Atmospheric Loss Processes of Dimethyl and Diethyl Carbonate

A combined study of the OH gas phase reaction and uptake on aqueous surfacesof two carbonates, dimethyl and diethyl carbonate has been carried out todetermine the atmospheric lifetimes of these compounds. Rate coefficients havebeen measured for gas phase reactions of OH radicals with dimethyl and diethylcarbonate. The experiments were carried out using pulsed laser photolysis– laser induced fluorescence over the temperature range 263–372K and the kinetic data were used to derive the following Arrhenius expressions(in units of cm³ molecule^–1 s^–1):for dimethyl carbonate, k₁ = (0.83±0.27)×10^–12 exp [–(247± 98)/T] and fordiethyl carbonate, k₂ = (0.46±0.15)×10^–12 exp [(503± 203)/T]. At 298 K, therate coefficients obtained (in units of 10^–12 cm³molecule^–1 s^–1) are: k₁ =(0.35± 0.04) and k₂ = (2.31± 0.29). The results arediscussed in terms of structure-activity relationships.The uptake coefficients of both carbonates on aqueous surfaces were measuredas a function of temperature and composition of the liquid phase, using thedroplet train technique coupled to a mass spectrometric detection. Dimethyland diethyl carbonate show very similar results. For both carbonates, themeasured uptake kinetics were found to be independent of the aqueous phasecomposition (pure water, NaOH solutions) but dependent on gas-liquid contacttime which characterises a surface saturation effect. The uptake coefficientvalues show a slight negative temperature dependence for both carbonates.These values vary from 1.4×10^–2 to0.6×10^–2 in the temperature range of 265–279 Kfor dimethyl carbonate, from 2.4×10^–2 to0.9×10^–2 in the temperature range of 270–279 Kfor diethyl carbonate. From the kinetic data, the following Henry's lawconstants were derived between 279 and 265 K: dimethyl carbonate,H₁ = 20–106 M atm^–1; and diethyl carbonate,H₂ = 30–98 M atm^–1. The reported data showthat the OH reaction is the major atmospheric loss process of these twocarbonates with lifetimes of 33 and 5 days, respectively, while the wetdeposition is a negligible process.     

150年来大气甲烷浓度的长期变化

应用作者建立的全球二维大气化学模式 ,采用 2种CH4 排放源的长期增长方案 ,同时考虑了CH4 排放源以及对OH自由基浓度有重要影响的CO和NOx 排放源的长期变化 ,模拟了CH4 和OH从 1840～ 2 0 2 0年的长期变化趋势。考虑了世界人口增长的排放源方案可以更好地模拟CH4 的长期变化 ,模拟结果表明 ,工业革命前的大气CH4 浓度和年排放总量分别为 76 0× 10 -9(V/V)和 2 80× 10 9kg ,1991年大气CH4 的浓度和年排放总量分别为16 11.9× 10 -9(V/V)和 5 33 .9× 10 9kg ,对流层OH自由基数浓度从 1840年的 7.17× 10 5分子数 /cm3 下降到 1991年的 5 .79× 10 5分子数 /cm3,降低了 19%。工业革命以来大气CH4 的增长一方面是由于CH4 排放源的增长 ,另一方面是由于大气OH浓度的下降。     

Boron isotopic fractionation in laboratory inorganic carbonate precipitation: Evidence for the incorpora-tion of B(OH)_3 into carbonate

A laboratory inorganic carbonate precipitation experiment at high pH of 8.96 to 9.34 was conducted, and the boron isotopic fractionations of the precipitated carbonate were measured. The data show that boron isotopic fractionation factors (αcarb-3) between carbonate and B(OH)3 in seawater range 0.937 and 0.965, with an average value of 0.953. Our results together with those reported by Sanyal and collabo-rators show that the αcarb-3 values between carbonate and B(OH)3 in solution are not constant but are negatively correlated with the pH of seawater. The measured boron isotopic compositions of carbonate precipitation (δ11Bcarb) do not exactly lie on the best-fit theoretical δ 11B4-pH curves and neither do they exactly parallel any theoretical δ 11B4-pH curves. Therefore, it is reasonable to argue that a changeable proportion of B(OH)3 with pH of seawater should also be incorporated into carbonate except for the dominant incorporation of B(OH)4- in carbonate . Hence, in the reconstruction of the paleo-pH of sea-water from boron isotopes in marine biogenic carbonates, the use of theoretical boron isotopic frac-tionation factor (α4-3) between B(OH)4- and B(OH)3 is not suitable. Instead, an empirical equation should be established.     

Oh Megamasers: Circumnuclear Gas in Starbursts

OH megamaser emission is known to be associated with the most central 100 parsecs of ultra-luminous infrared galaxies (ULIRGs). The masers are probing dense concentrations of gas, which presumably have accumulated during the merger event forming the ULIRG. Here we summarize the results from primarily high resolution observations of the 18 cm OH lines in a few OH megamaser galaxies. The maser emission is commonly distributed in disks or tori, but there is also some evidence for other components such as outflows. The appearance of the observed emission strongly depends on the observing resolution, and new theoretical modeling has made important steps toward understanding the observed emission. The radio continuum in OH megamaser galaxies is generally starburst related, and detailed studies of the continuum could perhaps be used to date the merger.     

The association of OH and methanol masers in W3(OH)

We present single-baseline Multi-Element Radio-Linked Interferometer Network (MERLIN) measurements of excited OH 6.0-GHz masers and methanol 6.7-GHz masers for the source W3(OH). These allow us to compare the positions of individual maser spots of these two species to ∼15 mas accuracy for the first time, and to compare these with previously published positions of ground-state OH masers near 1.7 GHz and excited-state OH masers near 4.7 GHz. There is a strong association between OH 6035-MHz and 1665-MHz masers. OH and methanol have very similar distributions, but associations of individual masers are relatively rare: most methanol 6.7-GHz masers are within 100 mas of OH 6.0-GHz masers, but only four methanol masers are within 15 mas of an OH 6.0-GHz maser. There are no correspondences of either species with excited OH 4.7-GHz masers. Zeeman splitting of the 6.0-GHz OH lines indicates an ordered magnetic field ranging from 3.2 to 14.4 mG. The magnetic fields estimated from co-propagating masers such as 6035 and 1665 MHz are generally in good agreement with each other.     

Using nicmos arrays to study galaxies

The 256×256 HgCdTe arrays developed for the NICMOS (Near-Infrared Camera and Multi-object Spectrometer) project have proven to be very capable devices for extragalactic imaging. This paper describes a sampling of extragalactic results from NICMOS arrays. A brief summary of the history of the development of these arrays, and their outstanding performance characteristics is also given.     

Extragalactic sources with asymmetric radio structure

We present total-intensity and linear-polarization observations with the Very Large Array (VLA) at λ6 and 2 cm of 17 sources, almost all of which were suspected to have extended emission only on one side of the nucleus. Five of them are still one-sided, three appear unresolved, while seven have radio lobes on both sides of the nucleus. The outer components in the double-lobed sources, however, have significantly different surface brightness or are very asymmetrically located with respect to the nucleus.     

针铁矿及其前体吸附亚砷酸根离子的反应及预处理方法的影响

观察了针铁矿及其前体对溶液中亚砷酸根离子的吸附过程和吸附性能。3种吸附剂分别为氢氧化铁凝胶、经微波真空干燥的凝胶和80℃烘干的凝胶,它们均转变成了针铁矿。氢氧化铁凝胶与亚砷酸钠溶液混和后,溶液的pH值在6min内从9.71上升到10.36,原因是亚砷酸根离子置换了针铁矿和氢氧化铁中的氢氧根;40min后开始持续下降,和亚砷酸根离子与吸附剂之间的缩合反应有关。pH值的转折点并不意味着吸附反应的结束,但代表了反应类型的转变。这两种类型的反应受温度和气体溶解组分的影响不大。吸附剂经超声波处理后,改善了其在介质中的分散性,吸附效率因此普遍提高,但也造成了固体微粒难以分离的问题。经真空微波处理的凝胶对砷阴离子的吸附率优于另外两种吸附剂,去除率分别提高了53.18%和17.22%。其主要原因可能是凝胶中的水分子在微波辐射场作用下的高频振动,使其内部在干燥脱水过程中保持了较高的孔隙度;此外,吸附剂的表面活性在微波处理过程中亦有可能得到了改善。     

OH-bearing planar defects in olivine produced by the breakdown of Ti-rich humite minerals from Dabie Shan (China)

The partial breakdown of Ti-chondrodite and Ti-clinohumite during exhumation from ultra-high pressure to amphibolite facies conditions in garnet-pyroxenites from Dabie Shan (China) produces coronas of olivine coexisting with ilmenite blebs. Fourier transform infrared (FTIR) spectra of this newly formed olivine exhibit absorption bands in the hydroxyl-stretching region. Two intense peaks were observed at 3,564 and 3,394 cm⁻¹, identical in energy to peaks in Ti-clinohumite. Transmission electron microscopy (TEM) of the same olivine domains revealed the presence of a complex (001) planar intergrowth. These interlayers have a 1.35 nm repeat distance, which is characteristic of clinohumite. Such interlayers are also enriched in Ti with respect to the adjacent olivine as shown by energy dispersive spectrometry. The combined evidence from FTIR spectroscopy and TEM indicates that OH is incorporated along Ti-clinohumite planar defects. This study provides evidence that the nominally anhydrous phase olivine may contain OH as a humite-type defect beyond the breakdown of the hydrous humite minerals and confirms earlier suggestions that Ti plays a key role in OH incorporation in mantle olivine. We suggest that olivine containing Ti-clinohumite defects is an important phase for water transport in subduction zones and for the storage of water in cold subcontinental mantle. However, these defects are unlikely to be stable in hotter parts of the oceanic mantle such as where basaltic magmas are generated.     

Hierarchical dark matter from fragmenting macroscopic superstrings

Dark matter is explained within our scenario of the formation of the universe from the decay of macroscopic superstrings. The observed increase of the fraction of dark matter with the hierarchical rank of astronomical objects is explained by assuming that about 90% of superstrings of each rank decay into unbound fragments. The dark matter consists essentially of asteroids and smaller objects which are not bound to stars.