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.     

新疆东天山十里坡自然铜矿化区马头滩组玄武岩锆石LA-ICPMS U-Pb年龄及其意义

新疆北部东天山十里坡地区近年来新发现了与玄武岩有关的自然铜矿化这一新类型。自然铜的赋矿地层-马头滩组中的赋矿玄武岩锆石 LA-ICPMS 年龄为307±4Ma,对应于晚石炭世,显示该套赋矿地层属于上石炭统。从该区自然铜赋矿火山岩所限定的时间看,成矿背景应属于后碰撞环境。东天山十里坡地区自然铜矿化的构造背景、成矿系统和矿化类型与峨眉山玄武岩自然铜矿化和美国基威诺铜矿床均存在差异,自然铜矿化的成因可能也存在差异。     

Pressure dependence of hydrogen bonding in metal deuteroxides: a neutron powder diffraction study of Mn(OD)2 and β-Co(OD)2.

The structures of deuterated pyrochroite, Mn(OD)₂ and β−Cο(OD)₂ have been refined using the Rietveld method and neutron powder diffraction data collected in an opposed-anvil high pressure (Paris-Edinburgh) cell from room pressure to 9 GPa. The equation of state for Mn(OD)₂ was determined (K=41(3) GPa for fixed K′=4.7) and found to be consistent with previous studies of the isostructural brucite, Mg(OD)₂. The compressibility of β−Cο(OD)₂ on the other hand is apparently anomalous. The c-axis initially decreases at 3 times the rate of decrease of the a-axis; the ratio decreases to about 1.5 at an estimated 6 GPa before increasing again beyond this pressure. There is no obvious corresponding anomaly in the details of the atomic structure. In both materials there is an increase in the D-site disorder with pressure. A split-site model for the D-positions best fits the data at pressures above 8 GPa. There is no statistically significant increase in the O-D interatomic distance at increased pressure while the hydrogen bonding interaction D...O appears to increase as this distance decreases and the O-D...O angle increases. The intramolecular O-D bond valences, determined indirectly from the intermolecular D...O distances, decrease steadily for both materials as pressure is increased. Received: 31 October 1996 / Revised, accepted: 27 February 1997     

Photometric survey of binary near-Earth asteroids

Photometric data on 17 binary near-Earth asteroids (15 of them are certain detections, two are probables) were analysed and characteristic properties of the near-Earth asteroid (NEA) binary population were inferred. We have found that binary systems with a secondary-to-primary mean diameter ratio Ds/Dp?0.18 concentrate among NEAs smaller than 2 km in diameter; the abundance of such binaries decreases significantly among larger NEAs. Secondaries show an upper size limit of Ds=0.5-1 km. Systems with Ds/Dp?0.5 are abundant but larger satellites are significantly less common. Primaries have spheroidal shapes and they rotate rapidly, with periods concentrating between 2.2 to 2.8 h and with a tail of the distribution up to ∼4 h. The fast rotators are close to the critical spin for rubble piles with bulk densities about 2 g/cm³. Orbital periods show an apparent cut-off at Porb∼11 h; closer systems with shorter orbital periods have not been discovered, which is consistent with the Roche limit for strengthless bodies. Secondaries are more elongated on average than primaries. Most, but not all, of their rotations appear to be synchronized with the orbital motion; nonsynchronous secondary rotations may occur especially among wider systems with Porb>20 h. The specific total angular momentum of most of the binary systems is similar to within ±20% and close to the angular momentum of a sphere with the same total mass and density, rotating at the disruption limit; this suggests that the binaries were created by mechanism(s) related to rotation near the critical limit and that they neither gained nor lost significant amounts of angular momentum during or since formation. A comparison with six small asynchronous binaries detected in the main belt of asteroids suggests that the population extends beyond the region of terrestrial planets, but with characteristics shifted to larger sizes and longer periods. The estimated mean proportion of binaries with Ds/Dp?0.18 among NEAs larger than 0.3 km is 15±4%. Among fastest rotating NEAs larger than 0.3 km with periods between 2.2 and 2.8 h, the mean proportion of such binaries is (66⁺¹⁰₋₁₂)%.     

Geochemical evidence (C,N and Pb isotopes) of recent anthropogenic impact in south‐central Chile from two environmentally distinct lake sediment records

In this paper, we compare the elemental and isotopic (C, N, Pb) geochemistry of lake sediments from two contrasted environments in south‐central Chile. The first lake, Laguna Chica de San Pedro (LCSP), is situated in the urbanised area of the Biobio Region (36°S). The second lake, Lago Puyehue (40° S), is located 400 km to the southeast of LCSP and within an Andean national park. Our aim is to identify environmental impacts associated with increasing industrial activities and land degradation during the last 150 a. In LCSP, shifts in C/N atomic ratios, δ¹³C and δ¹⁵N from 1915–1937 to the late 1980s are attributed to successive land degradation episodes in the lake watershed. Based on a Pb isotopic mixing model, we estimate that up to 20% of lead in LCSP sediments is supplied from urban atmospheric pollution. By contrast, human impact in the watershed of Lago Puyehue is very limited. We observe no change in organic geochemistry during the last 150 a and lead contamination remains lower than 5%, even during the last decades. Although contamination levels are much higher in LCSP than in Lago Puyehue, a peak in anthropogenic Pb is recorded during the same period (1974–1976) at both sites. This maximum contamination level is consistent with increased industrial activity in the vicinity of Concepción. Copyright © 2010 John Wiley & Sons, Ltd.     

Characterization of Galena and Vein Paragenesis in the Penjom Gold Mine, Malaysia: Trace Elements, Lead Isotope Study and Relationship to Gold Mineralization Episodes

The Penjom Gold Mine is located 30 km from the Bentong-Raub Suture at the western boundary of the Central Belt in Peninsular Malaysia. Gold mineralization hosted within the vein system is associated with pyrite, arsenopyrite, and minor base metals including galena. Trace element and lead isotope analysis was undertaken on nine samples that represent two stages of galena formed during two tectonic events. Both the Pb isotopes and the trace elements show that the first stage galena within the mineralized areas at the footwall has different geochemical characteristics compared with galena in non mineralized areas in the hanging wall, suggesting that galena crystallized from two different ore fluids and probably at two different times. Higher Te, Se and Bi in the galena from the mineralized area may indicate hydrothermal fluids that migrate through the structural conduit and leached out the metal along the pathway that consist of dominant carbonaceous unit. The Pb isotopic ratio composition are transitional between the bulk crustal growth and an upper crustal growth curve, indicating that derivation was from arc rocks associated with continental crust or a crustal source that includes arc volcanic and old continental sedimentary rocks.     

High resolution simulation of the South Asian monsoon using a variable resolution global climate model

This study examines the feasibility of using a variable resolution global general circulation model (GCM), with telescopic zooming and enhanced resolution (~35 km) over South Asia, to better understand regional aspects of the South Asian monsoon rainfall distribution and the interactions between monsoon circulation and precipitation. For this purpose, two sets of ten member realizations are produced with and without zooming using the LMDZ (Laboratoire Meteorologie Dynamique and Z stands for zoom) GCM. The simulations without zoom correspond to a uniform 1° × 1° grid with the same total number of grid points as in the zoom version. So the grid of the zoomed simulations is finer inside the region of interest but coarser outside. The use of these finer and coarser resolution ensemble members allows us to examine the impact of resolution on the overall quality of the simulated regional monsoon fields. It is found that the monsoon simulation with high-resolution zooming greatly improves the representation of the southwesterly monsoon flow and the heavy precipitation along the narrow orography of the Western Ghats, the northeastern mountain slopes and northern Bay of Bengal (BOB). A realistic Monsoon Trough (MT) is also noticed in the zoomed simulation, together with remarkable improvements in representing the associated precipitation and circulation features, as well as the large-scale organization of meso-scale convective systems over the MT region. Additionally, a more reasonable simulation of the monsoon synoptic disturbances (lows and disturbances) along the MT is noted in the high-resolution zoomed simulation. On the other hand, the no-zoom version has limitations in capturing the depressions and their movement, so that the MT zone is relatively dry in this case. Overall, the results from this work demonstrate the usefulness of the high-resolution variable resolution LMDZ model in realistically capturing the interactions among the monsoon large-scale dynamics, the synoptic systems and the meso-scale convective systems, which are essential elements of the South Asian monsoon system.     

The Helioseismic and Magnetic Imager (HMI) Vector Magnetic Field Pipeline: Overview and Performance

The Helioseismic and Magnetic Imager (HMI) began near-continuous full-disk solar measurements on 1 May 2010 from the Solar Dynamics Observatory (SDO). An automated processing pipeline keeps pace with observations to produce observable quantities, including the photospheric vector magnetic field, from sequences of filtergrams. The basic vector-field frame list cadence is 135 seconds, but to reduce noise the filtergrams are combined to derive data products every 720 seconds. The primary 720 s observables were released in mid-2010, including Stokes polarization parameters measured at six wavelengths, as well as intensity, Doppler velocity, and the line-of-sight magnetic field. More advanced products, including the full vector magnetic field, are now available. Automatically identified HMI Active Region Patches (HARPs) track the location and shape of magnetic regions throughout their lifetime. The vector field is computed using the Very Fast Inversion of the Stokes Vector (VFISV) code optimized for the HMI pipeline; the remaining 180^° azimuth ambiguity is resolved with the Minimum Energy (ME0) code. The Milne–Eddington inversion is performed on all full-disk HMI observations. The disambiguation, until recently run only on HARP regions, is now implemented for the full disk. Vector and scalar quantities in the patches are used to derive active region indices potentially useful for forecasting; the data maps and indices are collected in the SHARP data series, hmi.sharp_720s. Definitive SHARP processing is completed only after the region rotates off the visible disk; quick-look products are produced in near real time. Patches are provided in both CCD and heliographic coordinates. HMI provides continuous coverage of the vector field, but has modest spatial, spectral, and temporal resolution. Coupled with limitations of the analysis and interpretation techniques, effects of the orbital velocity, and instrument performance, the resulting measurements have a certain dynamic range and sensitivity and are subject to systematic errors and uncertainties that are characterized in this report.     

The role of minor mergers in the recent star formation history of early-type galaxies

We demonstrate that the large scatter in the ultraviolet (UV) colours of intermediate-mass early-type galaxies in the local Universe and the inferred low-level recent star formation (RSF) in these objects can be reproduced by minor mergers in the standard Λ cold dark matter (ΛCDM) cosmology. Numerical simulations of mergers with mass ratios ≤1:4, with reasonable assumptions for the ages, metallicities and dust properties of the merger progenitors, produce good agreement with the observed UV colours of the early-type population, if the infalling satellites are assumed to have (cold) gas fractions ≥20 per cent. Early-types that satisfy  ( NUV − r ) ≲ 3.8  are likely to have experienced mergers with mass ratios between 1:4 and 1:6 within the last ∼1.5 Gyr, while those that satisfy  3.8 < ( NUV − r ) < 5.5  are consistent with either recent mergers with mass ratios ≤1:6 or mergers with higher mass ratios that occurred more than ∼1.5 Gyr in the past. We demonstrate that the early-type colour–magnitude relations and colour distributions, in both the UV and optical spectral ranges, are consistent with the expected frequency of minor merging activity in the standard ΛCDM cosmology at low redshift. We present a strong plausibility argument for minor mergers to be the principal mechanism behind the large UV scatter and associated low-level RSF observed in early-type galaxies in the nearby Universe.