ICP-MS 法直接测定冰芯样品中超痕量镉

采用 ICP- MS法对冰芯样品中超痕量 Cd的直接测定进行了研究。确定了直接测定浓度为 pg/m L 级的 Cd的最佳仪器参数、载气流速、进样速度等与灵敏度之间的关系以及浓度和扫描参数对分析精度的影响。本方法对浓度 5～2 0 0 pg/m L Cd的分析 ,RSD<1 0 % ,回收率在 88%～ 1 0 5%之间 ,检测限为0 .1 5pg/m L     

Direct competitive ELISA for the determination of polychlorinated biphenyls in soil samples

A direct competitive ELISA for determination of polychlorinated biphenyls (PCB) in soil samples was described. The standard calibration curve based on Delor 103 (Aroclor 1242) was constructed in the dynamic range of 10-1000 micro g L(-1) and a detection limit of 5.0-12.9 micro g L(-1) (or 0.5-1.29 micro g g(-1) soil) was achieved. When spiked soil samples were extracted with methanol recoveries were 90.6-106.3 %. The effect of methanol and DMSO on assay signal and sensitivity was established. Eight PCB-contaminated soil samples were analyzed by ELISA and gas chromatography (GC). The ELISA results from Soxhlet extraction were in a good agreement with those of GC (correlation coefficient 0.9866; n=8). Except for one soil sample the results from ELISA with methanol extraction were not significantly different from those from GC.     

Comparison of different methods for the determination of volatile organic compounds in water samples

The aim of this work was to compare the characteristics of three methods, membrane inlet mass spectrometry (MIMS), purge-and-trap gas chromatography-mass spectrometry (P&T) and static headspace gas chromatography (HSGC), for the determination of volatile organic compounds in water samples as used in routine analysis. The characteristics examined included linear dynamic ranges, detection limits of selected environmentally hazardous volatile organic compounds (e.g. toluene, benzene and trichloroethene) in water, required analysis time and reproducibility of the analytical methods. The MIMS and P&T methods had the lowest detection limits for all the tested compounds, ranging from 0.1 to 5 mug 1(-1). Linear dynamic ranges using the MIMS method were about four orders of magnitude and using the P&T method about two orders of magnitude. Detection limits of the HSGC method were 10-100 times higher than those of the other two methods, but the linear dynamic ranges were larger, even up to six orders of magnitude. The analysis time per sample was shortest for the MIMS method, from 5 to 10 min, and ranged around from 35 to 45 min for the HSGC and P&T methods. The reproducibilities of the methods were of the same order of magnitude, in the range of 1-13%. Agreement between the analytical results obtained for spiked samples and for environmental water samples by the three different methods was very good.     

Direct determination of pesticides in vegetable samples using gold nanoelectrode ensembles

Gold nanowires were produced by electrodeposition in polycarbonate membrane, with an average diameter of 200 nm and a height of about 2 μm. The nanowire array prepared by the proposed method can be considered as nanoelectrode ensembles (NEEs). An amperometric pesticides sensor based on gold NEEs has been developed and used for determination of phoxim and dimethoate in vegetable samples. The electrochemical performance of the gold NEEs has also been studied by the amperometric method. The electrode provided a linear response over a concentration range of 5.9 × 10^?5 to 1.2 × 10^?2 M for phoxim with a detection limit of 4.8 × 10^?6 M and 6.3 × 10^?5 to 1.1 × 10^?2 M for dimethoate. This sensor displayed high sensitivity and selectivity, long-term stability and wide linear range. In addition, the ellipsis of enzyme and the reactivation of enzyme make the operation simple. This sensor has been used to determine pesticides in a real vegetable sample.     

Direct flame atomic absorption spectrophotometric determination of alkalis in geochemical samples

Flame atomic absorption spectrometry has been used for the estimation of the alkali metal content (as Na₂O and K₂O) in 95 reference materials with diverse matrices (including recently introduced Polish and Chinese standard samples awaiting certification through collaborative studies) using 1000 μg ml⁻¹ of lanthanum and 2000 μg ml⁻¹ of rubidium as matrix buffers for sodium and potassium, respectively. The ±t (Student's values for the samples with known recommended values (degree of freedom n − 1 = 9), at the 95% and 99% confidence levels) indicate that within the confidence levels 95–99% there is no statistical difference between the data presented and the reference data for most of the samples. The agreement between the reported data and the results obtained are generally good.     

Aqueous sulfuric acid as the mobile phase in cation ion chromatography for determination of histamine, putrescine, and cadaverine in fish samples

Aqueous sulfuric acid can be used as the mobile phase in cation ion chromatography to separate the three biogenic amines, putrescine, cadaverine, and histamine, from fish. Various concentrations of aqueous sulfuric acid were investigated to optimize the separation of these three biogenic amines. Aqueous sulfuric acid (5.0 mM) was found to be optimum for the separation and was used to determine the three biogenic amines in fish. The LOQ, defined as the lowest level of the standard calibration curve, was 0.055 ppm (equivalent to 0.55 microg/g sample) for putrescine, 0.05 ppm (equivalent to 0.5 microg/g sample) for cadaverine, and 1.0 ppm (equivalent to 10 microg/g sample) for histamine. From statistical analysis of the LOQ, the method detection limit was 0.003 ppm for putrescine, 0.009 ppm for cadaverine, and 0.16 ppm for histamine. For sample preparation, the fish was composited, homogenized in methanol-water (75 + 25, v/v), incubated for 15 min at 60 degrees C, and centrifuged. The sample solution was micron-filtered before injection. The mobile phase flow rate was 0.8 mL/min under isocratic conditions at room temperature (15-25 degrees C). The three biogenic amines were separated in the order of increasing retention time, i.e., putrescine, cadaverine, and histamine, within 30 min. The chromatograms showed complete peak separation of the three amines regardless of the difference in fish matrixes.     

GC determination of volatile organoiodine and organobromine compounds in Arctic seawater and air samples

Summary During September 1992 seawater and air samples were collected on Spitzbergen, Norway, and the concentrations of volatile organoiodine and organobromine compounds of biogenic origin were determined by a GC system supplied with a capillary column and an electron capture detector. A purge and trap technique was used to isolate the organohalogen compounds from the seawater samples, whereas the air samples were collected by an adsorption tube filled with Carbosieve S-III. The iodinated compounds CH₃I, CH₂I₂, CH₂C1I, CH₃CH₂CH₂I and CH₃CHICH₃ were determined in Arctic seawater and air samples with mean concentrations in the range of (0.3–6.2) ng/l and (0.7–2) pptv, respectively. This is the first time that 1- and 2-propyl iodide could be analysed both in atmospheric samples and in seawater samples of the Arctic. CH₂Br₂, CHBr₃, CH₂BrCl, CHBrCl₂ and CHBr₂Cl were determined as biogenic brominated methanes in mean concentrations of (0.1–164) ng/l and (0.1–0.5) pptv in seawater and air samples, respectively. The highest concentrations in seawater samples were found for CH₂I₂ and CHBr₃, respectively, whereas in air samples the most abundant iodinated compound was CH₃I and the most abundant brominated compounds with equal mean concentrations were CH₂Br₂ and CHBr₃. Significant differences were found in the seawater concentration from the middle of the fjord and the shore site, compared with samples from a field of algae. In all cases the concentration was higher for the samples from the field of algae with an especially high excess by a factor of 4–9 for CH₂I₂ and CHBr₃. This result shows that algae are an important biological species in the polar region for the production of these halogenated substances. Whereas the brominated compounds in seawater samples correlate well with each other, CH₃I or any other iodinated compound does not correlate with the bromomethanes. This indicates a different biogenic mechanism for their formation. Under certain preconditions the annual flux from the Arctic Ocean to the atmosphere could be calculated for CH₃I to be 4×10⁹ g, for CHBr₃ to be 5.4×10¹⁰ g, which is an essential contribution to the total global budget of these important atmospheric trace gases.Dedicated to Professor Dr. Wilhelm Fresenius on the occasion of his 80th birthday     

Direct introduction of slurry samples in multi-syringe flow injection analysis: determination of potassium in plant samples.

The present work explores the slurry sampling approach for automatic, flow-based plant analysis. For this purpose, pinch valves were introduced into a multi-syringe flow injection analysis manifold to provide the repeatable aspiration of a few microliters of plant suspension before the material was further processed through the flow system. For validation of the proposed approach, the determination of potassium by flame emission spectrometry was implemented. Several parameters were studied: the concentration of plant particles in the sample suspension and the utilization of matrix modifiers. Microwave digestion was also implemented; no significant difference was found when certified reference material was analyzed with or without the in-line digestion step. The system was successfully applied to 13 samples within a concentration range of 2.5 to 100 mg g(-1). A determination frequency of 28 h(-1) was achieved and the precision was better than 4.0% (n = 12).     

Direct determination of total carbonate salts in soil samples by continuous-flow piezoelectric detection

Two new methods for the determination of total carbonate salts, as CaCO₃, in soil by continuous-flow piezoelectric (PZ) detection are proposed. Both use a piezoelectric flow cell and a manifold including a dynamic gas extraction device to purge gaseous CO₂ released by the sample solution upon acidification. One of the methods involves monitoring the pressure generated by the CO₂ produced upon addition of hydrochloric acid; in the other, the CO₂ is quantified by using a quartz crystal coated with tetramethylammonium fluoride tetrahydrate (TMAF). The precision of both methods is compared with that of the officially endorsed method. The proposed methods allow calcium carbonate amounts over the ranges 10-100 mg and 2-15 mg, respectively, to be determined. Both were applied to the determination of CaCO₃ in soil samples. The standard deviation and throughput achieved were 2.7% and 30 samples per hour, respectively, with the pressure-based method; and 6.0% and six samples per hour, respectively, with the mass-based method.     

Direct determination of five fluoroquinolones in chicken whole blood and in veterinary drugs by HPLC

A direct, accurate, and sensitive chromatographic analytical method for the quantitative determination of five fluoroquinolones (enoxacin, ofloxacin, norfloxacin, ciprofloxacin, and enrofloxacin) in chicken whole blood is proposed in the present study. For quantitative determination lamotrigine was used as internal standard at a concentration of 20 ng/microL. The developed method was successfully applied to the determination of enrofloxacin, as the main component of commercially available veterinary drugs. Fluoroquinolone antibiotics were separated on an Inertsil (250 x 4 mm) C8, 5 microm, analytical column, at ambient temperature. The mobile phase consisted of a mixture of citric acid (0.4 mol L(-1))-CH3OH-CH3CN (87:9:4% v/v) leading to retention times less than 14 min, at a flow rate 1.4 mL min(-1). UV detection at 275 nm provided limits of detection of 2 ng/mL per 20 microL injected volume for enoxacin, norfloxacin, and ciprofloxacin, 0.4 ng/mL for ofloxacin, and 4 ng/mL for enrofloxacin. Preparation of chicken blood samples is based on the deproteinization with acetonitrile while the pharmaceutical drug was simply diluted with water. Peaks of examined analytes in real samples were identified by means of a photodiode array detector. The method was validated in terms of within-day (n=6) precision and accuracy after chicken whole blood sample deproteinization by CH3CN. Using 50 microL of chicken blood sample, recovery rates at fortification levels of 40, 60, and 80 ng ranged from 86.7% to 103.7%. The applicability of the method was evaluated using real samples from chicken under fluoroquinolone treatment.     

Direct FIA-AS determination of potassium and magnesium in cement samples by use of the slurries approach

A direct procedure has been developed for the flame atomic determination of potassium and magnesium in cement samples. A 50-mg sample is dispersed in 25 ml of 0.13M nitric acid; 100 mul of this slurry is injected in a double channel FIA manifold simultaneously with 100 mul of a 10% (w/v) lanthanum solution. This procedure allows the rapid extraction of potassium and magnesium by leaching of the sample; nitric acid is not necessary if only potassium must be determined and the sample can be diluted with only distilled water. Aqueous standards are used. The manifold employed includes a well-stirred mixing chamber, which provides an adequate on-line dilution of the sample, in order to obtain emission or absorbance measurements in the dynamic range of the elements to be determined. The results obtained in the analysis of real samples agree with those found by flame atomic spectrometry after a previous alkaline fusion with lithium carbonate, and exhibit better precision. The limit of detection of the procedure is 0.007% for K(2)O and 0.01% for MgO and the precision of the entire procedure corresponds to a relative standard deviation of 1%.     

Headspace sampling of the volatile fraction of vegetable matrices

The evolution of vapour phase sampling of the volatile fraction of vegetable matrices, or of products directly related to them, over the period 1996-2007 is reviewed. High concentration capacity headspace (HCC-HS) and dynamic headspace (D-HS) techniques, that is headspace sampling approaches where the analytes in the vapour phase are concentrated into a sorbent, an adsorbent or a solvent, are considered. Advantages, disadvantages and applications to the vegetable field of several successful techniques based on these approaches are critically presented, including in-tube sorptive extraction (INCAT, HS-SPDE), headspace sorptive extraction (HSSE), solid-phase aroma concentrate extraction (SPACE), large surface area HCC-HS sampling (MESI, MME, HS-STE), headspace liquid-phase microextraction (HS-LPME) and dynamic headspace samplings (D-HS). The developments necessary to overcome some of the limits of the above approaches and techniques are also discussed in view of their application to new fields.     

Direct determination of ammoniacal nitrogen in water samples using corona discharge ion mobility spectrometry

In this study, direct determination of ammoniacal nitrogen residues in water samples using corona discharge ion mobility spectrometry (CD-IMS) was investigated. Pyridine was used as an alternate reagent gas to enhance selectivity and sensitivity of the method. The results indicate that the limit of detection (LOD) was about 9.2x10(-3)mugmL(-1) and the linear dynamic range was obtained from 0.03 to 2.00mugmL(-1). The relative standard deviation was about 11%. Furthermore, this method was successfully applied to the direct determination of ammoniacal nitrogen in river and tap water samples and the results were compared with the Nessler method. The comparison of the results validates the potential of the proposed method as an alternative technique for the analysis of the ammoniacal nitrogen in water samples.     

Sample preparation for gas chromatographic determination of halogenated volatile organic compounds in environmental and biological samples

In this review, the wide spectrum of the techniques of isolation and/or preconcentration and final determination of halogenated volatile organic compounds (HVOCs) in water, air, soil, sediment and biological fluids are presented and discussed. The techniques discussed are solvent microextraction, solid phase extraction, gas extraction (static and dynamic techniques), membrane processes and passive sampling. Also, direct techniques, such as direct aqueous injection into gas chromatography (GC) column and membrane inlet mass spectrometry, are presented. Main attention is paid to the practical application of these techniques during all HVOCs determination.     

Enantiomeric fraction determination of chiral drugs in environmental samples using chiral liquid chromatography and mass spectrometry

When it was recognized that chiral drug residues have stereospecific toxicity towards environmental organisms the attention given to enantiomeric fraction determination of chiral drugs in the environment increased. Among various analytical techniques, chiral liquid chromatography (LC) coupled with mass spectrometry (MS) has been widely used due to its simplicity, wide applicability and high sensitivity. In this review, we aim to provide a comprehensive overview and comparison of the types of chiral stationary phases, elution modes and MS detection techniques employed and address the advances and limitations. The impact of the mobile phase composition on enantioseparation and MS detection are discussed based on the different methods developed. In addition, diverse applications for the enantiomeric fraction determination of chiral drugs in environmental matrices using chiral LC and MS are discussed in depth.     

Application of solid-phase microextraction and gas chromatography-mass spectrometry to the determination of volatile organic compounds in end-exhaled breath samples

Analysis of exhaled air is of particular interest as an indicator of health as well as a tool for the diagnosis of diseases. It is also a very attractive procedure for the biological control of the exposition to hazardous solvents. This kind of analysis presents numerous advantages over other methods, the most important being that it is not an invasive procedure and, therefore, it is well accepted and can be applied to a wide range of compounds. Furthermore, the analysis is simplified since the matrix is less complex that in the case of blood or urine. In spite of these obvious advantages and the good results obtained, analysis of exhaled air is not in daily use, probably due to the fact that there are no normalized systems of sampling, thus making the interpretation of the results difficult. In this paper, a method for the determination of tetrachloroethylene in exhaled air using solid-phase microextraction is presented. This method, which can be applied to other volatile organic compounds, was developed with special emphasis of end-exhaled breath sampling. The sample is collected in a glass tube whose ends are closed once the exhalation is finished. The tube has an orifice sealed with a septum through which the fiber is inserted. Then, the fiber is desorbed in the injector of a gas chromatograph and the analysis is accomplished using mass spectrometry for the identification and quantification of the components. The proposed system avoids the need of complex sampling equipment and allows analysis of the alveolar fraction. Additionally, the system is economical and easy to handle, thus facilitating the development of normalized methods and its routine use in field studies.     

Construction and validation of an automated spray-and-trap gas chromatograph for the determination of volatile organic compounds in aqueous samples

An automated spray-and-trap (ST) chromatographic system was constructed for fast and efficient extraction of volatile organic compounds (VOCs) in aqueous samples with the capability to be deployed in the field for unattended continuous monitoring of surface or ground water. This system was built upon a commercial gas chromatograph with full automation capability using self-developed hardware and software. For sample analysis, fine droplets of the aqueous solution were generated in the extraction chamber by pressure expansion of a clean air stream through a spray nozzle. A portion of the VOCs distributed into the gas phase was retained by a multi-sorbent micro-trap kept at ambient temperature. Flash heating of the sorbent trap desorbed the enriched VOCs onto the gas chromatography (GC) with flame ionization detection (FID) for hydrocarbons or electron-capture detection (ECD) for halocarbons. In order to validate the performance of the ST method. it was compared with a more conventional method, i.e., a purge-and-trap (PT), by analyzing a serious of standard solutions containing benzene, toluene, ethylene. and o-, m-xylenes. Using a purge-and-trap method as a reference for complete extraction, the ST method showed less sensitivity. Extraction recoveries are in consistent with Henry's law constants. To test response time the ST-GC-ECD was periodically switched between tap and underground waters. Negligible carry-over of halogenated species and reproducibility better than 2% relative standard deviation (R.S.D.) can be achieved regardless of large concentration difference between the two sources, thus demonstrating applicability of the ST system for on-site monitoring.     

Direct thermal extraction and gas chromatographic-mass spectrometric determination of volatile compounds of extra-virgin olive oils

The instrumental performances of a Thermo Desorption-Cooled Injection System coupled with a gas chromatography-mass spectrometer (GC-MS) were improved by a Plackett-Burman experimental design for the direct thermal extraction of volatile compounds from extra-virgin olive oils. The obtained experimental conditions were applied to the analysis of samples from West Liguria (cv. Taggiasca > or = 90%) and Spain (cv. Arbequina), which shared such similar sensorial features that Taste Panel did not distinguish them. Principal component analysis (PCA) was then applied to the experimental data. Three linear combinations of the amounts of the lipoxygenase oxidation products proved to be decisive and sufficient in the differentiation of the two groups of samples.