气相色谱-质谱法快速测定牙膏中的二甘醇

建立了气相色谱-质谱法（GC-MS）快速测定牙膏中的二甘醇的方法。牙膏样品经三氯甲烷提取后,应用气相色谱-质谱联用仪,以选择离子监测（SIM）模式对其中的二甘醇进行分析。二甘醇的线性范围为21.24-1062 mg/L,线性相关系数（r）为0.9995;检出限和定量限分别为2.0、5.0 mg/L;高、中、低3种浓度下的回收率在88.51%-101.6%之间,相对标准偏差（RSD）在1.6%-8.11%之间;仪器对二甘醇的响应在24 h内保持稳定。     

Simultaneous determination of diethylene glycol and propylene glycol in pharmaceutical products by HPLC after precolumn derivatization with p-toluenesulfonyl isocyanate

A simple and reliable HPLC method was developed for the simultaneous quantitative analysis of diethylene glycol (DEG) and propylene glycol (PG) in pharmaceutical products by precolumn derivatization. The derivatization reagent p-toluenesulfonyl isocyanate (TSIC, 10 microL, 20% in ACN v/v) was added to 100 microL of the sample, and then 10 muL of water was added. The resulting derivatives were separated using a C(18)analytical column and a mobile phase composed of 0.01 M KH(2)PO(4)buffer (adjusted to pH 2.5 with phosphoric acid) and ACN (47:53 v/v) at 1 mL/min and 25 degrees C. For detection, UV light at 227 nm was used. The derivatization conditions including reaction time, temperature, and concentration of TSIC were optimized. The calibration curves were linear from 0.062 to 18.6 microg/mL (r(2)= 0.9999) and from 0.071 to 21.3 microg/mL (r(2) = 0.9999) for DEG and PG, respectively. The RSD values of intra- and interday assays were all below 4% for DEG and PG. The proposed method was then successfully applied to analyze two Armillarisin A injection samples and two spiked syrup samples.     

A means of analysing glycols,especially ethylene glycol and diethylene glycol,by a method used for the determination of carbohydrates in alcoholic beverages

Summary This paper describes the separation of carbohydrates/glycerol/ethylene glycol/diethylene glycol in alcoholic liquids by TLC. An in situ reaction already proven in carbohydrate analysis is used for the detection among other things, of diethylene glycol in low, unpermitted concentrations and is compared with vanadium pentoxide derivatisation also described in the literature. Only the vanadium pentoxide reaction yields satisfactory results for diethylene glycol. The information capacity of HPTLC chromatograms is also demonstrated by the simultaneous analysis of 19 samples. Chromatogram filing is an important consideration, since the lifespans of chromatograms derivatised by the two methods vary considerably. Plates or sheets treated with dichlorofluorescein can still be evaluated over a period of years, whereas plates treated with vanadium pentoxide are unusable after only a few weeks. An advantage of the latter procedure, however, is the amenability of the chromatograms to normal photocopying.     

Sensitive and robotic determination of bromate in sea water and drinking deep-sea water by headspace solid-phase micro extraction and gas chromatography–mass spectrometry

A robotic method has been established for the determination of bromate in sea water and drinking deep-sea water. Bromate in water was converted into volatile derivative, which was measured with headspace solid-phase micro extraction and gas chromatography–mass spectrometry (HS-SPME GC–MS). Derivatization reagent and the HS-SPME parameters (selection of fibre, extraction/derivatization temperature, heating time and; the morality of HCl) were optimized and selected. Under the established conditions, the detection and the quantification limits were 0.016 μg L⁻¹ and 0.051 μg L⁻¹, respectively, and the intra- and inter-day relative standard deviation was less than 7% at concentrations of 1.0 and 10.0 μg L⁻¹. The calibration curve showed good linearity with r² = 0.9998. The common ions Cl⁻, NO₃⁻, SO₄²⁻, HPO₄²⁻, H₂PO₄⁻, K⁺, Na⁺, NH₄⁺, Ca²⁺, Mg²⁺, Ba²⁺, Mn⁴⁺, Mn²⁺, Fe³⁺ and Fe²⁺ did not interfere even when present in 1000-fold excess over the active species. The method was successfully applied to the determination of bromate in sea water and drinking deep-sea water.     

Simultaneous determination of glycol ethers and their acetates in cosmetics by gas chromatography with mass spectrometry

A gas chromatography with mass spectrometry method was developed for the simultaneous determination of ten kinds of glycol ethers and their acetates in cosmetics. The samples were extracted with methanol/ethyl acetate (80:20, v/v), further treated with vortex and ultrasound, and analyzed by gas chromatography with mass spectrometry. The concentration of each analyte was calibrated by the external standard method. Under the optimal conditions, the analytes showed linear relationship in the range of 0.05–25 mg/L with determination coefficients larger than 0.9987. The limits of detection and quantification were in the range of 0.09–0.59 and 0.31–1.95 mg/kg, respectively. The average recoveries of three spiked levels were 80.2–105.4% with intra‐ and interday precisions of 1.1–6.3 and 1.9–6.5%, respectively. Method validation from different labs confirmed the satisfactory recoveries and precisions. This method shows advantages of simple, high sensitivity, and high recovery, which can be applied to the detection of glycol ethers and acetates in cosmetics.     

Development and application of methods using SPE,HPLC-DAD,LC-ESI-MS/MS and GFAAS for the determination of herbicides and metals in surface and drinking water

A preliminary study of the pollution in surface and drinking waters caused by herbicides and metals in the Municipal Water Supply System (CORSAN) in Rio Grande city, RS, Brazil, is reported. The occurrence of 5 herbicides and 9 metals was studied in surface and drinking water through the analysis of 2 sampling spots at CORSAN. The analytical determination was performed by solid-phase extraction (SPE), high performance liquid chromatography-photodiode array detection (HPLC-DAD) and liquid chromatography coupled to electrospray ionisation tandem mass spectrometry (LC-ESI-MS/MS) for herbicides, and graphite furnace atomic absorption spectrometry (GFAAS) for metals. The concentrations of herbicides in the surface water were very low; however, the herbicide clomazone was detected in more than 50% of the samples analysed in concentration exceeding 1.0?µg L^?1. The concentration of metals was below the Maximum Contaminant Level (MCL) set by the Brazilian regulation.     

Ion-pair extraction and GC-MS determination of linear alkylbenzene sulphonates in aqueous environmental samples

A GC-MS method was developed for the determination of linear alkylbenzene sulphonates (LAS) and sulphophenylcarboxylic acids (SPC) in aqueous environmental samples. LAS and SPC were isolated from aqueous samples using methylene green (MG) as ion-pair reagent and derivatised with diazomethane for their chromatographic analysis. LAS and SPC were then analysed with GC-MS in EI mode as their methyl esters. The method eliminates positive and negative interferences found by the methylene blue method and considered to be selective and sensitive for the determination of LAS and SPC in aqueous samples. The recovery of LAS was 98% with a relative standard deviation (R.S.D.) of 2.0% and the detection limit obtained from calculations by using GC-MS results based on S/N:3 was lower than 10 ppb. Obtained results revealed that the method can also be employed in the analysis of organic compounds bearing sulphate and sulphonate groups.     

Determination of highly polar compounds in water samples around former ammunition plants

Summary A method was developed for the determination of nitrobenzoic acids and nitrophenols as well as of diaminoaromatics and was applied to the analysis of water samples from the former ammunition plant at Elsnig (Saxony, Germany). The procedure is based on a preseparation into a neutral, an acidic and a basic fraction by multi-step extraction at different pH values followed by HPLC analysis with UV and electrochemical detectors, coupled in series. Applying optimized enrichment conditions, all investigated compounds were extracted from spiked distilled water with recoveries >80% and variation coefficients <7%. Similar results were obtained with spiked ground water samples. After enrichment, all compounds can be analysed by HPLC with UV detection at concentrations below 100 ngL⁻¹. The electrochemical detector (ELCD) allowed a selective and sensitive detection of the nitrophenols and especially of the diaminoaromatics and, therefore, provides, some advantages in the analysis of real samples. Presented at the 21^st ISC held in Stuttgart, Germany, 15^th–20^th September, 1996     

Ethylenediamine in the voltammetric determination of copper in sea water at a rotating mercury film electrode

The use of ethylenediamine in the voltammetric study of copper in natural sea water was evaluated for applicability with rotating thin mercury film electrodes. It was shown that this method increases the analytical sensitivity for copper at such electrodes by at least a factor of 4, and improves the detection of pH 8 labile copper.     

Cloud-point extraction,preconcentration, and spectrophotometric determination of palladium in water samples

The possibility of using Thio-Michler's Ketone (TMK), 4,4′-bis(dimethylamino) thiobenzophenone, for palladium(II) concentrated by micellar extraction at the cloud-point temperature, and later spectrophotometric determination, was investigated. Under the optimum conditions, preconcentration of 50?mL of water samples in the presence of 0.1% (w/v) octylphenoxy polyethoxy ethanol (Triton X-114), 2?×?10^?6?mol?L^?1?TMK and 1?×?10^–3?mol?L^?1 buffer solution (pH?=?3.0) gave the limit of detection of 0.47?ng?mL^?1, and the calibration graph was linear in the range of 2–50?ng?mL^–1. The recovery under optimum working conditions was higher than 97%. The proposed method has been applied to the spectrophotometric determination of palladium(II) in natural water samples after cloud-point extraction with satisfactory results.     

磁性多壁碳纳米管固相萃取-气相色谱-质谱法检测水样中的13种邻苯二甲酸酯类化合物

建立了磁性多壁碳纳米管(MWCNTs)固相萃取结合气相色谱-质谱检测水样中13种邻苯二甲酸酯类化合物(PAEs)的方法。优化了萃取时间、水样pH值、解吸溶剂的种类和用量、解吸时间等影响萃取效率的主要条件。最终确定萃取时间为10 min,水样pH 5～7,解吸溶剂为2 mL丙酮,解吸时间为5 min。在优化的条件下,各组分的萃取回收率为89.7%～100.5%。方法具有较高的灵敏度,检出限(信噪比(S/N)为3)为0.08～0.47 μg/L。3种实际样品的加标回收率为84.5%～107.5%,相对标准偏差为1.9%～12.8%。该方法操作简便、省时,准确、灵敏、环保,可用于水样中PAEs的检测,并成功地应用于自来水、瓶装饮用水和湖水样品的分析,13种PAEs均未检出。     

Determination of ethylenediaminetetraacetic acid in sea water by solid-phase extraction and high-performance liquid chromatography

The chelating agent EDTA is widely used, and as a result is showing up widely in the aquatic environment. Here we describe a preconcentration procedure for measuring EDTA concentration in sea water samples by HPLC. The procedure consists of forming an Fe(III) complex followed by solid-phase extraction using an activated carbon cartridge. After the preconcentration, EDTA was quantified by HPLC with ultraviolet detection (260 nm). The enrichment permitted the determination of EDTA at concentrations as low as 1 nM. Good recoveries were obtained for both brackish and full-strength sea water with high repeatability (RSD < 6%). The method was applied to sea water samples taken from near the mouth of the Oyabe River in Japan.     

Preconcentration and determination of naphthalene in air and water using activated carbon adsorption,carbon disulfide extraction and gas chromatography

A new method for the determination of naphthalene in air and water has been developed. The naphthalene was preconcentrated using activated carbon adsorption with carbon disulfide extraction and determined by gas chromatography with flame ionization detection. The chromatographic peak of naphthalene was separated well from the potential interferents turpentine, terpenene, isoborneol, camphor and isobornyl acetate. The detection limit was 0.52 g/ml of CS₂, equivalent to 2.6 g/m³ of air or 0.05 g/ml in 50 ml of water. The precision for 10 g/ml naphthalene was 1.7%. The adsorption capacity, sampling efficiency and desorption efficiency of 100 mg of activated carbon for naphthalene in air were 8.8 mg, 98.8% and 95.2%, respectively. The extraction efficiency of 5 ml of carbon disulfide for naphthalene in water was 97.6%. The method was successfully applied to the determination of naphthalene in air and water from an industrial plant.     

Development of a pulsed-laser,fiber-optic-based fluorimeter: determination of fluorescence decay times of polycyclic aromatic hydrocarbons in sea water

A fiber-optic-based system for remote measurement of time-resolved fluorescence emission spectra is described and characterized. A pulsed nitrogen laser is used to induce fluorescence and a time-gated, one-dimensional photodiode array is used to measure the decay of the fluorescence emission spectra. The results compare favorably with reported values for well characterized compounds having fluorescence decay times in the range 4–50 ns. The potential of using time-resolved fluorimetry (TRF) over fiber-optic cables as a means of improving the specificity of remote fluorescence determinations of spectrally similar polycyclic aromatic hydrocarbons in sea water is demonstrated.     

固相萃取-气相色谱法测定北京市水样中的邻苯二甲酸酯

研究了使用毛细管柱（OV-1701）分离、FID作为检测器的气相色谱法测定水中5种邻苯二甲酸酯（PAEs）[邻苯二甲酸二乙酯（DEP）,邻苯二甲酸二丁酯（DBP）,邻苯二甲酸丁基苄基酯（BBP）,邻苯二甲酸二（2-乙基己基）酯（DEHP）,邻苯二甲酸二环己酯（DCHP）]的色谱条件。5种PAEs检出限在0．1～0．3μg／L之间,所测PAEs的质量浓度在0．5～100μg／L范围内,RSD在2．2％～3．3％之间,各物质校正曲线（质量浓度与峰面积）的相关系数在0．9970～0．9993之间。利用固相萃取技术萃取水中PAEs,回收率在82．5％～110．5％之间,RSD在1．1％～4．0％之间。北京市吴家村污水处理厂4个采样点中邻苯二甲酸酯浓度在（0．7～193．3）μg／L之间。北京市南护城河的3个采样点中邻苯二甲酸酯浓度在（0．1～241．8）μg／L之间。     

等离子体发射光谱法测定矿山水样中硫酸盐的研究

水质中硫酸盐的测定方法很多,但对于成分复杂且盐分很高的矿山水样,传统方法操作繁琐且不环保,本文建立了等离子体发射光谱法测定矿山水样中硫酸盐的方法,样品采用硝酸和盐酸进行加热消解后既可去除硫化物,降低水质的黏度,又可实现多元素同时测定。该方法检出限为0.03mg/L,相对标准偏差为0.1～0.4%(n=6),方法具有方便,快捷,检出限低,精密度、准确度高且线性范围广的优点。     

Validation of stir bar sorptive extraction for the determination of 24 priority substances from the European Water Framework Directive in estuarine and sea water

This paper describes the validation of a method for the determination of 24 priority substances from the European Framework Directive in estuarine and sea water using the new extraction technique known as stir bar sorptive extraction (SBSE), followed by thermal desorption using capillary gas chromatography-mass spectrometry. We studied linearity, detection and quantitation limits and accuracy (which includes determination of trueness and precision). Using the lack-of-fit method we tested linearity in the 0-200 ng L⁻¹ range for all the priority substances. The detection and quantification limits were less than 5 and 10 ng L⁻¹, respectively, for most of the compounds studied. Precision was assessed by variance analysis (ANOVA) and relative standard values of less than 10% were obtained for repeatability and less than 15% for intermediate precision. The recovery percentages in spiked estuarine and sea water were close to 100%. Finally, for quality control of the method (stability of precision and accuracy through time), we developed a method for calculating Shewhart control charts based on the information obtained in the validation process.     

Continuous solid-phase extraction and gas chromatography–mass spectrometry determination of pharmaceuticals and hormones in water samples

A semi-automatic flow-based method for the simultaneous determination of 9 pharmaceuticals and 3 hormones in water samples in a single analytical run is proposed. The analytes were retained on a solid-phase extraction sorbent column and 1 μL of the eluate analysed by gas chromatography in combination with electron impact ionization mass spectrometry in the SIM mode. The sorbent used, Oasis-HLB, provided near-quantitative recovery of all analytes. The proposed method was validated with quite good analytical results including low limits of detection (0.01–0.06 ng L⁻¹ for 100 mL of water) and good linearity (r² > 0.993) throughout the studied concentration ranges. The method provided good accuracy (recoveries of 85–103%) and precision (between- and within-day RSD values less than 7%) in the determination of the pharmaceuticals and hormones in tap, river, pond, well, swimming pool and wastewater.