A simple cleanup method for the isolation of nitrate from natural water samples for O isotope analysis.

The analysis of O-isotopic composition of nitrate has many potential applications in studies of environmental processes. O-isotope nitrate analysis requires samples free of other oxygen-containing compounds. More than 100% of non-NO3- oxygen relative to NO3- oxygen can still be found in forest soil water samples after cleanup if improper cleanup strategies, e.g., adsorption onto activated carbon, are used. Such non-NO3- oxygen compounds will bias O-isotopic data. Therefore, an efficient cleanup method was developed to isolate nitrate from natural water samples. In a multistep cleanup procedure using adsorption onto water-insoluble poly(vinylpyrrolidone), removal of almost all other oxygen-containing compounds, such as fulvic acids, and isolation of nitrate was achieved. The method supplied samples free of non-NO3- oxygen which can be directly combusted to CO2 for subsequent O-isotope analysis.     

主动声纳中目标回波的一种非线性提取方法

介绍了一种混沌时间序列的非线性动力学降噪方法——变尺度概率净化法,并将之优化应用于混响背景下目标回波的提取。该方法以近似条件下不含目标回波的混响数据作为参考,使目标回波分离后的混响背景数据与参考混响数据在相空间上具有一致的概率分布,从而实现目标回波的提取。在信混比不低于6dB的情况下,该方法具有较好的目标回波提取效果。文中对算法作了一些改进,降低了算法的运算量和运行所需计算机内存,而降噪性能并没有下降。     

一种自动提取IVUS图像血管包络的新方法

提取血管内超声(IVUS)图像的血管包络对冠状动脉疾病的诊断有一定的积极意义。本文综合考虑IVUS图像的灰度特征、序列时间特性、先验知识等三类信息,提出一种自动提取血管包络的方法。先由序列时间特性和先验知识减少噪声和伪像干扰,提取出第一帧图像的初始包络;然后用结合梯度、灰度方差、灰度均值信息的B样条GVFsnake对初始包络进行变形得到第一帧的最终包络;最后利用序列图像的时间特性提取后续帧的包络。通过实验表明:综合三类信息的包络自动提取方法在精度和鲁棒性等方面优于以往的方法。     

Application of struvite precipitation in treating ammonium nitrogen from semiconductor wastewater

Struvite precipitation was applied to the removal of NH(4)-N in semiconductor wastewater. Batch experiments were conducted to examine the effects of final pH, magnesium and orthophosphate dosages and the initial influent concentrations of NH(4)-N and F on the removals of NH(4)-N and PO(4)-P by forming struvite deposits. pH was an important parameter in the simultaneous removals of ammonium nitrogen and orthophosphate. In struvite precipitation, the amount of orthophosphate in the solution affected NH(4)-N removal much more than that of magnesium ions in some cases. It was revealed that the low and high initial concentrations of NH(4)-N and F inhibited NH(4)-N and PO(4)-P removal efficiencies in struvite precipitation, respectively. We also evaluated field-scale treatment plant incorporated by struvite precipitation process. On semiconductor wastewater with an NH(4)-N concentration of 155 mg/L, the results obtained showed that the incorporation of the struvite precipitation process brought about a high NH(4)-N removal efficiency of over 89% on average.     

Chemiluminescent method for detection of eutrophication sources by estimation of organic amino nitrogen and ammonium in water

An automatic method has been developed for the estimation of organic amino nitrogen (CH2-NH) and ammonium in water samples. We propose a continuous flow system in which nitrogen compounds react with hypochlorite reagent to produce chloramines. Subsequently, the mixture is mixed with luminol, generating a chemiluminescence signal. The signal emission at 425 nm, registered as a function of time, decreases as nitrogen concentration increases, due to the decrease on hypochlorite concentration. A large number of nitrogen compounds have been assayed and their sensitivities compared, in milligrams per liter nitrogen. The ammonium calibration graph, expressed as N, can be used for most of the assayed compounds. The linear interval was 0.24-4 mg L(-1) N, with the detection limit 0.07 mg L(-1) N. The chemiluminescence method was applied to the analysis of several kinds of real water samples, natural, lake, irrigation ditch, fountain, residual, and seawater in order to detect possible sources of eutrophication. The accuracy (% relative error) and precision were satisfactory, with mean values of 5 +/- 4 and 3 +/- 2, respectively. This procedure has been used to estimate nitrogen content in samples before and after Kjeldahl treatment. In the same samples, the N found for the untreated samples provided a good estimation of the N Kjeldahl. Sixty samples per hour can be analyzed, and the procedure can also be used for in situ monitoring.     

An efficient method for isolating individual long-chain alkenones for compound-specific hydrogen isotope analysis

Hydrogen isotope ratios (2H/H or D/H) of long-chain unsaturated ketones (alkenones) preserved in lake and marine sediments hold great promise for paleoclimate studies. However, compound-specific hydrogen isotope analysis of individual alkenones has not been possible due to chromatographic coelution of alkenones with the same carbon chain length but different numbers of double bonds. Published studies have only reported the deltaD values of the mixture of coeluting alkenones. We developed an efficient procedure to isolate individual alkenones based on double-bond numbers using silica gel impregnated with silver nitrate. The chromatographic procedure is simple, inexpensive, and highly reproducible, offers 87-100% sample recovery, and allows for the first time hydrogen isotopic measurement on individual alkenones. deltaD values of specific di-, tri- and tetraunsaturated C37 alkenones produced by an Emiliania huxleyi culture, as well as those isolated from Greenland lake sediments, differ consecutively by 43-65 per thousand. These findings suggest that alkenones with different numbers of carbon-carbon double bonds express significantly different deltaD values and that coelution of different alkenones may lead to erroneous source water deltaD reconstructions. Our alkenone isolation approach opens a new avenue for paleoclimate reconstructions using hydrogen isotope ratios of individual alkenones.     

Stable nitrogen isotope analysis of amino Acid enantiomers by gas chromatography/combustion/isotope ratio mass spectrometry

The analysis of the stable nitrogen isotope compositions of individual amino acid stereoisomers through the use of gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) is presented. Nitrogen isotopic compositions of single amino acids or of their enantiomers is possible without the labor-intensive and time-consuming preparative-scale chromatographic procedures required for conventional stable isotope analysis. Following hydrolysis and derivatization, single-component isotope analysis is accomplished on nanomole quantities of each of the stereoisomers of an amino acid, utilizing the effluent stream of gas chromatographic separation. Nitrogen isotope fractionation is minimal during acylation of the amino acid, with no additional nitrogen being added stoichiometrically to the derivative. Thus, the isotopic composition of the nitrogen in the derivative is that of the original compound. Replicate stable nitrogen isotope analyses of 11 amino acids, and their trifluoroacetyl (TFA)/isopropyl (IP) ester derivatives, determined by both conventional isotope ratio mass spectrometry (IRMS) and GC/C/IRMS, indicate that the GC procedure is highly reproducible (standard deviations typically 0.3-0.4‰) and that isotopic differences between the amino acid and its TFA/IP derivative are, in general, less than 0.5‰.     

An electrochemical method for the extraction of precipitates from age-hardenable aluminium alloys

An electrochemical method for the extraction of precipitates from age-hardenable aluminium alloys has been developed. Small anodic currents of 10mAcm^–2 are applied to samples suspended in a methanolic electrolyte containing benzoic acid, oxine, and chloroform. An analysis of extractions made using different current densities shows that the principal function of the anodic current is to break down the aluminium oxide film. The method should have considerable application in the study of high strength aluminium alloys.     

圆结构光光条中心亚像素级提取方法

从图像中准确提取光条中心对于主动视觉系统十分重要。分析微小物体内表面视觉检测系统中圆形结构光光条图像特征,将干扰光条分为漫反射和镜面反射两类。利用Hessian矩阵确定图像中光条法线方向,在光条法线方向上求解光条中心亚像素位置,用8方向搜索法剔除干扰光条。实验证明,光条提取和剔除干扰光条方法是有效的。     

Continuous extraction of trapped air from bubble ice or water for on-line determination of isotope ratios

We describe a new continuous extraction system for trapped air from bubble ice or water for on-line determination of the isotopic composition of the main air components nitrogen and oxygen (delta15N, delta18O, and delta17O). Studies of the composition of air from bubbles trapped in polar ice are providing fundamental information about ancient atmospheric composition and, therefore, are an important tool to learn more about Earth's climate. The new system proved to work reliably for standard air admixed and subsequently removed from a water stream. The precision (1 SD) of standard measurements is approximately 0.04/1000 for delta15N, approximately 0.1/1000 for delta18O, and approximately 0.15/1000 for delta17O. Ice measurements with the new on-line system are promising. Continuous measurements of nitrogen as well as oxygen isotope ratios can be performed with a spatial resolution of approximately 3 cm and nearly the same precision as for the standards. However, the measured delta values of ice are generally lower, as compared to ice measured with conventional techniques, as a result of a time-dependent dissolution process of air in water associated with kinetic fractionation, which affects standard and sample differently. By modeling the dynamics of the this dissolution process, we found a reason for the lack of accuracy and propose an improvement of the system that will lead to a better accuracy of the ice measurements.     

GC/multiple collector-ICPMS method for chlorine stable isotope analysis of chlorinated aliphatic hydrocarbons

Stable isotopic characterization of chlorine in chlorinated aliphatic pollution is potentially very valuable for risk assessment and monitoring remediation or natural attenuation. The approach has been underused because of the complexity of analysis and the time it takes. We have developed a new method that eliminates sample preparation. Gas chromatography produces individually eluted sample peaks for analysis. The He carrier gas is mixed with Ar and introduced directly into the torch of a multicollector ICPMS. The MC-ICPMS is run at a high mass resolution of >/=10 000 to eliminate interference of mass 37 ArH with Cl. The standardization approach is similar to that for continuous flow stable isotope analysis in which sample and reference materials are measured successively. We have measured PCE relative to a laboratory TCE standard mixed with the sample. Solvent samples of 200 nmol to 1.3 micromol (24-165 microg of Cl) were measured. The PCE gave the same value relative to the TCE as measured by the conventional method with a precision of 0.12 per thousand (2x standard error) but poorer precision for the smaller samples.     

A preconcentration/matrix reduction method for the analysis of rare earth elements in seawater and groundwaters by isotope dilution ICPMS

A simple method of simultaneous preconcentration and matrix reduction was developed for the analysis of rare earth elements (REEs) in seawater and groundwater by ID ICPMS. The method utilizes partitioning of the REEs with solid hydroxides to separate them from soluble matrix species (e.g., Ba2+, NOM, seawater salts). Acidified samples were spiked and equilibrated with an enriched isotope cocktail (142Ce, 145Nd, 161Dy, 171Yb). Aqueous NH3 was then added to the spiked samples to induce the coprecipitation of the REEs with a small fraction of the natural Mg2+ as Mg(OH)2. The samples were centrifuged and the precipitate was rinsed to remove more than 99.8% of the Ba2+ along with the matrix salts. The precipitate was dissolved in 400 microL of 10% HNO3 for ICPMS analysis. The four spiked elements, determined by isotope dilution, served as internal standards for the remaining REEs. Analysis of NASS-4 and NASS-5 seawater reference materials showed good agreement with published values. Calculated limits of detection for a 1.65-g sample ranged from 0.1 pg/g for the light REEs to 0.02 pg/g for the heavy REEs. The reagent blanks ranged from a high of 0.28 pg/sample for Ce to a low of 0.0036 pg/sample for Tb.     

A novel pattern extraction method for time series classification

Multivariate time series classification is of significance in machine learning area. In this paper, we present a novel time series classification algorithm, which adopts triangle distance function as similarity measure, extracts some meaningful patterns from original data and uses traditional machine learning algorithm to create classifier based on the extracted patterns. During the stage of pattern extraction, Gini function is used to determine the starting position in the original data and the length of each pattern. In order to improve computing efficiency, we also apply sampling method to reduce the searching space of patterns. The common datasets are used to check our algorithm and compare with the naive algorithms. Experimental results are shown to reveal that much improvement can be gained in terms of interpretability, simplicity and accuracy.     

IR laser extraction technique applied to oxygen isotope analysis of small biogenic silica samples

An IR-laser fluorination technique is reported here for analyzing the oxygen isotope composition (delta18O) of microscopic biogenic silica grains (phytoliths and diatoms). Performed after a controlled isotopic exchanged (CIE) procedure, the laser fluorination technique that allows one to visually check the success of the fluorination reaction is faster than the conventional fluorination technique and allows analyzing delta18O of small to minute samples (1.6-0.3 mg) as required for high-resolution paleoenvironmental reconstructions. The long-term reproducibility achieved with the IR laser-heating fluorination/O2 delta18O analysis is lower than or equal to +/-0.26 per thousand (1 SD; n = 99) for phytoliths and +/-0.17 per thousand (1 SD; n = 47) for diatoms. When several CIE are taken into account in the SD calculation, the resulting reproducibility is lower than or equal to +/-0.51 per thousand for phytoliths (1 SD; n = 99; CIE > 5) and +/-0.54 per thousand (1 SD; n = 47; CIE = 13) for diatoms. A minimum reproducibility of +/-0.5 per thousand leads to an estimated uncertainty on delta18Osilica close to +/-0.5 per thousand. Resulting uncertainties on reconstructed temperature and delta18Oforming water are, respectively, +/-2 degrees C and +/-0.5 per thousand and fit in the precisions required for intertropical paleoenvironmental reconstructions. Several methodological points such as optimal extraction protocols and the necessity or not of performing two CIE prior to oxygen extraction are assessed.     

A method for extraction and quantification of Ginkgo terpene trilactones

A method was developed for the extraction and quantification of pharmacologically active terpene trilactones (ginkgolides, bilobalide) from the tissues of Ginkgo biloba L. and pharmaceutical ginkgo products by RP-HPLC, based on the theory of terpene trilactones ionization. Four ginkgolides (GA, GB, GC, GJ) and bilobalide (BB) from both the ginkgo leaves and commercially available ginkgo extracts were quantitatively extracted by using this method. The recovery rate of the method was 97.5-100% with RSD of 1.2-2.8%. The detection limit was 0.05-0.1 microg, and the linear range was 0.1-12 microg. This detection limit represents a marked improvement over previously reported methods, suggesting the new method is a viable technique for routine analysis of ginkgo terpene trilactones in natural and commercial samples. The method reported by van Beek et al. in 1991 (van Beek, T. A.; Scheeren, H. A.; Rantio T.; Melger, W. C.; Lelyveld, G. P. J. Chromatogr. 1991, 543, 375-387.) was used as a reference method to monitor the accuracy of extraction and analysis in this study. SSI-MS technique was used to identify isolated target components. Carbohydrase treatment and solubility of terpene trilactones in various solvents were also discussed.     

海洋沉积物DNA提取前的简易脱腐方法研究

针对海洋沉积环境样品DNA提取中的腐殖酸去除难题,采取先脱除腐殖酸再提取DNA的策略,进行了海洋沉积物DNA提取前的简易脱腐方法研究.依据腐殖酸的理化性质, 遴选出由Tris-HCl、EDTA、Na4P2O7、NaCl、PVP、Triton X-100及脱脂奶粉组成脱腐缓冲液,有效地脱除了腐殖酸.之后采用温和的溶菌酶-蛋白酶K-SDS直接裂解法,获取了大片段(分子量21kb以上)可进行rpoB 基因PCR扩增的海洋沉积物DNA,为海洋沉积环境分子生态学研究与海洋生物活性物质开发奠定了基础.     

A new method of determining chlorine kinetic isotope effects

Two methods have been used to measure the chlorine leaving group kinetic isotope effect for the S(N)2 reduction of benzyl chloride to toluene by sodium borohydride in DMSO at 30.000 °C. The reaction was monitored by titrating the unreacted borohydride ion. One method involved determining the chlorine isotope effect using the classical IRMS method, which requires the conversion of the chloride ions into gaseous methyl chloride that is analyzed in an isotope ratio mass spectrometric analyses (Hill, J. W.; Fry, A. J. Am. Chem. Soc. 1962, 84, 2763. Taylor, J. W.; Grimsrud, E. P. Anal. Chem. 1969, 41, 805.). Two different measurements using this method yielded isotope effects of k(35)/k(37) = 1.007?19 ± 0.000?19 and 1.007?64 ± 0.000?19. The second method was a new technique where the ratio of the chlorine isotopes was obtained by fast atom bombardment mass spectrometry on the silver chloride recovered from the reaction, i.e., from the first step in the classical procedure. Therefore, the new method is much simpler and avoids the time-consuming preparation, purification, and recovery of the gaseous methyl chloride. Although the experimental error is larger (k(35)/k(37) = 1.008?03 ± 0.00?10 and 1.008?02 ± 0.000?65) when the new technique is used to analyze the silver chloride samples from the same set of experiments that were used to measure the isotope effect by the classical method, the chlorine isotope effect found by the two methods is identical within experimental error. This large chlorine kinetic isotope effect indicates there is considerable C(α)-Cl bond rupture in the S(N)2 transition state.     

Determination of origin of ephedrine used as precursor for illicit methamphetamine by carbon and nitrogen stable isotope ratio analysis

The sale of ephedrine, one of the precursors of methamphetamine, is strictly controlled and monitored in various countries to prevent the production of illicit methamphetamine. There are three kinds of production scheme for ephedrine manufacture, and it is very useful for precursor control to investigate the origin of ephedrine used for the synthesis of illicit methamphetamine. By means of stable isotope ratio mass spectrometry (IR-MS), we investigated the origin of ephedrine based on the delta(13)C and delta(15)N values. The various origins of ephedrine (biosynthetic, semisynthetic, or synthetic) could be discriminated clearly by using these values. The delta(15)N values of synthetic ephedrine were more negative than those of ephedrine from other sources. By the repeated distillation of methylamine in our laboratory, we confirmed that this could be due to isotope separation during distillation for the purification of methylamine used for ephedrine synthesis. The values for ephedrine used as the precursor were well-correlated with those for methamphetamine synthesized from it. This drug characterization analysis should be useful to illuminate the origin of the precursors used for clandestine methamphetamine and to trace the diversion of medicinal ephedrine for illicit manufacture of methamphetamine.