Analysis of alkenone unsaturation indices with fast gas chromatography/time-of-flight mass spectrometry

Extensively purified C37 alkenone references and mixtures thereof were analyzed by gas chromatography/flame ionization detection (GC/FID) and fast gas chromatography/time-of-flight mass spectrometry (GC/TOF-MS), to establish the latter as an alternative, fast, and reliable analysis method for alkenone unsaturation indices (U(k')(37)). This index is a tool for past sea surface temperature reconstructions with extensive use in paleoclimate and paleoceanographic research. TOF-MS was chosen because of its unique capability to acquire full-range spectra at high data rates (up to 500 spectra s(-1)) and to produce homogeneous spectra across a gaschromatographic peak, allowing faster separations than conventional GC/MS and the employment of enhanced peak deconvolution algorithms. Analysis time per sample could be reduced to run times of <10 min, i.e., by a factor of approximately 10 compared to conventional GC/FID (90-100 min) methods. However, %@mt;sys@%%@ital@%%@bold@%U%@reset@%%@rsf@%%@sx@%37%@be@%%@ital@%k%@rsf@%'%@sxx@%%@mx@% values from GC/TOF-MS showed deviations from those obtained by GC/FID, resulting from sensitivity differences between the C37:2 and C37:3 alkenone when analyzed by GC/TOF-MS. A solution to this bias is presented by determining compound-specific linear response factor equations to derive sensitivity ratios (SR) that allow conversion of GC/TOF-MS values into calibrated GC/FID data. Using alkenone mixtures of known composition and a variety of samples from natural environments, the applicability of this approach is demonstrated.     

Integration of continuous-flow accelerator mass spectrometry with chromatography and mass-selective detection

Physical combination of an accelerator mass spectrometry (AMS) instrument with a conventional gas chromatograph-mass spectrometer (GC/MS) is described. The resulting hybrid instrument (GC/MS/AMS) was used to monitor mass chromatograms and radiochromatograms simultaneously when (14)C-labeled compounds were injected into the gas chromatograph. Combination of the two instruments was achieved by splitting the column effluent and directing half to the mass spectrometer and half to a flow-through CuO reactor in line with the gas-accepting AMS ion source. The reactor converts compounds in the GC effluent to CO2 as required for function of the ion source. With cholesterol as test compound, the limits of quantitation were 175 pg and 0.00175 dpm injected. The accuracy achieved in analysis of five nonzero calibration standards and three quality control standards, using cholesterol-2,2,3,4,4,6-d6 as injection standard, was 100 +/- 11.8% with selected ion monitoring and 100 +/- 16% for radiochromatography. Respective values for interday precision were 1.0-3.2 and 22-32%. Application of GC/MS/AMS to a current topic of interest was demonstrated in a model metabolomic study in which cultured primary hepatocytes were given [(14)C]glucose and organic acids excreted into the culture medium were analyzed.     

Human dietary exposure to polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in Taiwan

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) levels in a total of 25 food items in Taiwan were surveyed. It was observed that shellfish and saltwater fish possessed the highest PCDD/Fs levels, 9.82 and 3.60 pg WHO-TEQ/g, respectively, on the lipid basis. The dietary intakes of humans at the ages of 12-18, 19-64, and over 65 were determined. The estimated intake were between 21.8 pg (female teenagers) and 37.6 pg (male seniors) WHO-TEQ/day; the levels varied with the dietary habits. The PCDD/F intakes for all human groups are far below the tolerable limit of 70 pg WHO-TEQ/kg b.w./month. In addition, the daily PCDD/F intake levels for duck-farmers consuming average and large amounts of PCDD/F contaminated duck eggs were examined. The result shows that consuming more than one duck egg with level higher than 10 pg WHO-TEQ/g lipid of PCDD/Fs per day could lead to a PCDD/F intake level higher than the tolerable limit. However, for normal population, there is a little risk to ingest intolerable amount of PCDD/Fs because of consuming contaminated duck eggs.     

GC/MS with post-column switching for large volume injection of headspace samples: sensitive determination of volatile organic compounds in human whole blood and urine

When volatile or semivolatile compounds are measured by headspace (HS) gas chromatography (GC)/mass spectrometry (MS), the maximum gas volume to be injected is usually 0.5-1.0 mL; over the volume, the MS detector automatically shuts down due to impairment of the vacuum rate of the MS ionization chamber. To overcome the problem, we modified the gas flow routes of a new type of GC/MS instrument to create a postcolumn switching system, which can eliminate the large volume of gas before introduction of target compounds into the MS ionization chamber. Our HS-GC/MS system enabled injection of as large as 5 mL of HS gas without any disturbance. As the first example analysis, we tried to establish the analysis of naphthalene and p-dichlorobenzene in human whole blood and urine by this method with large volume injection. The limits of detection for both compounds in whole blood and urine were as low as about 10 and 5 pg/mL, respectively. The validation data and actual measurements were also demonstrated. The new GC/MS system has great potential to analyze any type of volatile or semivolatile organic compounds in biological matrixes with very high sensitivity and full automation.     

Determination of Pentachlorophenol and Its Oil Solvent in Wood Pole Samples by SFE and GC with Postcolumn Flow Splitting for Simultaneous Detection of the Species

An alternative approach is described for the measurement of pentachlorophenol (PCP) and its oil solvent in wood samples by supercritical fluid extraction (SFE) and gas chromatography (GC). The determination is achieved over a single chromatographic run using postcolumn flow splitting for simultaneous ECD/FID detection of the SFE extracted species. First, PCP and oil components are quantitatively extracted from a 0.3-g wood sample using 10% MeOH/CO(2) supercritical fluid at 0.65 g/mL and 120 °C. An aliquot of the SFE solution is then mixed with 10 mL of a buffered aqueous phase at pH 9.4. After PCP is acetylated by the addition of 500 μL of acetic anhydride, it is followed by its extraction with 2.00 mL of hexane along with oil. Then, 0.5 μL of supernatant organic phase is injected into the GC for a selective and simultaneous determination of the species. The method has a linear response over 3 orders of magnitude for both species with a linear regression correlation coefficient higher than 0.98 (95% confidence limit) and an absolute detection limit of 60 ng of PCP and 80 μg of oil per 0.1-g wood sample. The precision (relative standard deviation) is 4% for PCP and 1% for oil as established for a typical average concentration sample. The accuracy of the SFE GC-ECD/FID combined technique for PCP and oil was assessed by analyzing wood samples collected from newly and in-service PCP/oil-impregnated red pine poles.     

顶空气相色谱/质谱法分析大豆油中正己醛含量

建立大豆油中正己醛含量的顶空气质分析方法。将大豆油试样放入密封的气化瓶中,在55℃温度下,使正己醛气化达到平衡时,取液上气体注入GC/MS,经非极性毛细管柱HP-5ms分离,质谱选择离子监测对正己醛进行定量测定。该方法在0.05~1.00μg/mL范围内线性关系良好,相关系数0.9997;最小检测限为3.15ng/mL,方法回收率在90.0~107%之间,相对标准偏差3.4%。该方法前处理简单、快速,定量准确,灵敏度高,可用于实验室检测大豆油中正己醛含量。     

Determination of [3H]-2,3,7,8-tetrachlorodibenzo-p-dioxin in human feces to ascertain its relative metabolism in man

Human feces samples from a self-dosing experiment were analyzed by gas chromatography/mass spectrometry (GC/MS) for [3H]-2,3,7,8-tetrachlorodibenzo-p-dioxin (3H-2378-TCDD) to determine that 36-44% of the radioactivity was attributable to the parent compound. This method, using isotope dilution analysis, proved to be difficult due to the unexpectedly higher native 2378-TCDD background which created abnormally large precision ranges around the calculated feces concentrations of 0.1-0.2 pg/g. These results were supported by additional analyses involving the GC/MS chemical cleanup method combined with liquid scintillation counting which showed that at most, 50% of the radioactivity was due to 2378-TCDD metabolites resulting in a minimum metabolism of 50% for these samples.     

Target and nontarget screening of organic micropollutants in water by solid-phase microextraction combined with gas chromatography/high-resolution time-of-flight mass spectrometry

The potential of gas chromatography coupled to high-resolution time-of-flight mass spectrometry (GC/TOF-MS) for screening of organic pollutants in water has been explored. After optimization of the solid-phase microextraction (SPME) step, where parameters such as fiber selection and addition of salt were studied, this extraction technique was applied to the analysis of different types of water samples. Investigation of 60 target organic pollutants, including pesticides, octyl/nonyl phenols, pentachlorobenzene, and polycyclic aromatic hydrocarbons (PAHs) was carried out by evaluating the presence of up to five representative m/z ions per analyte, measured at high mass accuracy, and the attainment of their Q/q (Q, quantitative ion; q, confirmative ion) intensity ratio. This strategy led to the detection of 4-t-octylphenol, simazine, terbuthylazine, chlorpyrifos, terbumeton, and terbutryn in several water samples at low part-per-billion levels. Full spectrum acquisition data generated by the TOF-MS analyzer also allowed subsequent investigation of the presence of polybrominated diphenyl ethers and several fungicides in samples after MS data acquisition, without the need to reanalyze the water samples. In addition, nontarget analysis was also tested by application of a deconvolution software. Several organic pollutants that did not form a part of the list of contaminants investigated were identified in the water samples, thanks to the excellent sensitivity of TOF-MS in full spectrum acquisition mode and the valuable accurate mass information provided by instrument. Bisphenol A, the antioxidant 3,5-di-tert-butyl-4-hydroxy-toluene (BHT), its metabolite 3,5-di-tert-butyl-4-hydroxybenzaldehyde (BHT-CHO), the polycyclic musk galaxolide, and the UV filter benzophenone were some of the compounds present in the water samples analyzed. SPME in combination with GC/TOF-MS has been proved to be an attractive and powerful approach for the rapid screening of multiclass organic pollutants in water, with very little sample manipulation and no solvent consumption. This combination provides to the analyst with information-rich MS data that facilitates the reliable identification of many different organic compounds in samples.     

液相色谱串联质谱法测定鸡蛋中利巴韦林及其代谢物总残留的不确定度评定

为提高鸡蛋食品安全检测结果准确性,建立了一种液相色谱串联质谱法(liquid chromatography-tandem mass spectrometry, LC-MS/MS)测定鸡蛋中的利巴韦林及其代谢物总残留量的不确定度数学模型。依据SN/T 4519-2016《出口动物源食品中利巴韦林残留量的测定》中的方法,对整个检测过程进行了不确定度评定。不确定度分量主要来源有测量的重复性、回收率、样品的称量、样品前处理稀释和定容、标准溶液配制、标准曲线拟合及仪器测定引入。经评定鸡蛋中利巴韦林及其代谢物总残留量结果为X=(9.94±0.88)μg/kg, k=2; 其中标准曲线拟合过程中引入的不确定度分量影响最大。     

Ultrasensitive determination of phencyclidine in body fluids by surface ionization organic mass spectrometry

Gas chromatography (GC)/surface ionization organic mass spectrometry (SIOMS) has been found to give much higher sensitivity for measurements of phencyclidine (PCP) than the conventional GC/electron impact (EI)-mass spectrometry (MS). Thus, we have established a detailed procedure for measurements of PCP in body fluids by both mass chromatography and selected-ion monitoring (SIM) of SIOMS using pethidine as an internal standard (IS). Good linearity was found in the range of 0.25-10 ng/mL of whole blood or urine, when measured by mass chromatography, and in the range of 0.025-1.0 ng/mL of whole blood by SIM. The recoveries of PCP and IS spiked to whole blood were 106 +/- 17% at 1 ng/mL and 113 +/- 11% at 5 ng/mL; that of IS was 97.8 +/- 10.4% at 5 ng/mL. The detection limits (signal-to-noise ratio = 3) were estimated to be 0.05 ng/mL of whole blood or urine by mass chromatography and 0.01 ng/mL of whole blood by SIM. The coefficients of intraday and interday variations were not greater than 10.3%. We could detect PCP from rat whole blood 2 h after subcutaneous injection of PCP (1 mg/kg) by mass chromatography. The mean PCP concentration in rat blood was 47.7 +/- 6.2 ng/mL (mean +/- SD, n = 4).     

Determination of parabens and triclosan in indoor dust using matrix solid-phase dispersion and gas chromatography with tandem mass spectrometry

A simple sample preparation method for the determination of four parabens and triclosan in indoor dust is presented. Analytes were extracted from the sample and isolated from interfering species using the matrix solid-phase dispersion technique. After that, they were silylated and determined by gas chromatography combined to tandem mass spectrometry (GC/MS/MS). The influence of several factors on the yield and selectivity of the extraction was evaluated in detail. Under final working conditions, samples (0.5 g) were mixed with the same amount of anhydrous sodium sulfate and dispersed on 1.25 g of C18. This blend was transferred to the top of a polypropylene cartridge containing 2 g of Florisil. After removing less polar species with 10 mL of dichloromethane, analytes were recovered using 10 mL of acetonitrile. This extract was concentrated to 1 mL, derivatized, and injected in the GC/MS/MS system. Derivatization was carried out at 45 degrees C in 5 min using 100 microL of N-methyl-N-(tert-butyldimethylsilyl) trifluoroacetamide. Quantification limits from 0.6 to 2.6 ng/g and absolute recoveries between 80 and 114% were achieved. Analysis of dust samples demonstrated the presence of the target species in indoor dust from private houses. The highest average concentration (702 ng/g) corresponded to triclosan.     

Chromatographic and ionization properties of polybrominated diphenyl ethers using GC/high-resolution MS with metastable atom bombardment and electron impact ionization

The chromatographic and ionization properties of 35 polybrominated diphenyl ether (PBDE) congeners were investigated using GC/HRMS with metastable atom bombardment (MAB) and electron impact (EI) ionization. A multiple linear regression model based on bromine substitution patterns and MOPAC calculated physical properties was developed to predict relative GC retention times of individual PBDE congeners. Although five different sources of metastable rare gas atoms (He, N2, Ar, Xe, and Kr) were investigated with MAB ionization, only MAB-N2 provided adequate ionization efficiency and predictability. Because of reduced background noise to the MS detector, MAB-N2 had a lower limit of detection for tetra- and penta-BDEs than EI, despite having a lower sensitivity. Using MAB-N2, the molecular ion was always the base peak, with little fragmentation taking place. Conversely, using EI ionization, the [M - nBr]+ peak (where n = 1-4, depending on the number of Br substituents) was the dominant ion for all PBDE congeners. Multiple linear regression models representing the molecular ion response of PBDE congeners analyzed by GC/ HRMS with MAB-N2 and EI ionization were also developed using the number and type of Br substituents and ionization potentials. A significantly higher level of predictability was obtained for the MAB-N2 response model than for EI.     

Long-term performance of a gas chromatography/tandem mass spectrometry assay for tebufelone in plasma

An automated gas chromatography/tandem mass spectrometry (GC/MS/MS) based method for the rapid determination of tebufelone (TE) in animal and human plasma has been routinely applied in our laboratory to more than 3000 samples over a 2-year period. The selectivity of MS/MS conducted on a triple quadrupole instrument, combined with the use of a stable-isotope-labeled internal standard, results in excellent analytical figures of merit, as well as minimal sample preparation, rapid analysis, and high assay reliability. The work described here goes beyond initial method development and validation studies by evaluating the long-term performance of quantitative GC/MS/MS. Electron ionization produces M.+ ions for TE and the [13C, 18O]TE internal standard, which are selected in Q1 and undergo collisionally activated dissociation in Q2. Quantitation is based on monitoring daughter ions at m/z 248 and 251, respectively, in Q3. A linear range of 1-3000 ng of TE/sample (20 pg to 60 ng injected) provides access to an effective concentration range of 0.5-30,000 ppb TE in plasma (0.1-2-g samples). The assay shows no bias and less than 10% relative standard deviation over this range. In the automated mode, less than 7 min elapse from injection to report printout and more than 70 plasma samples are routinely prepared and analyzed in a day. Such performance is consistently maintained throughout long-term application.     

虾类中五氯苯酚残留的气相色谱分析

本文建立了养殖虾类中PCP气相色谱检测方法,当样品中添加1.0～100μg/kg浓度梯度时,平均回收率在83.0%～101%,精密度在5.24%～11.3%,方法检测限为1.0μg/kg,该方法操作简单方便、重复性和稳定性好,适合实验室分析。     

Development of a method for dioxin analysis of small serum samples with reduced risk of volatilization

To analyze the dioxin content of samples, including dibenzo-p-dioxins/dibenzofurans, and coplanar polychlorinated biphenyls (Co-PCBs), a large volume is usually necessary. This is difficult, however, when analyzing clinical samples, such as serum and tissue. We therefore sought to increase the sensitivity of high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) in analyzing dioxins by injecting most of the extract from a small clinical sample. The concentration of each congener was estimated by injecting extracts of 5-g samples into a gas chromatography capillary precolumn (AT column) and by assaying extracts of 25-g samples by conventional splitless methods. We found that the limit of detection with the AT column was lower than that obtained by the splitless technique. In the AT column technique, 100 microL of the 110-microL final solution, equivalent to 4.5 g of the original sample, was injected into HRGC/HRMS. In contrast, 2 microL of the 20-microL final solution, equivalent to 2.5 g of original sample, was assayed using the splitless method. Moreover, when 25 fg of ultratrace dioxin was added to 100 microL of HRGC/HRMS sample and injected into the AT column, the peak area was almost the same as that obtained with 2 microL of HRGC/HRMS sample injected using the splitless method. Although assaying 10-20 microL of sample by the splitless method presents difficulties due to sample volatility, this problem can be reduced by using volumes larger than 100 microL. We tested this application by quantifying the parts-per-trillion levels, on a lipid weight basis, of each congener in a serum sample of 5 g using the AT column HRGC/HRMS method. We found this application to be successful and practical for mass screening of dioxin exposure in clinical samples.     

Picogram quantitation of polycyclic aromatic hydrocarbons adsorbed on aerosol particles by two-step laser mass spectrometry

Polycyclic aromatic hydrocarbons (PAHs) are emitted into the atmosphere mostly by anthropogenic combustion sources. Because of their carcinogenic and mutagenic properties, PAHs are often analyzed in air quality measurements. Atmospheric concentrations of PAHs, typically in the nanograms-per-cubic-meter range, require significant effort for sample collection and processing when conventional methods such as gas chromatography/mass spectrometry (GC/MS) or liquid chromatography/mass spectrometry are used. In contrast, two-step laser mass spectrometry (L2MS) is highly sensitive and selective for PAHs and requires almost no sample preparation. Here, we present for the first time a method based on L2MS to quantify PAHs adsorbed on aerosol particles collected on a filter. Linear ranges for quantitation were determined for five different PAHs in the mass range of 178-276 Da (i.e., phenanthrene, pyrene, chrysene, benzo[e]pyrene, benzo[ghi]perylene) covering more than 2 orders of magnitude with detection limits between 50 and 300 pg of a single PAH on a whole filter sample. A quantitative comparison with GC/MS was performed using model aerosols consisting of benzo[e]pyrene adsorbed on inorganic salt aerosol particles. On average, 25% less benzo[e]pyrene was determined with GC/MS than with L2MS, with a variability between the two methods of +/-68%. The general lower amount measured with GC/MS is attributed to losses during the sample preparation for the GC/MS measurements.     

Development and evaluation of a candidate reference measurement procedure for the determination of progesterone in human serum using isotope-dilution liquid chromatography/tandem mass spectrometry

Progesterone is a steroid hormone that is involved in regulating female reproductive processes. Its concentration in blood is measured to determine ovarian function. A candidate reference measurement procedure for progesterone in human serum involving isotope dilution coupled with liquid chromatography/tandem mass spectrometry (LC/MS/MS) has been developed and critically evaluated. The progesterone along with its internal standard (progesterone-13C2) was extracted from the serum matrix using liquid-liquid extraction prior to reversed-phase LC/MS/MS. The accuracy of the measurement was evaluated by a comparison of results of this method on a lyophilized human serum reference material for progesterone [Certified Reference Material (CRM) 347] with the certified values determined by gas chromatography/mass spectrometry (GC/MS) reference methods and by a recovery study for the added progesterone. The results of this method for progesterone agreed with the certified value within the uncertainty of the measurements for the CRM 347. The recovery of the added progesterone ranged from 100.1 to 100.9%. This method was applied to the determination of progesterone in frozen serum samples from three individual female donors with the progesterone concentrations ranging from 0.151 to 24.42 ng/g. Excellent reproducibility was obtained with within-set coefficients of variation (CVs) ranging from 0.1 to 1.4%, and between-set CVs ranging from 0.3 to 0.5%. Excellent linearity was also obtained with correlation coefficients of all linear regression lines (measured intensity ratios vs mass ratios) ranging from 0.9998 to 1.0000. The detection limit at a signal-to-noise ratio of approximately 3 was 1.8 pg of progesterone. This well-characterized LC/MS/MS method for serum progesterone, which demonstrates good accuracy and precision, low susceptibility to interferences, and comparability with GC/MS reference methods, qualifies as a reference measurement procedure that can be used to provide an accuracy base to which routine methods for progesterone can be compared and that will serve as a standard of higher order for measurement traceability.     

Picogram level quantitation of 2,3,7,8-tetrachlorodibenzo-p-dioxin in fish extracts by capillary gas chromatography/matrix isolation/Fourier transform infrared spectrometry

For the first time, gas chromatography/matrix isolation/Fourier transform infrared spectrometry (GC/MI/FTIR) has been reported to confirm the identity of 2,3,7,8-tetrachlorodibenzo-p-dioxin (2378-TCDD) and to quantify its level in fish extracts in the 170-220 pg range "on disk". When expressed on a fish tissue basis, analyte levels ranged from 15 to 45 pg/g. Spectroscopic identification was based on the position and relative intensity of seven absorption bands. Optical alignment as well as performance evaluation and optimization of the GC/MI/FTIR system are described. The use of [13C12]2378-TCDD as an internal standard was essential for quantitation, and quality assurance controls were used to verify system performance. GC/MI/FTIR quantitation of 2378-TCDD was compared with that independently found by GC with electron capture detection. Recovery of 2378-TCDD averaged 52% (n = 8, 30% relative standard deviation) for fish extracts.     

鸡蛋包装生产工艺的生命周期评价

鸡蛋包装多为一次性使用且消耗量很大,其材料一般为纸浆模塑和PVC等.基于生命周期评价(LCA)方法,利用eFootprint软件及数据库,对采用两种不同材料生产的鸡蛋包装分别建模,对二者的环境影响进行评价.研究选取的功能单位是可容装30枚鸡蛋的单个蛋托,尺寸为长292 mm、宽245 mm、高35 mm;系统边界包含该蛋托加工过程的主要工序,如包装材料加工、压制成型、分切、出厂包装等工艺过程.研究结果表明,评价对象在全球变暖潜值(GWP)、水资源消耗(WU)和初级能源消耗(PED)等环境影响方面贡献值较大,纸浆模塑蛋托这三类环境影响分别为90 g,0.17 kg,1.3 MJ,PVC蛋托这三类环境影响分别为720 g,4.27 kg,9.84 MJ.根据评价结果可知,纸浆模塑蛋托比PVC蛋托对环境产生的影响更小,故应优先选择纸浆模塑蛋托.建议在保证产品质量的前提下,优先选择对环境影响小的材料以及助剂进行产品设计、生产,并通过选择更高克重的PVC材料、修改蛋托结构设计等方式,降低包装产品对环境的影响.     

Picogram determination of "earthly-musty" odorous compounds in water using modified closed loop stripping analysis and large volume injection GC/MS

"Earthy-musty" off-flavor problems in water samples are due to organic compounds present at the sub-part-per-trillion level. Numerous analytical methods such as purge and trap, liquid/liquid extraction, and closed-loop stripping analysis (CLSA) followed by GC/MS analysis have been used to determine these compounds. However, these methods offer poor sensitivity (detection limits of approximately 1 to 10 ng/L) when compared to the 20-30 pg/L of sensorial sensitivity. The purpose of this study was to develop a new method involving a modified CLSA preconcentration technique together with large volume injection GC/MS in order to attain analytical sensitivity equal to or better than olfactory sensitivity. For eight target compounds that cause taste and odor problems in water at trace levels, the method developed was linear in the 0.05-10 ng/L range and provided recoveries greater than 70% together with satisfactory repeatability. Detection limits as low as 15-30 pg/L were achieved, representing a 50-fold improvement in sensitivity as compared to current methods. The accuracy and sensitivity of the method were demonstrated in different aqueous matrixes, including raw surface water. The method was successfully applied to earthy-musty water samples that had remained unsolved by conventional techniques, thus proving its effectiveness.