Numerical study on the impacts of heterogeneous reactions on ozone formation in the Beijing urban area

The air quality model CMAQ-MADRID （Community Multiscale Air Quality-Model of Aerosol Dynamics, Reaction, Ionization and Dissolution） was employed to simulate summer O3 formation in Beijing China, in order to explore the impacts of four heterogeneous reactions on O3 formation in an urban area. The results showed that the impacts were obvious and exhibited the characteristics of a typical response of a VOC-limited regime in the urban area. For the four heterogeneous reactions considered, the NO2 and HO2 heterogeneous reactions have the most severe impacts on O3 formation. During the O3 formation period, the NO2 heterogeneous reaction increased new radical creation by 30%, raising the atmospheric activity as more NO→NO2 conversion occurred, thus causing the O3 to rise. The increase of O3 peak concentration reached a maximum value of 67 ppb in the urban area. In the morning hours, high NO titration reduced the effect of the photolysis of HONO, which was produced heterogeneously at night in the surface layer. The NO2 heterogeneous reaction in the daytime is likely one of the major reasons causing the O3 increase in the Beijing urban area. The HO2 heterogeneous reaction accelerated radical termination, resulting in a decrease of the radical concentration by 44% at the most. O3 peak concentration decreased by a maximum amount of 24 ppb in the urban area. The simulation results were improved when the heterogeneous reactions were included, with the O3 and HONO model results close to the observations.     

大别山双河长英质片麻岩在1.0～4.5GPa下的结晶实验及其地质意义

在７５０～１２００℃、１．０～４．５ＧＰａ条件下对取自于大别山双河的长英质片麻岩进行了重结晶实验。在７５０℃时,随压力增加矿物生成顺序为：角闪石在１．７５ＧＰａ时出现,２．５ＧＰａ时消失;黑云母在１．７５ＧＰａ时通过水化反应生成多硅白云母;绿帘石可以稳定到＞３．５ＧＰａ,在４ＧＰａ时转变成硬柱石;石榴石和绿辉石在１．５ＧＰａ时开始出现,而斜长石在１．７５ＧＰａ时消失;石英在３ＧＰａ时转变为柯石英。这表明角闪岩相与榴辉岩相的转变发生在１．５～１．７５ＧＰａ,并且,榴辉岩相可进一步划分出角闪榴辉岩相、柯石英榴辉岩相和硬柱石榴辉岩相等,它们分别指示不同的压力区间。多硅白云母是长英质岩石在高压－超高压条件下的主要共生矿物,其水化反应特性及结构水的保存致使陆壳在深俯冲过程中未发生明显的脱水作用,这是大别山碰撞带未能形成钙碱性岩浆弧的主要原因。     

Variation in mantle lithology and composition beneath the Ngao Bilta volcano,Adamawa Massif,Cameroon volcanic line,West-central Africa

Mantle peridotites entrained as xenoliths in the lavas of Ngao Bilta in the eastern branch of the continental Cameroon Line were examined to constrain mantle processes and the origin and nature of melts that have modified the upper mantle beneath the Cameroon Line.The xenoliths consist mainly of lherzolite with subordinate harzburgite and dunite.They commonly contain olivine,orthopyroxene,clinopyroxene and spinel although the dunite is spinel-free.Amphibole is an essential constituent in the lherzolites.Mineral chemistry differs between the three types of peridotite:olivines have usual mantle-like Mg#of around 90 in lherzolites,but follow a trend of decreasing Mg#(to 82)and NiO(to 0.06 wt.%)that is continuous in the dunites.Lherzolites also contain orthopyroxenes and/or clinopyroxenes with low-Mg#,indicating a reaction that removes Opx and introduces Cpx,olivine,amphibole and spinel.This is attributed to reaction with a silica-undersaturated silicate melt such as nephelinite or basanite,which originated as a low-degree melt from a depleted source as indicated by low Al2O3 and Na2O in Cpx and high Na2O/K2O in amphibole.Thermobarometric estimates place the xenoliths at pressures of 11–15 kbar(35–50 km)and temperatures of 863–957
C,along a dynamic rift geotherm and shallower than the region where carbonate melts may occur.The melt/rock reactions exhibited by the Ngao Bilta xenoliths are consistent with their peripheral position in the eastern branch of the Cameroon Volcanic Line in an area of thinned crust and lithosphere beneath the Adamawa Uplift.     

Petrographic and geochemical characterization of seep carbonate from Bush Hill (GC 185) gas vent and hydrate site of the Gulf of Mexico

Authigenic carbonates are common at cold seep sites as a result of microbial oxidation of hydrocarbons. Seep carbonate samples were collected from the surface of the Bush Hill (Green Canyon Block 185, Gulf of Mexico), a mound containing gas hydrate. The carbonates consisted of oily, porous limestone slabs and blocks containing bioclasts and matrix. Analysis by X-ray diffraction shows that aragonite is the dominant mineral (89–99 wt% with an average of 94 wt%) in the matrix of seep carbonate. This cement occurs in microcrystalline, microspar, and sparite forms. The moderate ¹³C depletion of the seep carbonate (the most depleted one has δ¹³C value of −29.4‰, and 26 of 38 subsamples have δ¹³C values >−20.0‰) indicates that the non-methane hydrocarbons was incorporated during seep carbonate precipitation. Relative enrichment of ¹⁸O may be related to localized destabilization of gas hydrate or derived from ¹⁸O-enriched pore water originated from smectite–illite transition in the deep sediments. The total content of rare earth elements (REE) of the 5% HNO₃-treated solution of the carbonates is from 0.40 ppm to 30.9 ppm. The shale-normalized REE patterns show varied Ce anomalies from significantly negative, slightly negative, and no to positive Ce anomalies. Variable content of trace elements, total REE, and Ce anomalies in different samples and even in the different carbonate mineral forms (microcrystalline, microspar and sparite) of the same sample suggest that the formation condition of the Bush Hill seep carbonate is variable and complex, which is possibly controlled by the rate of fluid flux.     

The effect of the 19F(α, p)22Ne reaction rate uncertainty on the yield of fluorine from Wolf–Rayet stars

In the light of recent recalculations of the  ¹⁹F(α, p)²²Ne  reaction rate, we present results of the expected yield of ¹⁹F from Wolf–Rayet (WR) stars. In addition to using the recommended rate, we have computed models using the upper and lower limits for the rate, and hence we constrain the uncertainty in the yield with respect to this reaction. We find a yield of  3.1 × 10⁻⁴ M_⊙  of ¹⁹F with our recommended rate, and a difference of a factor of 2 between the yields computed with the upper and lower limits. In comparison with previous work we find a difference in the yield of a factor of approximately 4, connected with a different choice of mass loss. Model uncertainties must be carefully evaluated in order to obtain a reliable estimate of the yield, together with its uncertainties, of fluorine from WR stars.     

Iron oxide precipitate in seepage of groundwater from a landslide slip zone

Orange precipitate was collected at the mouth of groundwater drainage tubes from the Kumanashi Landslide slip zone in Toyama prefecture, Northwest Japan. Data from XRF, X-ray diffraction, and Mössbauer spectroscopy determined the precipitate as hydrous ferric oxide (HFO) bearing multi-elements such as phosphorous, silica, calcium, etc. The occurrence of HFO may indicate an oxidation of ferrous iron in the percolated groundwater from the slip zone. Moreover, the precipitate iron should be mobilized with groundwater circulation from the slip zone, whose reducing condition was determined by the iron speciation on the same type of landslide profiles within the study area in previous studies. The HFO precipitate may be considered as a secondary reliable indicator to locate the seepage of a slip zone on surface, especially for a landslide newly investigated under wet-warm climate.     

Transition from confined to phreatic conditions as the factor controlling salinization and change in redox state, Upper subaquifer of the Judea Group, Israel

An increase in salinity and change from oxic to anoxic conditions are observed in the Upper subaquifer of the Judea Group in the Kefar Uriyya pumping field at the western foothills of the Judea Mountains, Israel. Hydrogeological data indicate that the change, which occurs over a distance of only a few kilometers, coincides with a transition from confined to phreatic conditions in the aquifer. The deterioration in the water quality is explained as a result of seepage of more saline, organic-rich water from above, into the phreatic "roofed" part of the aquifer. The latter is derived from the bituminous chalky rocks of the Mount Scopus Group, which confine the aquifer in its southeastern part. In this confined part, water in perched horizons within the Mount Scopus Group cannot leak down and flow westward while leaching organic matter and accumulating salts. However, upon reaching the transition area from confined to phreatic conditions, seepage to the Judea Upper subaquifer is possible, thereby allowing it to be defined as a leaky aquifer. The incoming organic matter consumes the dissolved oxygen and allows bacterial sulfate reduction. The latter accounts for the H₂S in the aquifer, as indicated by sulfur isotopic analyses of coexisting sulfate and sulfide. Thus, from an aquifer management point of view, in order to maintain the high quality of the water in the confined southeastern part of the Kefar Uriyya field, care should be taken not to draw the confined-roofed transition area further east by over pumping. Electronic Publication     

Time of explosive decay of a daemon-containing nucleus

We start from the hypothesis that the dark matter of the Galactic disc contains Planckian particles carrying a negative electric charge of up to Z =10, which we call dark electric matter objects (daemons). Daemons are capable of catalysing proton-fusion reactions, which may account for the observed solar neutrino deficiency. The inevitable poisoning of the catalytic property of daemons as they capture heavy nuclei ( A 20) in the interior of the Sun is used to estimate the decay time of a daemon-containing nucleus (nucleon) in quantum-relativistic processes, which remain largely unknown. This time is τ _ex∼10⁻⁷ s. This may mean that the lower limit on the mass of an intranucleonic particle interacting with a daemon is ∼10⁸–10¹⁰ GeV and, possibly, even ∼10¹⁴–10¹⁵ GeV. The desirability of a search for multiple events occurring with an interval ∼ τ _ex along the 'slow' daemon trajectories on operating installations dedicated to detection of the proton decay is pointed out.     

Reaction‐induced nucleation and growth v. grain coarsening in contact metamorphic,impure carbonates

The understanding of the evolution of microstructures in a metamorphic rock requires insights into the nucleation and growth history of individual grains, as well as the coarsening processes of the entire aggregate. These two processes are compared in impure carbonates from the contact metamorphic aureole of the Adamello pluton (N‐Italy). As a function of increasing distance from the pluton contact, the investigated samples have peak metamorphic temperatures ranging from the stability field of diopside/tremolite down to diagenetic conditions. All samples consist of calcite as the dominant matrix phase, but additionally contain variable amounts of other minerals, the so‐called second phases. These second phases are mostly silicate minerals and can be described in a KCMASHC system (K₂O, CaO, MgO, Al₂O₃, SiO₂, H₂O, CO₂), but with variable K/Mg ratios. The modelled and observed metamorphic evolution of these samples are combined with the quantification of the microstructures, i.e. mean grain sizes and crystal size distributions. Growth of the matrix phase and second phases strongly depends on each other owing to coupled grain coarsening. The matrix phase is controlled by the interparticle distances between the second phases, while the second phases need the matrix grain boundary network for mass transfer processes during both grain coarsening and mineral reactions. Interestingly, similar final mean grain sizes of primary second phase and second phases newly formed by nucleation are observed, although the latter formed later but at higher temperatures. Moreover, different kinetic processes, attributed to different driving forces for growth of the newly nucleated grains in comparison with coarsening processes of the pre‐existing phases, must have been involved. Chemically induced driving forces of grain growth during reactions are orders of magnitudes larger compared to surface energy, allowing new reaction products subjected to fast growth rates to attain similar grain sizes as phases which underwent long‐term grain coarsening. In contrast, observed variations in grain size of the same mineral in samples with a similar T–t history indicate that transport properties depend not only on the growth and coarsening kinetics of the second phases but also on the microstructure of the dominant matrix phase during coupled grain coarsening. Resulting microstructural phenomena such as overgrowth and therefore preservation of former stable minerals by the matrix phase may provide new constraints on the temporal variation of microstructures and provide a unique source for the interpretation of the evolution of metamorphic microstructures.     

Organic matter accumulation,redox, and diagenetic history of the Marcellus Formation,southwestern Pennsylvania,Appalachian basin

Variations in the concentration of redox sensitive elements combined with pyrite framboid size data documented from a Marcellus Formation (Middle Devonian) core recovered from southwestern Pennsylvania elucidate the redox, organic matter accumulation, and diagenetic history of these deposits in this region of the basin. Uranium and Mo enrichment and Fe/Al display sharp increases coincident with diminishing Th/U upward through the initial 3rd order trangressive systems tract (lower Union Springs Member). These data as well as abundant small (<6 μm) pyrite framboids record establishment of strongly reducing benthic conditions, perhaps related to the expansion of an oxygen minimum zone induced by increased surface productivity. Strongly anoxic, even euxinic, conditions were interrupted by episodes of dysoxia, perhaps seasonal or longer term. Overlying regressive systems tract (RST) deposits record modestly improved redox conditions, likely a reflection of a receding oxygen minimum zone as base level dropped. A subsequent 3rd order base level rise and renewed expansion of the oxygen minimum zone triggered by increased surface productivity resulted in the accumulation of the organic-rich lower Oatka Creek Member. Still, the mix of abundant small and subordinate large (>10 μm) framboids preserves the record of oxygen deficient to sulfidic bottom conditions frequently interrupted by episodes of (dys)oxia. Improving redox conditions through the overlying RST were accompanied by a two-fold increase in Al and consequent dilution of the organic matter flux and authigenic trace metal uptake at the sediment–water interface. The upper half of the Oatka Creek comprises a depositional sequence not obvious from core inspection or gamma-ray signature but revealed by Mo enrichment and Al concentration profiles. Diagenetic modification of the Marcellus includes several horizons of authigenic calcium carbonate concretions and marked Ba enrichment. Both features reflect the effects of non-steady state microbial diagenesis within a methane-rich sedimentary column.