ON THE SIGNIFICANCE OF WAVELENGTH POSITIONING ACCURACY IN MULTICOMPONENT ANALYSIS TECHNIQUES FOR THE CORRECTION OF LINE INTERFERENCES IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

The present paper reports some definite evidence for the significance of wavelength positioning accuracy in multicomponent analysis techniques for the correction of line interferences in inductively coupled plasma atomic emission spectrometry (ICP-AES). Using scanning spectrometers commercially available today, a large relative error, DELTA(A) may occur in the estimated analyte concentration, owing to wavelength positioning errors, unless a procedure for data processing can eliminate the problem of optical instability. The emphasis is on the effect of the positioning error (deltalambda) in a model scan, which is evaluated theoretically and determined experimentally. A quantitative relation between DELTA(A) and deltalambda, the peak distance, and the effective widths of the analysis and interfering lines is established under the assumption of Gaussian line profiles. The agreement between calculated and experimental DELTA(A) is also illustrated. The DELTA(A) originating from deltalambda is independent of the net analyte/interferent signal ratio; this contrasts with the situation for the positioning error (dlambda) in a sample scan, where DELTA(A) decreases with an increase in the ratio. Compared with dlambda, the effect of deltalambda is generally less significant.

WAVELENGTH POSITIONING ERRORS AND TRUE DETECTION LIMIT IN RELATION TO MULTICOMPONENT ANALYSIS TECHNIQUES FOR THE CORRECTION OF LINE INTERFERENCES IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

The present paper deals with the evaluation of the relative error (DELTA(A)) in estimated analyte concentrations originating from the wavelength positioning error in a sample scan when multicomponent analysis (MCA) techniques are used for correcting line interferences in inductively coupled plasma atomic emission spectrometry. In the theoretical part, a quantitative relation of DELTA(A) with the extent of line overlap, bandwidth and the magnitude of the positioning error is developed under the assumption of Gaussian line profiles. The measurements of eleven samples covering various typical line interferences showed that the calculated DELTA(A) generally agrees well with the experimental one. An expression of the true detection limit associated with MCA techniques was thus formulated. With MCA techniques, the determination of the analyte and interferent concentrations depend on each other while with conventional correction techniques, such as the three-point method, the estimate of interfering signals is independent of the analyte signals. Therefore. a given positioning error results in a larger DELTA(A) and hence a higher true detection limit in the case of MCA techniques than that in the case of conventional correction methods. although the latter could be a reasonable approximation of the former when the peak distance expressed in the effective width of the interfering line is larger than 0.4. In the light of the effect of wavelength positioning errors, MCA techniques have no advantages over conventional correction methods unless the former can bring an essential reduction ot the positioning error.

PREPARATION AND STRUCTURE OF HALF-OPEN VANADOCENE, V[2,4-(CH3)2C5H5](C5H5)CO

The half-open vanadocene, V[2,4-(CH3)2C5H5](C5H5)CO, was obtained by the reaction of V[2,4-(CH3)2C5H5](C5H5)PMe3 with CO in petroleum ether at room temperature. Its crystal structure was determined by X-ray diffraction technique. The crystal was monoclinic with space group P2(1)/n, a = 16.614(3), b = 7.636(1), c = 19.128(6) angstrom, beta = 99.92(2)-degrees, V = 2390.5(9) angstrom3, and Z = 8. The final R value was 0.043. The V(1)-CPD(1) (half) (PD = 2,4-(CH3)2C5H5) bonds were shorter (0.038 angstrom) than the V(1)-CCP(1) (half) (CP = C5H5) bonds, averaging 2.224(4) versus 2.262(4) angstrom, respectively. 4V[2,4-(CH3)2C5H5](C5H5)CO has been characterized by IR and EPR methods.

白垩纪超静磁带地球磁场古强度测定

The long-term variations in the strength of the geomagnetic field provide important constraints on the chemical-physical processes of the Earth’s interior. Especially, the intensity of the geomagnetic field during the Cretaceous normal superchron (CNS) is crucial to understand the geodynamo. But a paucity of paleointensity further limits to obtain essential knowledge interior process in the deep earth. In order to improve the experimental efficiency, this study tried to apply two new rock magnetic methods (FORC diagram and low-temperature demagnetization technique) to determine the paleointensity. First, some problems in the theory and technique in paleointensity experiments were introduced. A combined palaeomagnetic and geochronologic study was further conducted on a basaltic lava sequence at Jianchang in Liaoning Province, northeastern China. Radiometric 40Ar/39Ar dating indicates that the volcanism occurred at about 119 Ma within the marine anomaly C34n in Cretaceous normal superchron (CNS). Rock magnetic investigations show that pseudo-single domain (PSD) titanium-poor titanomagnetite is dominant in the studied lava flows. Both stepwise thermal and alternating field demagnetizations isolate the well-defined normal characteristic remanent magnetization (ChRM) in three independent lava flows with a mean direction of D/I = 6.0/51.9 degree(a95 = 12.3degree). Palaeointensity was determined using the modified Thellier method with systematic partial thermoremanent magnetization (pTRM) checks on total 72 samples, but only 10 samples exhibit ideal linear behavior on the Arai-plot in the temperature interval of 300-560 C and yield an average paleointensity of (25.8+/-1.4)uT. In addition, slopes of the line defined by the initial and the final points on the Arai-plot for the other 18 samples with characteristic PSD features give an average paleointensity estimation value of (24.8+/-1.9)uT. The consistency of these two approaches confidently demonstrates the fidelity of our results. The overall mean field strength determined using both approaches are thus estimated to be (25.2+/-0.7 )uT. This value corresponds to the virtual dipole magnetic moments (VDM) of (4.5+/-0.1)E22 Am^2, which is about half of the value of present field. This finding suggests that palaeointensity just at the onset of the CNS is characterized by a weak magnetic field.

人工源频率域大地电磁法正反演研究

The CSAMT method is playing an important role in the exploration of geothermal and the pre-exploration in tunnel construction project recently. In order to instruct the interpretation technique for the field data, the forward method from ID to 3D and inversion method in ID and 2D are developed in this paper for the artificial source magnetotelluric in frequency domain. In general, the artificial source data are inverted only after the near field is corrected on the basis of the assumption of half-homogeneous space; however, this method is not suitable for the complex structure because the assumption is not valid any more. Recently the new idea about inversion scheme without near field correction is published in order to avoid the near field correction error. We try to discuss different inversion scheme in ID and 2D using the data without near field correction.The numerical integration method is used to do the forward modeling in ID CSAMT method o The infinite line source is used in the 2D finite-element forward modeling, where the near-field effect is occurred as in the CSAMT method because of using artificial source. The pseudo-delta function is used to modeling the source distribution, which reduces the singularity when solving the finite-element equations. The effect on the exploration area is discussed when anomalous body exists under the source or between the source and exploration area; A series of digital test show the 2D finite element method are correct, the results of modeling has important significant for CSAMT data interpretation. For 3D finite-element forward modeling, the finite-element equation is derived by Galerkin method and the divergence condition is add forcedly to the forward equation, the forward modeling result of the half homogeneous space model is correct.The new inversion idea without near field correction is followed to develop new inversion methods in ID and 2D in the paper. All of the inversion schemes use the data without near field correction, which avoid introducing errors caused by near field correction. The modified grid parameter method and the layer-by-layer inversion method are joined in the ID inversion scheme. The RRI method with artificial source are developed and finite-element inversion method are used in 2D inversion scheme. The inversion results using digital data and the field data are accordant to the model and the known geology data separately, which means the inversion without near field correction is accessible. The feasibility to invert the data only in exploration area is discussed when the anomalous body exists between the source and the exploration area.

中老年危机热线来电者的应激源与自杀危险性

Objective: Psychosocial crisis and psychiatric disorders are two stressors for suicide action. This study will explore the differences on demographic characteristics, severity of depression, and suicidality of middle-aged and elder crisis line callers under the influences of psychosocial crisis or psychiatric disorders or two simultaneously-mixed stressors, in order to develop effective intervention strategies for crisis line. Methods: Analysis data of 1,092 cases selected from national crisis line callers aged 45 and over who were assessed with “Suicide risk assessment” during the period from December, 2002 to December, 2008. The sample were divided into three groups of psychosocial crisis, mental health problems, and mixed-stressors of three types of general callers (48.2%, 32.3%, 19.5%), callers with current suicide ideation (43.7%, 33.0%, 23.3%) and callers attempted suicide 2 weeks prior to the call (33.6%, 42.3%, 24.1%) respectively according to the operators’ judgments of the callers’ claimed difficult situations and classification system of crisis line database. X2 test and Tukey-type and Multinomial Logistic Regression multiple comparison methods are applied to analysis the differences of the three groups. Results: In agreement with previous studies, more females (71.3%, X2=13.45, P<0.001), especially females influenced by relationship stressors (76.8%, X2=25.12, P<0.001) made the call for crisis. Among general callers, the check-out rates of Major Depression Episode of mixed-stressor callers (78.5%, P<0.001) and problem callers (68.7%, P<0.05) were significantly higher than that of crisis callers (57.1%). The check-out rates of suicide ideation of mixed-stressor callers (71.4%) were significantly higher than that in crisis callers (53.8%, P<0.001) and problem callers (60.9%, P<0.05). The check-out rates of prior suicide attempts of mixed-stressor (16.6%, P<0.05) and problem callers (18.5%, P<0.01) were significantly higher than that of crisis callers (9.8%). More than half of the mixed-stressor callers (51.8%) reported over 50% degree of hopelessness, which was significantly higher than that of crisis callers (35.6%, P<0.01) and problem callers (38.2%, P<0.05). Fewer crisis callers sought medical help than problem and mixed-stressor callers among three types of callers (X2=241.35, 146.56, 50.87; P<0.001). Compare to non-compound crisis callers, the proportion of minor, severe depression and prior depression diagnosis (14.0% vs. 17.4%; 54.9% vs. 65.2%; 0 vs. 2.2%; X2=14.35，P<0.01), suicide ideation (51.1% vs. 64.0%, P<0.05) and prior suicide attempts (8.4% vs. 15.0%, P<0.05) in compound crisis callers were significantly higher. There were more compound crisis callers with over 50% hopelessness (51.9% vs. 31.0%，X2=11.96，P<0.01). Conclusion: As predicted, among middle-aged and elderly participants, mixed-stressor and compound crisis callers were higher in degree of severity of depression and suicidality. Intervention strategies should be developed addressing to specific stressor or stressors. The promotions of crisis callers’ medical help seeking behavior need to be emphasized.

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.

On-line concentration of peptides and proteins with the hyphenation of polymer monolithic immobilized metal affinity chromatography and capillary electrophoresis

An iminodiacetic acid (IDA)-type adsorbent is prepared at the one end of a capillary by covalently bonding IDA to the monolithic rods of macroporous poly(glycidyl methacrylate-co-ethylene dimethacrylate). Cu(II) is later introduced to the support via the interaction with IDA. By this means, polymer monolithic immobilized metal affinity chromatography (IMAC) materials are prepared. With such a column, IMAC for on-line concentration and capillary electrophoresis (CE) for the subsequent analysis are hyphenated for the analysis of peptides and proteins. The reproducibility of such a column has been proved good with relative standard deviations (RSDs) of dead time of less than 5% for injection-to-injection and 12% for column-to-column (n = 3). Through application on the analysis of standard peptides and real protein samples, such a technique has shown promising in proteome study.