泥河湾盆地磁性地层学研究——以东谷索和岑家湾剖面为例

The Nihewan Basin is a key area for research into human occupation at high northern latitudes in northeast Asia after the initial expansion of early humans out of Africa. Well-developed late Cenozoic lacustrine deposit sequence in this basin offers a unique opportunity to address this issue. In this thesis, detailed magnetostratigraphic investigation coupled with mineral magnetism was conducted on the Donggutuo and Cenjiawan sections in the eastern basin, where lacustrine deposits sequences containing the Donggutuo, Maliang and Cenjiawan Paleolithic sites are well developed. The sequences are mainly composed of grayish-white clays, grayish-green clayey silts, grayish-yellow silts and fine-grained brown sands, which have recorded reliable polarity variations of geomagnetic field.Characteristics of the anisotropy of magnetic susceptibility show that the sediments have preserved typical original magnetic fabric for sediments, indicating that the strata were developed in a low-energy lake environment and were never perturbed by tectonic stress since deposition. High-temperature magnetic susceptibility measurements (x-T) of representative specimens and demagnetization experiments indicate that the dominant magnetic mineral and remanent carrier at the two sections is magnetite. In addition, hematite and possibly minor maghemite exists in some portions of the sequences. The majority of the samples have relatively simple demagnetization behaviors. After removal of soft magnetic components, the stable characteristic remanent magnetizations (ChRMs) are isolated, which can represent the original remanences.The Donggutuo section mainly records the Brunhes chron, the Matuyama chron and the Jaramillo subchron. The Maliang stone artifact layer occurs just below the Brunhes/Matuyama boundary; and the Donggutuo artifact layer, just below the Jaramillo onset. Accordingly, the Maliang and Donggutuo sites can be dated at about 0.78 Ma and 1.1 Ma, respectively. The Cenjiawan section has recorded a portion of the Matuyama chron. After correlations with the magnetic polarity sequence of the Majuangou section adjacent to this section, the Cenjiawan stone artifact layer is determined below the Jaramillo onset, with an estimated age of 1.1 Ma.To establish the magnetic stratigraphy framework for the lacustrine sediments in the eastern Nihewan Basin, this thesis draws on the magnetic polarity sequences of the Donggutuo and Cenjiawan sections as well as previously obtained results from the Majuangou, Haojiatai, Xiaochangliang and Donggou sections for magnetostratigraphic correlations. The accumulation of the lacustrine sequences at the east margin of the basin commenced from about 2.0 Ma. These sequences record not only the coarse magnetostratigraphy of the Brunhes normal chron and the middle to late Matuyama reverse chron (that is, the Jaramillo and Olduvai subchrons) but also some of the fine structure (that is, the Kamikatsura, Santa Rosa, Punaruu and Cobb Mountain geomagnetic events). The development of the Nihewan paleolake experienced at least twice large expansion periods, split by a large-scale shrinking event in the middle period of the paleolake development. The accumulation of the lacustrine strata was controlled by fault activities.After temporal control for the Donggutuo, Maliang and Cenjiawan Paleolithic sites were established, the three sites along with other well-dated Paleolithic/hominin sites of the Early Pleistocene in North China were combined to construct a chronological sequence of early human occupation in northeastern Asia. Furthermore, after incorporation of paleoclimate changes retrieved from Chinese loess/paleosol sequences and marine sediments, it could be possibly proposed that human groups of the Early Pleistocene in North China might have survived repeated warm/humid interglacials and cold/dry glacials, which were paced by earth orbital variations of the Eastern paleomonsoon.

On-line concentration of proteins in pressurized capillary electrochromatography coupled with electrospray ionization-mass spectrometry

Pressurized capillary electrochromatography (pCEC) and electrospray ionization-mass spectrometry (ESI-MS) have been hyphenated for protein analysis. Taken cytochrome c, lysozyme, and insulin as samples, the limits of detection (LODs) for absolute concentrations are 10(-11) mol (signal-to-noise ratio S/N = 3) with relative standard deviations (RSDs) of retention time and peak area, respectively, of less than 1.7% and 4.8%. In order to improve the detection sensitivity, on-line concentration by field-enhanced sample-stacking effect and chromatographic zone-sharpening effect has been developed, and parameters affecting separation and detection, such as pH and electrolyte concentration in the mobile phase, separation voltage, as well as enrichment voltage and time, have been studied systematically. Under the optimized conditions, the LODs of the three proteins could be decreased up to 100-fold. In addition, the feasibility of such techniques has been further demonstrated by the analysis of modified insulins at a concentration of 20 mu g/mL.

Determination of urinary nucleosides by direct injection and coupled-column high-performance liquid chromatography

A coupled-column liquid chromatographic method for the direct analysis of 14 urinary nucleosides is described. Efficient on-line clean-up and concentration of 14 nucleosides from urine samples were obtained by using a boronic acid-substituted silica column (40 turn x 4.0 mm I.D.) as the first column (Col-1) and a Hypersil ODS2 column (250 mm x 4.6 mm I.D.) as the second column (Col-2). The mobile phases applied consisted of 0.25 mol/L ammonium acetate (pH 8.5) on Col-1, and of 25 mmol/L potassium dihydrogen phosphate (pH 4.5) on Col-2, respectively. Determination of urinary nucleosides was performed on Col-2 column by using a linear gradient elution comprising 25 mmol/L potassium dihydrogen phosphate (pH 4.5) and methanol-water (60:40, v/v) with UV detection at 260 nm. Urinary nucleosides analysis can be carried out by this procedure in 50 min requiring only pH adjustment and the protein precipitation by centrifugation of urine samples. Calibration plots of 14 standard nucleosides showed excellent linearity (r > 0.995) and the limits of detection were at micromolar levels. Both of intra- and inter-day precisions of the method were better than 6.6% for direct determination of 14 nucleosides. The validated method was applied to quantify 14 nucleosides in 20 normal urines to establish reference ranges. (c) 2005 Elsevier B.V. All rights reserved.

Quantitative determination of compounds in tobacco essential oils by comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry

A quantitative analysis of the individual compounds in tobacco essential oils is performed by comprehensive two-dimensional gas chromatography (GC x GC) combined with flame ionization detector (FID). A time-of-flight mass spectrometer (TOF/MS) was coupled to GC x GC for the identification of the resolved peaks. The response of a flame ionization detector to different compound classes was calibrated using multiple internal standards. In total, 172 compounds were identified with good match and 61 compounds with high probability value were reliably quantified. For comparative purposes, the essential oil sample was also quantified by one-dimensional gas chromatography-mass spectrometry (GC/MS) with multiple internal standards method. The results showed that there was close agreement between the two analysis methods when the peak purity and match quality in one-dimensional GC/MS are high enough. (c) 2005 Elsevier B.V. All rights reserved.

Interface of chip-based capillary electrophoresis-inductively coupled plasma-atomic emission spectrometry (CE-ICP-AES)

An interface of chip-based capillary electrophoresis (CE)-inductively coupled plasma-atomic emission spectrometry (ICP-AES) that is based on cross-flow nebulization has been developed. A polydimethylsiloxane (PDMS) CE-chip with conventional cross channel layout was used. A stainless steel tube was placed orthogonal to the exit of the CE separation channel for cross flow nebulization. A supplementary flow of buffer solution at the channel exit was used to improve nebulization efficiency. Two capillaries were inserted into the CE chip near the inlet of the separation channel for sample and buffer solution injection. Syringe pumps were used to manipulate the flow rate and flow direction of the sample, buffer, and supplementary buffer solution. Peak broadening due to the shape (bulb and tube-shaped) and size of the spray chambers was studied. The smaller tube-shaped spray chamber was used because of smaller peak broadening effect due to aerosol transport. The nebulization and transport efficiency of the CE-ICP interface was approximately 10%. Ba2+ and Mg2+ ions were eluted from the CE-chip within 30 s. Resolution of the Ba2+ and Mg2+ peaks was 0.7 using the chip-based CE-ICP-AES system.