多组分体系同时定性定量测定的逐步回归分析法

阐述了逐步回归分析法用于多组分体系同时定性定量分析的原理、实验及数据处理方法。分析了硝基酚类人工样、未知样及合成样。该法可用于仅知可能含有的组分范围的样品分析。     

农业样品分析

本文是本刊“农业样品分析”第三篇定期评述，对１９９４年４月至１９９８年６月（着重于近两年）国内农业测试分析的进展作了评述，包括分子光谱、原子光谱、色谱、电化学、电泳分析，共引用文献６７５篇。     

Development of a mild mercaptoethanol extraction method for determination of mercury species in biological samples by HPLC–ICP-MS

A mild, efficient and convenient extraction method of using 2-mercaptoethanol contained extractant solution combined with an incubator shaker for determination of mercury species in biological samples by HPLC–ICP-MS has been developed. The effects of the concentration of 2-mercaptoethanol, the composition of the extractant solution and the shaking time on the efficiency of mercury extraction were evaluated. The optimization experiments indicated that the quantitative extraction of mercury species from biological samples could be achieved by using 0.1% (v/v) HCl, 0.1% (v/v) 2-mercapoethanol and 0.15% (m/v) KCl extractant solution in an incubator shaker for shaking overnight (about 12 h) at room temperature. The established method was validated by analysis of various biological certified reference materials, including NRCC DOLT-3 (dogfish liver), IAEA 436 (tuna fish), IAEA MA-B-3/TM (garfish filet), IAEA MA-M-2/TM (mussel tissue), GBW 08193 (bovine liver) and GBW 08572 (prawn). The analytical results of the reference materials were in good agreement with the certified or reference values of both methyl and total mercury, indicating that no distinguishable transformation between mercury species had occurred during the extraction and determination procedures. The limit of detection (LOD) for methyl (CH₃Hg⁺) and inorganic mercury (Hg²⁺) by the method are both as 0.2 μg L⁻¹. The relative standard deviation (R.S.D.s) for CH₃Hg⁺ and Hg²⁺ are 3.0% and 5.8%, respectively. The advantages of the developed extraction method are that (1) it is easy to operate in HPLC–ICP-MS for mercury species determination since the extracted solution can be directly injected into the HPLC column without pH adjustment and (2) the memory effect of mercury in the ICP-MS measurement system can be reduced.     

Simultaneous sample preparation for high-performance liquid chromatographic determination of Vitamin A and β-carotene in emulsified nutritional supplements after solid-phase extraction

Determination of small amounts of the fat-soluble species Vitamin A (VA) (2.5 μg/g) and β-carotene (9 μg/g) from emulsified nutritional supplements containing 50 kinds of co-existing compounds and a fat content between 2000 and 8000 times higher was performed by solid-phase extraction (SPE) and high-performance liquid chromatography (HPLC) with fluorescence detection set at ex. 350 nm and em. 480 nm, and visible detection at 450 nm using an Inertsil ODS 80A (5 μm) analytical column. Mobile phases of methanol-ethanol (50:50) and acetonitrile-ethanol (70:30) were used for the both vitamins. A Bond Elut C₁₈ cartridge was chosen for SPE after comparison with eight other types of SPE cartridge. Retention time of VA and β-carotene was 7 and 8 min, respectively, giving a limit of detection of ca. 0.1 ng per injection at a signal-to-noise ratio 3:1. Recoveries of VA and β-carotene were over 90% by the standard addition method. Relative standard deviation of VA and β-carotene were ca. 2.9 (n=5) and 2.3% (n=5), respectively.     

Selenium and mercury bioaccessibility in fish samples: an in vitro digestion method

The assessment of hazard from selenium (Se) and mercury (Hg) contaminants in the food chain based on their potential bioaccessibility and on estimate of their actual content in fish is reported under an in vitro model. Atomic fluorescence spectroscopy (AFS) was applied for total selenium and mercury quantification. Selenium and mercury bioaccessibility varied depending on the type of fish analyzed. Se solubility in the gastrointestinal supernatants was higher in swordfish and sardine (76 and 83%, respectively) than in tuna (50%). A low Hg bioaccessibility (9-17%) was found for all the samples.Simulated human gastric and intestinal digestion led to the identification of selenomethionine (SeMet) and organic mercury in the three digested fish. Furthermore, these species were not modified during the digestion. Speciation of selenium compounds was done by liquid chromatography in conjunction with inductively coupled plasma mass spectrometry (LC-ICP-MS).Sardine had the most favorable Se:Hg, [Se:Hg]_{bioaccessible} and [SeMet:Hg]_{bioaccessible} molar ratios, making it preferable to tuna and swordfish.The effect of cooking was also evaluated.     

Determination of diethanolamine or <Emphasis Type="Italic">N</Emphasis>-methyldiethanolamine in high ammonium concentration matrices by capillary electrophoresis with indirect UV detection: application to the analysis of refinery process waters

Alkanolamines such as diethanolamine (DEA) and N-methyldiethanolamine (MDEA) are used in desulfurization processes in crude oil refineries. These compounds may be found in process waters following an accidental contamination. The analysis of alkanolamines in refinery process waters is very difficult due to the high ammonium concentration of the samples. This paper describes a method for the determination of DEA in high ammonium concentration refinery process waters by using capillary electrophoresis (CE) with indirect UV detection. The same method can be used for the determination of MDEA. Best results were achieved with a background electrolyte (BGE) comprising 10 mM histidine adjusted to pH 5.0 with acetic acid. The development of this electrolyte and the analytical performances are discussed. The quantification was performed by using internal standardization, by which triethanolamine (TEA) was used as internal standard. A matrix effect due to the high ammonium content has been highlighted and standard addition was therefore used. The developed method was characterized in terms of repeatability of migration times and corrected peak areas, linearity, and accuracy. Limits of detection (LODs) and quantification (LOQs) obtained were 0.2 and 0.7 ppm, respectively. The CE method was applied to the determination of DEA or MDEA in refinery process waters spiked with known amounts of analytes and it gave excellent results, since uncertainties obtained were 8 and 5%, respectively.     

金橙G螯合形成树脂分离富集地质样品中的微量贵金属

主要研究了金橙Ｇ螯合形成树脂分离富集地质样品中金、铂、钯的最佳实验条件。在柱高大于１６ｃｍ，０．１ｍｏｌ／Ｌ ＨＣｌ介质的样品溶液以小于或等于０．５ｍＬ／ｍｉｎ流速过柱，用０．１ｍｏｌ／Ｌ ＨＣｌ的３％硫脲溶液以小于或等于０．５ｍＬ／ｍｉｎ流速洗脱金、铂、钯（和铑），都能同时定量富集。用火焰原子吸收光谱法测定，回收率均在９５％￣１１０％之间。经地质样品加标准回收实验，结果令人满意。证明这种以磺酸基     

全自动QuEChERS样品制备系统结合高效液相色谱-串联质谱法检测植物源性食品中34种农药残留

建立了全自动QuEChERS样品制备系统结合高效液相色谱-串联质谱（HPLC-MS/MS）同时检测植物源性食品中34种农药残留的分析方法。方法利用全自动QuEChERS样品制备系统涡旋振动和离心功能，将手动QuEChERS方法中样品提取和分散固相萃取相结合；优化了操作参数及前处理步骤，在多反应监测（MRM）模式下检测，基质匹配外标法定量。从方法学验证角度对全自动QuEChERS法与手动QuEChERS法进行了比较。结果表明：该方法中大多数农药在一定范围内呈现良好的线性关系，相关系数（R²）均大于0.99，检出限为0.76~3.60 μg/kg，定量限为2.28~10.80 μg/kg，加标回收率为53.0%~125.2%，相对标准偏差（RSD）<15.9%（n=5）。该方法与手动QuEChERS法的方法验证比对结果显示差异不明显，用于植物源性食品中多农药残留检测可有效降低劳动强度和出错概率。     

岩石的核磁共振自旋密度微成像

岩，心是油气储层的基本单元，其内部结构和渗流性质反映了油藏的基本特征．岩。心的精细描述是油藏描述、储层动态监测及设计强化采油方案的重要基础．本文利用核磁共振（NMR）自旋密度做成像，快速无损地观测到两类基本储油岩石——砂岩和灰岩的内部结构，提供了岩石渗透性、孔隙性及灰岩沉积环境等重要信息．1实验方法以自旋回波单片NMR成像脉冲序列为基础，设。P平面内样品的目施密度为P（。，v）．演化期t。，在。方向梯度场G。作用下，各处横向磁化矢量获得的相移为式中，7为共振核（在成像中一般为质子）的旋磁比，g为坐标位置·…     

Application of capillary electrophoresis with different sample stacking strategies for the determination of a group of nonsteroidal anti-inflammatory drugs in the low microg x L(-1) concentration range

Several on-column sample preconcentration modes--large-volume sample stacking using the EOF pump (LVSEP), LVSEP with anion-selective exhaustive injection (LVSEP-ASEI) and field-amplified sample injection with sample matrix removal using the electroosmotic flow (EOF) pump (FAEP)--were used to analyze some nonsteroidal anti-inflammatory drugs (NSAIDs) by capillary electrophoresis, and then compared. Methanol was the background electrolyte solvent to suppress the EOF. The effect of the type and length of the solvent plug, and the sample injection time were investigated in FAEP to determine the conditions that provided the best response. LVSEP, LVSEP-ASEI, and FAEP improved the sensitivity of the peak area by 100-, 1200-, and 1800-fold, respectively. The methodology developed, in combination with solid-phase extraction (SPE), was applied to the analysis of water samples.