,角闪石黑云母花岗岩中黑云母的结晶温度、氧逸度(logfO2)分别为680℃～740℃、-16.00～-15.31,黑云母花岗岩中黑云母的结晶温度、氧逸度分别为530℃～650℃、-19.20～-17.50.从角闪石黑云母花岗岩到黑云母花岗岩,岩浆结晶温度和氧逸度逐渐降低.与花岗岩有关的共存流体性质的研究发现,与角闪石黑云母花岗岩共存的热液流体log(fH2O/fHF)fluid,log(fH2O/fHCl)fluid,log(fHF/fHCl)fiuid值分别为4.22～4.39,2.78～3.24,-1.82～-1.73,而与黑云母花岗岩共存的热液流体log(fH2O/fHF)fluid,log(fH2OfHCl)fluid,log(fHF/fHCl)fluid值分别为3.27～3.53,2.85～3.22,-0.75～-0.22,可见与两种岩石类型共存热液流体的性质存在明显差异,且热液中Cl、Sn含量变化与岩浆结晶分异指数呈正相关关系.骑田岭岩体从角闪石黑云母花岗岩到黑云母花岗岩,随着岩浆的演化.岩浆结晶期后分异出的热液流体向富Cl和Sn方向演化.芙蓉锡矿田的成矿流体应主要来源于黑云母花岗岩岩浆结晶期后分异出的岩浆热液.     

氨基氰在高温高压水流体中反应化学的实验研究

氨基氰在水热环境,尤其在超临界水中的反应化学实验结果表明,氨基氰可以通过自聚合作用,生成较高分子量的氮杂环混合物,进而水解并最终转化成ＣＯ２和ＮＨ３。实验还证明,超临界水可以有效地破坏那睦含有危险的或剧毒的有机资料,使之转化成无毒无在的Ｈ２Ｏ,ＣＯ２,ＮＨ３和无机盐等,根据实验结果,提出水解反应的可能机制是水的亲核加合。