MEASUREMENTS AND MODEL SIMULATIONS OF SURFACE OZONE VARIATIONS AT DIFFERENT BACKGROUND CONCENTRATIONS OF THE PRECURSORS

Ozone photochemical production and loss in very different environments at Waliguan baselinestation and Lin'an background station were simulated by using the measurement data and photo-chemical box model.The results show that net ozone photochemical production rate is negative,about 0.5 ppb/d,at Waliguan baseline sation,because of very low precursor concentrations.Butat Lin'an background station,the net photochemical ozone production is positive,about 2—3 ppb/h.which is very closed with the measurement at Lin'an.That means ozone production was con-trolled by photochemical reactions at Lin'an background station,because of the higher precursorconcentrations.The net destruction rate,at Waliguan Mt.,is not large,so that future increase inanthropogenic emission of reactive nitrogen will lead to larger production rates of steady-state O_3concentration.     

Processing of oxidised nitrogen compounds by passage through winter-time orographic cloud

Four case studies are described, from a three-site field experiment in October/November 1991 using the Great Dun Fell flow-through reactor hill cap cloud in rural Northern England. Measurements of total odd-nitrogen nitrogen oxides (NO _y ) made on either side of the hill, before and after the air flowed through the cloud, showed that 10 to 50% of the NO _y , called NO _z , was neither NO nor NO₂. This NO _z failed to exhibit a diurnal variation and was often higher after passage through cloud than before. No evidence of conversion of NO _z to NO₃ ^- in cloud was found. A simple box model of gas-phase chemistry in air before it reached the cloud, including scavenging of NO₃ and N₂O₅ by aerosol of surface area proportional to the NO₂ mixing ratio, shows that NO₃ and N₂O₅ may build up in the boundary layer by night only if stable stratification insulates the air from emissions of NO. This may explain the lack of evidence for N₂O₅ forming NO₃ ^- in cloud under well-mixed conditions in 1991, in contrast with observations under stably stratified conditions during previous experiments when evidence of N₂O₅ was found. Inside the cloud, some variations in the calculated total atmospheric loading of HNO₂ and the cloud liquid water content were related to each other. Also, indications of conversion of NO _x to NO _z were found. To explain these observations, scavenging of NO _x and HNO₂ by cloud droplets and/or aqueous-phase oxidation of NO₂ ^- by nitrate radicals are considered. When cloud acidity was being produced by aqueous-phase oxidation of NO _x or SO₂, NO₃ ^- which had entered the cloud as aerosol particles was liberated as HNO₃ vapour. When no aqueous-phase production of acidity was occurring, the reverse, conversion of scavenged HNO₃ to particulate NO₃ ^-, was observed.     

Two-dimensional modelling of some CFC replacement compounds

The Cambridge 2-D Eulerian model has been used to study the potential atmospheric distributions and lifetimes of a number of CFC replacement compounds and their degradation products. The study has focused on HFC 134a and HCFCs 123, 141b and 142b and the major products formed by their atmospheric degradation. The loss of these compounds and their products by hydroxyl radical attack, photolysis and in-cloud hydrolysis have been investigated. The study has shown that HCFCs 141b and 142b have sufficiently long lifetimes to enter the stratosphere in significant quantities, where degradation leads to an increase in the total stratospheric chlorine concentration. The study has also highlighted areas where further experimental work would be valuable, in particular characterisation of the product channels for the degradation reactions and determination of the removal rates of the products in the aqueous phase.     

Boundary-layer ozone depletion as seen in the Norwegian Arctic in spring

Several years of measurements of ozone, hydrocarbons, sulphate and meteorological parameters from Spitsbergen in the Norwegian Arctic are presented. Most of the measurements were taken on the Zeppelin Mountain at an altitude of 474 m a.s.l. The focus is the episodes of ozone depletion in the lower troposphere in spring, which are studied in a climatological way. Episodes of very low ozone concentrations are a common feature on the Zeppelin Mountain in spring. The low ozone episodes were observed from late March to the beginning of June. When the effect of transport direction was subtracted, the frequenty of the low ozone episodes was found to peak in the beginning of May, possibly reflecting the seasonal cycle in the actual depletion process. Analyses based on trajectory calculations show that most of the episodes occurred when the air masses were transported from W-N. Ozone soundings show that the ozone depletion may extend from the surface and up to 3–4 km altitude. The episodes were associated with a cold boundary layer beneath a thermally stable layer, suppressing mixing with the free troposphere. The concentration of several individual hydrocarbons was much lower during episodes of low ozone than for the average conditions. The change in concentration ratio between the hydrocarbons was in qualitative agreement with oxidation of hydrocarbons by Br and Cl atoms rather than by OH radicals.     

区域酸性沉降的数值研究 I. 模式

建立了一个三维时变的欧拉型区域酸性污染物沉降模式，模式包括源排放、平流输送、湍流扩散、干沉积、气相化学、液相化学及湿清除等六大部分。考虑到计算条件的承受能力和应用性的要求，在把握酸沉降形成的关键过程的前提下，合理地简化设计模式。相对于国内已有的工作，本模式在干沉积、气相化学、液相化学和湿清除等方面均有所改进。     

The late Quaternary development of three ancient tarns on southwestern Cumberland Peninsula, Baffin Island, Arctic Canada: paleolimnological evidence from diatoms and sediment chemistry

Sediment diatom and chemical analyses of cores from three poorly buffered extra-glacial lakes on the northeastern margin of the Canadian Shield (Cumberland Peninsula, Baffin Island) record interactions between aquatic and terrestrial spheres that were influenced by late Quaternary climatic conditions. Although differences exist between each of the lakes, notably with regards to the intensity of pre-Holocene catchment erosion and the timing of the onset of organic sedimentation, an underlying pattern of lake ontogeny, common to all three lakes, is identified. Although intensified watershed erosion characterized the Late Wisconsinan and Neoglacial cold periods, the lakes nonetheless remained viable ecosystems at these times. Sudden catchment stabilization during the late-glacial to earliest Holocene is associated with incipient organic sedimentation. Lake-water pH increased at this time, likely in response both longer base cation residence times as lake flushing rates decreased, and enhanced alkalinity production from sediment biogeochemical reactions. Subsequently, as the catchments remained stable during the productive early Holocene (c.9–7 ka BP), then gradually received a renewed increase of minerogenic sedimentation, the breakdown of sources of lake alkalinity resulted in natural acidification. Burial of cation-rich mineral sediments and the loss of permanent sedimentary sinks for the products of microbial reduction likely impeded within-lake alkalinity production, and catchment-derived base cations appeared ineffective in curtailing pH declines. The general nature of the Holocene development of these lakes is similar to that observed elsewhere on crystalline terrains, following deglaciation. Our data therefore suggest that catchment glaciation is not a necessary precursor for models of lake development characterized by initial base cation enrichment and subsequent gradual acidification.     

对变质岩区加强岩石学研究的几点看法

文章对1:5万区调工作中变质岩区加强基础岩石学工作的以下3个方面提出了一些看法,1．岩石薄片的研究;2．矿物化学和地质温压计;3．变质岩的岩石组合和构造环境。     

Crystal chemistry of some Mg,Cr, V normal spinels from Sludyanka (Lake Baikal,Russia): the influence of V<Superscript>3+</Superscript> on structural stability

A suite of vanadian magnesiochromites from the Sludyanka metamorphic complex (South Lake Baikal, Russia) were investigated by means of X-ray single-crystal structural refinements and microprobe analyses. Various morphological types of Cr–V-bearing Mg spinels are located in calc–silicate metamorphic rocks, in an assemblage that also contains other Cr–V minerals such as escolaite–karelianite, uvarovite–goldmanite, Cr–V-bearing clinopyroxene, tourmaline, amphibole, mica, etc. Along the suite there is widespread V–Cr substitution (0.14 V³⁺ 0.95 afu, 1.02 Cr³⁺ 1.80 afu), and minor, variable Al contents. The Mg content of slightly lesser than 1 afu, is almost constant. Cell parameters and octahedral bond distances increase with V³⁺. Unexpectedly, the Mg–O tetrahedral bond distance also increases slowly with V³⁺. This weak dragging effect contributes towards maintaining distortion of the oxygen array with respect to the ideal CCP, thus providing a shielding effect, which reduces V³⁺–V³⁺ repulsion. This leads to the energetic stabilization of the structure, in spite of the increase of bond strain with increasing V³⁺ contents.     

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.