北京石花洞滴水沉积的季节变化及影响因素

Because of the high resolution, stalagmite laminae can play an important role in the paleoclimate reconstructions. However, few investigations for the formation mechanisms of stalagmite lamilae have been done. Based on two-year observation on calcite growth rate at the drip sites, three-year monitoring of hydrodynamics, physics and chemistry of drip waters at different drip sites and the surrounding environments inside and outside the Beijing Shihua Cave, the seasonal variations of calcite growth rate are revealed and the results can be concluded as follows: 1. The drip waters inside the Cave are mostly sourced from the summer rain, and its minimal response-time to the atmospheric precipitation is less than one day. There are three types of response relationships between the precipitation and the drip rate variations: rapid response type, time-lag response type and stable response type. For rapid response type, the drip discharge is recharged through the flow routes along intensive fractures and interconnectivities; for time-lag response type, the drip discharge is recharged by double-porosity system composed of a high conductivity, low storage capability conduit network and a low-conductivity high-storage capability rock matrix under variable boundary conditions; for stable response type, the drip discharge is mainly recharged by seepage flow and base flow. 2. The observation shows that, inside the Cave, the growth rate of calcite is generally lower in rainy seasons and higher in dry seasons. During the rainy seasons, the drip water is characterized by a lower pH value, higher [Ca2+], [Mg2+], [SO42-] and electrical conductivity (EC) values. According to the calculations of saturation index of calcite (SIc), pCO2 of the drip water, as well as the synthetical analysis of other possible factors, the calcite growth rate is found to be principally influenced by the drip water saturation index of calcite (SIc). And the drip rate and pCO2 in the drip water and in the cave air play the secondly important roles in this process. The recharge mode of heavy rainfall events in the rainy seasons should probably be the main driving force that controls the physicochemical properties and calcite sediment of the drip waters. The abrupt decrease of sedimentary rate and the sharp peak of DOC in drip water in the rainy season probably forms the thin opaque (luminescent under ultraviolet radiation) layers observed in the stalagmites, whereas the relatively higher sedimentary rate in the dry seasons may be responsible for the thicker bright layers. The investigation elucidated here preliminarily reveals the formation mechanism of the stalagmite laminae in Beijing Shihua Cave.

Coadsorption of nitric oxide and oxygen on the Ag(110) surface

The coadsorption of NO and O-2 on Ag(110) surface has been studied by X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS) and in situ Raman spectroscopy. The existence of oxygen enhances the adsorption of NO by forming the NOx species, that is, NO2 and NO3, and the NO in turn as a promotor facilitates the cleavage of the dioxygen bond, forming the surface atomic oxygen species having the same spectral characteristics as those produced using oxygen at high pressure. The oxygen species generated by the interaction is composed of two parts. One is produced directly by the decomposition of surface NO-O-2 complex at ca 625 K, which raised an O 1s feature at 530.5 eV and is absent at ca 800 K, while the another with an O 1s binding energy of 529.2 eV emerges at higher temperatures and shows similar properties as the reported gamma-state oxygen which bound tightly on restructured silver surface. The exposure to NO and O-2 causes noticeable changes in the morphology of the Ag(110) surface and the flat terraces superseded by small (ca 0.1 mu m) pits, and particles with typical diameters of a few micrometres were formed at elevated temperatures. (C) 1999 Elsevier Science B.V. All rights reserved.

Coke formation during the methanol conversion to olefins in zeolites studied by UV Raman spectroscopy

Coke formation on/in ZSM-5, USY and SAPO-34 zeolites was investigated during the methanol conversion to olefins at temperatures from 298 to 773 K using ultraviolet (UV) Raman spectroscopy. The fluorescence interference that usually obscures the Raman spectra of zeolites in the conventional Raman spectroscopy, particularly for coked catalysts, can be successfully avoided in the UV Raman spectroscopy. Raman spectra are almost the same for adsorbed methanol on the three zeolites at room temperature. However, the Raman spectra of the surface species formed at elevated temperatures are quite different for the three zeolites. Coke species formed in/on SAPO-34 are mainly polyolefinic species, and in/on ZSM-5 are some aromatic species, but polyaromatic or substituted aromatic species are predominant in USY at high temperatures. Most of the coke species can be removed after a treatment with O-2 at 773 K, while some small amount of coke species always remains in these zeolites, particularly for USY. The main reason for the different behavior of coke formation in the three zeolites could be attributed to the different pore structures of the zeolites. (C) 2000 Elsevier Science B.V. All rights reserved.

Identifying framework titanium in TS-1 zeolite by UV resonance Raman spectroscopy

Framework titanium in Ti-silicalite-1 (TS-1) zeolite was selectively identified by its resonance Raman bands using ultraviolet (W) Raman spectroscopy. Raman spectra of the TS-1 and silicalite-1 zeolites were obtained and compared using continuous wave laser lines at 244, 325, and 488 nm as the excitation sources. It was only with the excitation at 244 nm that resonance enhanced Raman bands at 490, 530, and 1125 cm(-1) appeared exclusively for the TS-1 zeolite. Furthermore, these bands increased in intensity with the crystallization time of the TS-1 zeolite. The Raman bands at 490, 530, and 1125 cm(-1) are identified as the framework titanium species because they only appeared when the laser excites the charge-transfer transition of the framework titanium species in the TS-1. No resonance Raman enhancement was detected for the bands of silicalite-1 zeolite and for the band at 960 cm(-1) of TS-1 with any of the excitation sources ranging from the visible tb UV regions. This approach can be applicable for the identification of other transition metal ions substituted in the framework of a zeolite or any other molecular sieve.

Quantitative and qualitative analysis of flavonoids in leaves of Adinandra nitida by high performance liquid chromatography with UV and electrospray ionization tandem mass spectrometry detection

The extract of Adinandra nitida leaves, named as Shiyacha in China, was studied by high performance liquid chromatography (HPLC)-ultraviolet detection-electrospray ionisation (ESI) tandem mass spectrometry (MS). Under the optimized condition, the analysis could be finished in 45 min on a Hypersil C18 column combined with negative ion detection using information-dependent acquisition (IDA) mode of a Q TRAP (TM) instrument. Six flavonoids were identified as epicatechin, rhoifolin, apigenin, quercitrin, camellianin A, and camellianin B among which rhoifolin was for the first time found in Shiyacha. And the fragment pathways of these flavonoids were elucidated. Furthermore, with epicatechin, rhoifolin, and apigenin as markers, the quality control method for Shiyacha and its relevant product was firstly established. Calibration linearity was good (R-2 > 0.9992) over a three to four orders of magnitude concentration range with an S/N = 3 detection limit of 2.5 ng. (c) 2004 Elsevier B.V. All rights reserved.