大气压力对煤样解吸气含量测试结果的影响

以自然解吸样品为对象,研究大气压力对煤样解吸气含量测试结果的影响。结果表明:当样品从大气压力较低的采样地点返回大气压力较高的实验室后,每24 h的解吸气含量测试结果明显减小,减小的幅度明显大于采样地点每24 h减小的幅度;对于开始7 d解吸气含量测试结果为零或者较小、按照标准可以结束测试的样品,建议将测试时间延长在3周左右,若按照标准仍旧可以结束测试时,再停止实验;如果样品在采样地点进行解吸实验直到结束,总解吸气含量测试结果将大于实验室。     

原子荧光光度法测定植物样品中的铋

植物样品经硝酸-高氯酸1次湿法消解后,用氢化物发生-原子荧光光谱法测定铋。测定时加入消泡剂磷酸三丁酯,可有效消除泡沫,降低记忆效应,提高精密度。方法精密度(RSD=12)铋1.50%。经加标回收试验和国家一级标准物质验证,测定结果与标准值吻合。     

Direct Current Plasma Emission Spectrometric Determination of Major, Minor and Trace Elements in Microwave Oven Acid Leachates of Powdered Whole Coal Samples

Major concentrations of Al₂O₃, Fe₂O₃, MgO, CaO, Na₂O and K₂O, minor levels of TiO₂, P₂O₅ and thirty petrologically, geochemically and environmentally significant trace elements have been determined in microwave oven acid leachates of whole powdered coal samples by direct current plasma‐atomic emission spectrometry (DCP‐AES). A single sample preparation procedure was suitable for all the determinations with no additional dilution step for major elements solution. Dried samples (0.5 g) were treated in low‐pressure PFA digestion vessels with HF/HCl/HNO₃/HClO₄ acids to quantitatively extract the analytes from the bulk material, while leaving the major part of organic matrix as a residue. The major constituents of geological samples, in particular the easily ionised elements (EIEs) such as alkali and alkaline earths, may complicate the instrumental determinations in DCP‐AES because of differential enhancements of elemental emission intensities and stray light interferences. Taking account of these factors, the coal matrix is considered to have very low major oxide totals as compared to many other common geo‐environmental and related materials (rocks, sediments, soil, ashes etc.). The sample size employed here, while yielding a relatively concentrated solution to cover a wide range of elemental determinations, provided a sample matrix that significantly diminished interferences for DCP measurements. The need for closely matching the unknowns and calibrators was eliminated except for overall acidity and an excess quantity of caesium for EIE buffering. Calibration of the spectrometer was accomplished by simple aqueous single element solutions as high concentration calibrators in addition to a reagent blank as a low concentration calibrator. Two point working curves were established to allow for the maximum concentrations of each element expected in the unknowns. The precision of determinations under routine conditions as well as the reproducibility of the leaching and precision of instrumental measurements have been evaluated. Relative standard deviations (RSD) were of 1–2% for those elements whose concentrations in solid samples were well above the limits of quantification. Method detection limits in the buffered solutions were also evaluated. To evaluate the accuracy of the microwave oven‐DCP method a suite of eight certified coal reference materials of differing rank, were analysed with good agreement with the certified and/or available published data. Results are presented for the uncertified major oxides in the AR series reference materials.     

提高连续墙抓斗入岩效率若干问题的探讨

越来越多的连续墙工程提出了入岩要求,而现阶段广泛使用的连续墙抓斗入岩效率低下,针对这种状况,以抓斗抓取地层的特点为出发点,对其现阶段在岩石地层抓取效率低下的原因进行分析,然后以岩石破碎学为理论支撑,从抓斗自重、油缸闭合力、斗齿布置规格以及抓取方式等方面着手,提出了若干可用于提高抓斗入岩效率的改进建议。     

单绳冲抓锥自动脱挂装置的设计

介绍了单绳冲抓锥自动脱挂装置的结构和操作原理，通过对脱挂过程进行了的平衡分析，找出了影响脱钩灵活性和挂钩可靠性的主要因素，阐明了自动脱挂装置的设计原理。     

Partial L-moments for the analysis of censored flood samples / Utilisation des L-moments partiels pour l’analyse d’échantillons tronqués de crues

Abstract

Abstract A parameter estimation method is proposed for fitting the generalized extreme value (GEV) distribution to censored flood samples. Partial L-moments (PL-moments), which are variants of L-moments and analogous to ?partial probability weighted moments?, are defined for the analysis of such flood samples. Expressions are derived to calculate PL-moments directly from uncensored annual floods, and to fit the parameters of the GEV distribution using PL-moments. Results of Monte Carlo simulation study show that sampling properties of PL-moments, with censoring flood samples of up to 30% are similar to those of simple L-moments, and also that both PL-moment and LH-moments (higher-order L-moments) have similar sampling properties. Finally, simple L-moments, LH-moments, and PL-moments are used to fit the GEV distribution to 75 annual maximum flow series of Nepalese and Irish catchments, and it is found that, in some situations, both LH- and PL-moments can produce a better fit to the larger flow values than simple L-moments.     

离散点集（地震）空间分布多重分形计算的精度估算

地震是一种非线性现象,因而很多人计算地震分布的分形维数,但具体各种计算方法的误差（或精度）是多少,还没有定量的估计。鉴于地震空间分布具有有限、离散、点集的特点,用双标度Contor 多分形集理论模型数值模拟来估算其精度（误差）,并判定各种方法的优劣。理论模型数值模拟得出如下结论:① 随着样本容量的增大,计算精度会提高;② 固定半径法（RAD） 计算误差偏大,固定质量法（MAS）和最小生成树法（MST）较好;③ 当样本容量达到约200时,MAS法和MST 法计算误差大体可稳定在0.05的范围内。     

土壤有机碳同位素样品制备过程的影响因素讨论

土壤有机碳同位素地球化学在气候和植被恢复方面的研究已得到广泛应用,但目前对不同类型、不同时代的土壤总有机碳同位素样品制备过程的系统研究较少.本文选取黄土高原不同地区、不同类型的现代土壤和古土壤,对其有机碳同位素样品制备过程进行了较系统的研究.( 1)去除土壤中无机碳酸盐对有机碳同位素组成的干扰:对于现代土壤样品,在室温条件下,用 0.5～ 6 mol/L HCl反应 1 d去除碳酸盐,均可获得理想数据;在 70 ℃反应条件下,用 0.5～ 2 mol/L HCl反应 2 h去除碳酸盐可获得理想数据,但用 6 mol/L HCl,δ 13C值偏负 0.65‰;( 2)在 850 ℃氧化温度条件下,样品制备加铜丝,对现代土壤及古土壤样品的δ 13C值均没有影响,结果表明在用封管法进行现代土壤及古土壤的有机碳同位素样品制备时,可以不加铜丝;( 3)对于有机碳含量较高的有机碳标准物质、植物和现代土壤样品,在 850 ℃氧化条件下,恒温 2.5 h,足以保证样品有机质氧化完全,不会产生同位素分馏;对于深层黄土和红粘土样品,由于样品体系复杂,在上述氧化条件下难以获得理想数据,合适的氧化条件有待进一步深入研究.     

植物样品中无机元素分析的样品前处理方法和测定技术

植物样品中无机元素的分析测定在环境地球化学和生物地球化学的研究中起着重要作用。植物样品中元素含量一般较低,须选用科学合理的前处理技术和灵敏度高、精密度好、检出限低的测定方法。本文针对植物样品前处理方法和无机元素分析测定技术的研究进展、优势与不足进行评述。前处理方法主要根据样品和待测元素的性质进行选择:干法灰化所用试剂少、空白值低,但组织致密型的样品不易灰化完全、高温下易造成元素挥发损失;湿法消解样品消解较为完全,但试剂消耗大、空白值高、操作繁琐;微波消解可以防止部分易挥发元素损失,用酸量少、消解速度快,但称样量相对较小,不适于需要大称样量的样品分析。几乎所有针对元素分析的仪器分析技术都可以用于植物样品分析,主要根据仪器适用的元素、必要的干扰校正以及基体改进等方面进行选择:电感耦合等离子体质谱法可同时测定植物样品中40种以上的元素,高分辨质谱的检出限可达fg/mL;电感耦合等离子体发射光谱法适用于某些植物样品中含量较高的P、K、Na等元素的测定;原子吸收光谱法可分析元素达70余种,是普及程度最高的仪器分析技术之一;原子荧光光谱法与氢化物发生技术的联用,在元素含量较低的植物样品分析中技术优势更加明显;新兴的激光诱导击穿光谱技术已被应用于植物样品分析,无需复杂的样品前处理,操作简单快速,可实现原位、在线、实时、多元素同时检测;其他选择性强、灵敏度高的分析技术,满足了一些特定元素不能用常规分析技术测定的需求。当前主流分析技术的样品前处理方法都存在着缺陷,固体进样技术将成为植物样品分析领域的发展方向之一。