Performance characteristics and applications of a proton transfer reaction-mass spectrometer for measuring volatile organic compounds in ambient air

Data illustrating the performance characteristics of a proton transfer reaction-mass spectrometer (PTR-MS) under both laboratory and field conditions are presented. Under laboratory conditions, we demonstrate that PTR-MS measures (within 10%) a 2.6 ppbv concentration of gaseous dimethyl sulfide. Using a stepwise dilution of a gaseous isoprene standard, we demonstrate the linearity of the response of PTR-MS across 3 orders of magnitude of mixing ratios, from 100 ppbv to less than 100 pptv. By combining this data set with that of its monosubstituted 13C isotopic analogue, we demonstrate the ability of the instrumentto reliably measure concentrations as low as approximately 50 pptv and to detect concentrations at significantly lower levels. We conclude our laboratory characterization by investigating the components of the instrument noise signal (drift, mean, and range) and develop an expression (noise statistic) that reliably predicts the instrumental noise associated with any signal across a wide range of masses. In the field, we deployed a PTR-MS at a clean-air coastal site and an urban kerbside monitoring station to demonstrate the measurement of atmospheric dimethyl sulfide and benzene concentrations, respectively. At both sites, we were able to monitor diurnal variations in concentrations at unprecedented temporal resolutions (<5 min between successive measurements). We then demonstrate how the noise statistic can be applied to enable real fluctuations in atmospheric VOC concentrations to be reliably distinguished from instrument noise. We conclude by demonstrating how PTR-MS can be used to measure real-time VOC emission rate changes from vegetation in response to external forcing by examining the effect varying photon-flux density has upon emissions of isoprene from a Sitka spruce tree.     

Validation of atmospheric VOC measurements by proton-transfer-reaction mass spectrometry using a gas-chromatographic preseparation method

Proton-transfer-reaction mass spectrometry (PTR-MS) has emerged as a useful tool to study volatile organic compounds (VOCs) in the atmosphere. In PTR-MS, proton-transfer reactions with H30+ ions are used to ionize and measure VOCs in air with a high sensitivity and fast time response. Only the masses of the ionized VOCs and their fragments, if any, are determined, and these product ions are not unique indicators of VOC identities. Here, a combination of gas chromatography and PTR-MS (GC-PTR-MS) is used to validate the measurements by PTR-MS of a number of common atmospheric VOCs. We have analyzed 75 VOCs contained in standard mixtures by GC-PTR-MS, which allowed detected masses to be unambiguously related to a specific compound. The calibration factors for PTR-MS and GC-PTR-MS were compared and showed that the loss of VOCs in the sample acquisition and GC system is small. GC-PTR-MS analyses of 56 air samples from an urban site were used to address the specificity of PTR-MS in complex air masses. It is demonstrated that the ions associated with methanol, acetonitrile, acetaldehyde, acetone, benzene, toluene, and higher aromatic VOCs are free from significant interference. A quantitative intercomparison between PTR-MS and GC-PTR-MS measurements of the aforementioned VOCs was performed and shows that they are accurately measured by PTR-MS.     

PTR-ToF-MS, A Novel, Rapid, High Sensitivity and Non-Invasive Tool to Monitor Volatile Compound Release During Fruit Post-Harvest Storage: The Case Study of Apple Ripening

In the present study, the potential of PTR-ToF-MS for addressing fundamental and technical post-harvest issues was tested on the non-destructive and rapid monitoring of volatile compound evolution in three apple cultivars (‘Golden Delicious’, ‘Braeburn’ and ‘Gold Rush’) during 25 days of post-harvest shelf life ripening. There were more than 800 peaks in the PTR-ToF-MS spectra of apple headspace and many of them were associated with relevant compounds. Besides the ion produced upon proton transfer, we used the ion at mass 28.031 (C₂H ₄ ⁺ ) produced by charge transfer from residual O ₂ ⁺ as a monitor for ethylene concentration. ‘Golden Delicious’ apples were characterised by higher ethylene emission rates than ‘Gold Rush’ and ‘Braeburn’, and quantitative comparison has been supported by two segment piecewise linear model fitting. Ester evolution during post-harvest ripening is strongly dependent on endogenous ethylene concentration levels. For ‘Golden Delicious’ and ‘Braeburn’, sesquiterpenes (alpha-farnesene) exhibited a fast response to ethylene emission followed by a rapid decline after the endogenous ethylene maximum peak. Carbonyl compounds displayed a different time evolution as compared to esters and terpenes and did not show any evident relationship with ethylene. Methanol and ethanol concentrations during the entire storage period did not change significantly. We show how multivariate analysis can efficiently handle the large datasets produced by PTR-ToF-MS and that the outcomes obtained are in agreement with the literature. The different volatile compounds could be simultaneously monitored with high time resolution, providing advantages over the more established techniques for the investigation of VOC dynamics in fruit post-harvest storage trials.     

Factors contributing to the variation in the volatile composition of chocolate: Botanical and geographical origins of the cocoa beans,and brand-related formulation and processing

The intrinsic characteristics of chocolate and the complex technological process complicate the assessment of the typical features of this product and the verification of its authenticity. In this study, the influence of the botanical and geographical origin of the cocoa beans, as well as the impact of brand-related processing on the volatile organic compound (VOC) composition of the resulting chocolates was examined. A total of ninety dark chocolates available on the Dutch market were analysed using Proton-Transfer-Reaction-Mass Spectrometry (PTR-MS). The VOC profiles generated by PTR-MS (136 masses per sample) were used as fingerprints and investigated using chemometric tools to elucidate information on production factors of cocoa and subsequent processing, in the finished product. Principal component analysis (PCA) showed some clustering of the chocolates according to the botanical and geographical origins of beans as well as according to the brand. Partial least square discriminant analysis (PLS-DA) further discriminated the samples according to the three classes (botanical origin, geographical origin, brand) and the models with the best classification results were used to investigate the relevant masses for each class. PCA clustering and PLS-DA classification highlighted that chocolate profiles are strongly affected by the processing applied by the different brands. However, reflection of the botanical and geographical origins of the beans was also mirrored in the VOC composition of the chocolates. PTR-Time of Flight-MS (PTR-ToF-MS) was used to tentatively identify the VOCs of the chocolates. These measurements allowed the identification of 36 spectrometric peaks which relate to the main classes of chocolate odorant compounds, in particular, aldehydes and pyrazines, products of Maillard reactions. Several compounds already present in unroasted beans were tentatively identified in the chocolates as well, such as, acetic acid, methylpropanoic acid, 2- and 3-methylbutanoic acid, 2-phenylethanol, and tetramethylpyrazine. The results of this study emphasize the impact of the brand-related formulation and processing on VOC profiles of dark chocolates. However, using chemometrics, VOC reflection of the botanical origin and geographical origin of the beans in the chocolates was revealed, which may be useful for a future cocoa/chocolate traceability.     

Volatile organic compound emissions from dairy cows and their waste as measured by proton-transfer-reaction mass spectrometry

California dairies house approximately 1.8 million lactating and 1.5 million dry cows and heifers. State air regulatory agencies view these dairies as a major air pollutant source, but emissions data are sparse, particularly for volatile organic compounds (VOCs). The objective of this work was to determine VOC emissions from lactating and dry dairy cows and their waste using an environmental chamber. Carbon dioxide and methane were measured to provide context for the VOCs. VOCs were measured by proton-transfer-reaction mass spectrometry (PTR-MS). The compounds with highest fluxes when cows plus waste were present were methanol, acetone + propanal, dimethylsulfide, and m/z 109 (likely 4-methyl-phenol). The compounds with highest fluxes from fresh waste (urine and feces) were methanol, m/z 109, and m/z 60 (likely trimethylamine). Ethanol fluxes are reported qualitatively, and several VOCs that were likely emitted (formaldehyde, methylamine, dimethylamine) were not detectable by PTR-MS. The sum of reactive VOC fluxes measured when cows were present was a factor of 6-10 less than estimates historically used for regulatory purposes. In addition, ozone formation potentials of the dominant VOCs were -10% those of typical combustion or biogenic VOCs. Thus dairy cattle have a comparatively small impact on ozone formation per VOC mass emitted.     

Intercomparison of volatile organic carbon measurement techniques and data at La Porte during the TexAQS2000 Air Quality Study

The Texas Air Quality Study 2000 (TexAQS2000) investigated the photochemical production of ozone and the chemistry of related precursors and reaction products in the vicinity of Houston, TX. The colocation of four instruments for the measurement of volatile organic carbon compounds (VOCs) allowed a unique opportunity for the intercomparison of the different in-situ measuring techniques. The instruments included three gas chromatographs, each with a different type of detector, and a Proton-Transfer-Reaction Mass Spectrometer (PTR-MS) with each system designed to measure a different suite of VOCs. Correlation plots and correlation statistics are presented for species measured by more than one of these instruments. The GC instruments were all in agreement to within 10-20% (slope) with coefficients of variation (r2) of > or = 0.85. The PTR-MS agreement with other instruments was more dependent on species with some very good agreements (r2 values of approximately 0.95 for some aromatics), but isoprene, acetaldehyde and propene were substantially less highly correlated (0.55 < r2 < 0.80). At least part of these differences were undoubtedly due to the timing of sample acquisition in an environment in which VOC levels changed very rapidly on both quantitative and temporal scales.     

Investigation of alpha-pinene + ozone secondary organic aerosol formation at low total aerosol mass

We present a method for measuring secondary organic aerosol (SOA) production at low total organic mass concentration (COA) using proton-transfer reaction mass spectrometry (PTR-MS). PTR-MS provides high time resolution measurements of gas-phase organic species and, coupled with particle measurements, allows for the determination of aerosol yield in real time. This approach facilitates the measurement of aerosol production at low COA; in fact aerosol mass fractions can be measured during alpha-pinene consumption as opposed to only at the completion of gas-phase chemistry. The high time resolution data are consistent with both the partitioning theory of Pankow (Atmos. Environ. 1994, 28,185 and 189) and the previous experimental measurements. Experiments including the effect of UV illumination and NOx reveal additional features of alpha-pinene + ozone product photochemistry and volatility. The high time resolution data also elucidate aerosol production from alpha-pinene ozonolysis at COA < 10 microg m(-3) and show that extrapolations of current partitioning models to conditions of low COA significantly underestimate SOA production under dark, low-NOx conditions. However, extrapolations of current models overestimate SOA production under illuminated, higher-NOx conditions typical of polluted regional air masses.     

Performance assessment of proton-transfer-reaction time-of-flight mass spectrometry (PTR-TOF-MS) for analysis of isobaric compounds in food-flavour applications

Characterisation of food-flavour release using quadrupole-based on-line mass spectrometers such as proton-transfer-reaction mass spectrometry (PTR-MS, or PTR-QMS) can be complicated when nominally isobaric aroma compounds are present in complex food matrices. The recent combination of PTR-MS with time-of-flight mass spectrometry (PTR-TOF-MS) offers an analytical tool potentially capable of overcoming this problem because of its enhanced mass resolution. In this context, four pairs of isobaric compounds (cis-3-hexenol and 2,3-pentanedione, benzaldehyde and m-xylene, ethyl butanoate and 2-methylbutanol, and isobutyl isopentanoate and 1-hexanol) were investigated by PTR-TOF-MS to assess its mass-resolving power for food-flavour applications. Headspace analyses of aqueous solutions containing nominally isobaric aroma compounds that are unresolvable by PTR-QMS demonstrated that the PTR-TOF-MS mass-resolving power, which is m/z-dependent, enabled discrimination between isobaric peaks at a centre of mass separation down to at least 0.030 Da. Visual discrimination between these isobaric compound peaks in the headspace of aqueous solutions down to a concentration range of a few tens of ng mL⁻¹ was also possible, enabling an empirical method for determining the limit of quantitation in solution for single compounds. PTR-TOF-MS offers distinct advantages over conventional PTR-MS for certain flavour release applications.     

Quality changes during storage of cooked and sliced meat products measured with PTR-MS and HS-GC–MS

The changes in the VOC composition of industrially produced saveloy were measured with Proton-Transfer-Reaction Mass-Spectrometry (PTR-MS) and HeadSpace Gas chromatography–mass spectrometry (HS-GC–MS) during a six weeks storage period. A decrease in the volatile organic compounds contributing to the fresh aroma of saveloy was the main change observed with both PTR-MS and HS-GC–MS. Samples of four other types of cooked and sliced meat product were measured with PTR-MS in the middle and at the end of the four week shelf-life period. These measurements showed an increase in m/z 69, 71, 87 and 89 for the pork loin and in m/z 61 for the herbal saveloy samples. These ions were assigned to the microbial spoilage markers: acetic acid, 2- and 3-methylbutanol, 2- and 3-methylbutanal, diacetyl and acetoin. Overall, this study shows that PTR-MS has potential for quality control of cooked and sliced meat products.     

质子转移反应质谱在食品挥发性有机物检测分析中的应用

挥发性有机化合物(volatile organic compounds,VOCs)是食品风味的主要组成成分,同时也包含了食品特性的大量信息。直接检测食品释放的VOCs来进行食品科学和技术方面的研究具有便利的优点,已成为食品检测领域的重要研究方向。质子转移反应质谱(proton transfer reaction-mass spectrometry,PTR-MS)作为一种痕量VOCs检测技术,具有灵敏度高、响应时间短、操作简单且样品无需前处理等优点,可以在几秒钟内获得VOCs的绝对浓度,因此能够实时监测食品相关过程中VOCs的变化情况,对食品安全监督、质量控制以及新产品的研发等提供有力帮助。本文首先介绍了PTR-MS的工作原理、基本结构及发展现状,然后按照PTR-MS的全谱图扫描检测和VOCs实时监测两种检测方式详细总结了其在食品领域的应用和研究现状,并对其发展前景做出了展望。     

Rapid Evaluation of Poultry Meat Shelf Life Using PTR-MS

The use of proton transfer reaction mass spectrometry (PTR-MS) for freshness classification of chicken and turkey meat samples was investigated. A number of volatile organic compounds (VOCs) were selected based on the correlation (>?95%) of their concentration during storage at 4 °C over a period of 5 days with the results of the microbial analysis. In order to verify if the selected compounds are not sample-specific, a number of samples sourced from various retailers were classified using the concentration of these compounds in the samples’ volatile fraction as input variables. The classification was performed using the support vector machines (SVM) supervised pattern recognition algorithm. It was concluded that it is possible to evaluate the shelf life of meat samples obtained from the same source based on the results of a prior analysis. The PTR-MS fingerprint approach might supplement the currently used methods of shelf life evaluation of poultry due to the short time and non-destructive nature of measurement and ease of quantitative analysis.     

Full-scale chamber investigation and simulation of air freshener emissions in the presence of ozone

Volatile organic compound (VOC) emissions from one electrical plug-in type of pine-scented air freshener and their reactions with O3 were investigated in the U.S. Environmental Protection Agency indoor air research large chamber facility. Ozone was generated from a device marketed as an ozone generator air cleaner. Ozone and oxides of nitrogen concentrations and chamber conditions such as temperature, relative humidity, pressure, and air exchange rate were controlled and/or monitored. VOC emissions and some of the reaction products were identified and quantified. Source emission models were developed to predict the time/concentration profiles of the major VOCs (limonene, alpha-pinene, beta-pinene, 3-carene, camphene, benzyl propionate, benzyl alcohol, bornyl acetate, isobornyl acetate, and benzaldehyde) emitted bythe air freshener. Gas-phase reactions of VOCs from the air freshener with O3 were simulated by a photochemical kinetics simulation system using VOC reaction mechanisms and rate constants adopted from the literature. The concentration-time predictions were in good agreement with the data for O3 and VOCs emitted from the air freshener and with some of the primary reaction products. Systematic differences between the predictions and the experimental results were found for some species. Poor understanding of secondary reactions and heterogeneous chemistry in the chamber is the likely cause of these differences. The method has the potential to provide data to predict the impact of O3/VOC interactions on indoor air quality.     

Real-Time Detection of Volatiles Released During Meat Spoilage: a Case Study of Modified Atmosphere-Packaged Chicken Breast Fillets Inoculated with <Emphasis Type="Italic">Br. thermosphacta</Emphasis>

The microbial spoilage of meat is accompanied by the release of volatile organic compounds (VOCs), many of which are odorous. These compounds give spoiled meat its characteristic pungent, sour, sulphury odour that provides consumers with an indication that the meat is unpalatable. Characterising meat spoilage based on volatile markers is of interest to the food industry in view of developing food freshness indicators (FFIs) to maintain food quality and reduce food waste. Conventional analytical methods for detecting VOCs developing during food spoilage involve intermittent sampling that delivers only snapshots of the release processes and thereby only limited information on the kinetics of their production and release. Proton-transfer-reaction mass spectrometry (PTR-MS) is an on-line technique that enables the detection of VOCs in real-time, thereby offering the possibility to follow the release of VOCs with a high time resolution. An analytical method using PTR-MS was developed to enable the continuous detection of VOCs released from chicken breast fillets inoculated with Brochothrix thermosphacta and stored under modified atmosphere (30 % CO₂, 70 % O₂) at 4 °C for 1 week. The meat spoilage VOCs detected by PTR-MS displayed different temporal dynamics of production and release, depending on the extent of spoilage. This paper describes the development of an analytical set-up for real-time detection of volatile spoilage markers using PTR-MS. This case study using inoculated chicken breast fillets demonstrates the applicability of this method to characterise individual VOC release patterns, which is of potential utility in the development of FFIs for the consumer market.     

Transient changes of volatile organic compounds (VOCs) during dulce de leche preparation by a direct injection mass spectrometer based on proton transfer reaction (PTR-MS)

The capacity of a direct injection mass spectrometer based on proton transfer reaction (PTR-MS) to monitor the transient changes of the volatile organic compounds (VOCs) during dulce de leche production was investigated. We found a correlation between the mass fingerprint and some physio-chemical properties of the dulce de leche samples. The intensity of the selected mass fragments related to VOCs was positively correlated with the changes of solids content but negatively with that of water activity. Rheological and textural changes were also highly correlated with the intensity observed for several mass fragments. Hence, this relationship could be useful to predict the textural and rheological changes during heating a complex fluid. Although not all the correlations between physical changes and VOCs formation reflected a direct cause–effect relationship, but those results demonstrated the suitability of the PTR-MS technique to monitor the quality changes even in complex food mixture during thermal processing.     

Online volatile organic compound measurements using a newly developed proton-transfer ion-trap mass spectrometry instrument during New England Air Quality Study--Intercontinental Transport and Chemical Transformation 2004: performance, intercomparison, and compound identification

We have used a newly developed proton-transfer ion-trap mass spectrometry (PIT-MS) instrument for online trace gas analysis of volatile organic compounds (VOCs) during the 2004 New England Air Quality Study-Intercontinental Transport and Chemical Transformation study. The PIT-MS instrument uses proton-transfer reactions with H3O+ ions to ionize VOCs, similarto a PTR-MS (proton-transfer reaction mass spectrometry) instrument but uses an ion trap mass spectrometer to analyze the product ions. The advantages of an ion trap are the improved identification of VOCs and a near 100% duty cycle. During the experiment, the PIT-MS instrument had a detection limit between 0.05 and 0.3 pbbv (S/N = 3 (signal-to-noise ratio)) for 2-min integration time for most tested VOCs. PIT-MS was used for ambient air measurements onboard a research ship and agreed well with a gas chromatography mass spectrometer). The comparison included oxygenated VOCs, aromatic compounds, and others such as isoprene, monoterpenes, acetonitrile, and dimethyl sulfide. Automated collision-induced dissociation measurements were used to determine the contributions of acetone and propanal to the measured signal at 59 amu; both species are detected at this mass and are thus indistinguishable in conventional PTR-MS.     

Using proton transfer reaction mass spectrometry for online analysis of secondary organic aerosols

Proton-transfer-reaction mass spectrometry (PTR-MS) is a useful tool in ambient trace gas analysis, especially for the analysis of oxygenated volatile organic compounds (OVOC). Many OVOCs are produced during photooxidation of volatile organic compounds and contribute to both the gas phase and secondary organic aerosols (SOA). The inlet system of the PTR-MS instrument was modified to allow also for the measurement of the particulate phase of an aerosol with a high time resolution. The new inlet consists mainly of a denuder to strip off the gas phase, and a heater (120/150 degrees C) to vaporize the aerosol particles. This inlet system was tested with pinonic acid particles generated with a nebulizer and SOA particles formed during the photooxidation of 1,3,5-trimethylbenzene and alpha-pinene with NO(x) in a smog chamber. The performance of this new technique is discussed and the partitioning coefficients for the oxidation products are estimated.     

Ozone-initiated reactions with mixtures of volatile organic compounds under simulated indoor conditions

This study examines the primary and secondary products resulting from reactions initiated by adding ozone to complex mixtures of volatile organic compounds (VOC). The mixtures were representative of organic species typically found indoors, but the concentrations tended to be higher than normal indoor levels. Each 4-h experiment was conducted in a controlled environmental facility (CEF, 25 m3) ventilated at approximately 1.8 h(-1). The mixture investigated included 23 VOC (no O3), O3/23 VOC, O3/21 VOC (no d-limonene or alpha-pinene), and O3/terpene only (d-limonene and alpha-pinene). The net O3 concentration was approximately 40 ppb in each experiment, and the total organic concentration was 26 mg/m3 for the 23 VOC mixture, 25 mg/m3 for the 21 VOC mixture, and 1.7 mg/m3 for the d-limonene and alpha-pinene mixture. When the 23 VOC were added to the CEF containing no O3, no compounds other than those deliberately introduced were observed. When O3 was added to the CEF containing the 23 VOC mixture, both gas and condensed phase products were found, including aldehydes, organic acids, and submicron particles (140 microg/m3). When O3 was added to the CEF containing the 21 VOC without the two terpenes (O3/21 VOC condition), most of the products that were observed in the O3/23 VOC experiments were no longer present or present at much lower concentrations. Furthermore, the particle mass concentration was 2-7 microg/m3, indistinguishable from the background particle concentration level. When O3 was added to the CEF containing only two terpenes, the results were similar to those in the O3/23 VOC experiments, but the particle mass concentration (190 microg/m3) was higher. The results indicate that (i) O3 reacts with unsaturated alkenes under indoor conditions to generate submicron particles and other potentially irritating species, such as aldehydes and organic acids; (ii) the major chemical transformations that occurred under our experimental conditions were driven by O3/d-limonene and O3/alpha-pinene reactions; and (iii) the hydroxyl radicals (OH) that were generated from the O3/terpene reactions played an important role in the chemical transformations and were responsible for approximately 56-70% of the formaldehyde, almost all of the p-tolualdehyde, and 19-29% of the particle mass generated in these experiments.     

An investigation of the adsorption of C5-C12 hydrocarbons in the ppmv and ppbv ranges on Carbotrap B

The effects of concentration and temperature on the breakthrough volumes (Vb) of 23 volatile organic compounds on Carbotrap B have been determined using the frontal chromatography method. From the measured Vb, original isotherms have been produced and adsorption parameters based on the Langmuir, Freundlich, and Dubinin-Polyani adsorption models have been calculated. The calculated adsorption parameters describe the behavior of these VOC on Carbotrap B under the experimental conditions and are useful data for VOC sampling applications including adsorption modeling of pumped and diffusive sampling. Each of the adsorption models give similar results and are in good agreement with the experimental data in the ppmv concentration range. It will be shown that contrary to previous assumptions the Langmuir adsorption parameters obtained at ppmv concentrations cannot be used to predict Vb at ppbv concentrations and the calculated parameter mmax does not represent the maximum adsorbent capacity. The Freundlich and Dubinin-Polyani models are shown to be more successful in describing the adsorption behavior of the VOC at ppbv levels where Vb is independent of concentration. The isosteric heats of adsorption (-delta Hst) for some of the compounds have been determined using the Van't Hoff equation which can be used to predict the effect of temperature on Vb.     

Dynamic changes in the volatiles and sensory properties of chilled milk during exposure to light

Exposure of milk to light causes photo-oxidation and off-flavour generation. To characterise these reactions, semi-skimmed (1.5% fat) and whole (3.8% fat) extended shelf-life cows' milk were exposed to light for 20–48 h at 4 °C and volatiles in the milk headspace were measured on-line using proton-transfer-reaction mass spectrometry (PTR-MS). The flavour of the whole-milk was assessed by aroma profile analysis on both orthonasal/retronasal odour and taste after 0, 0.25, 1, 6 and 24 h light-exposure. Sensory changes perceived in milk exposed to light for up to 6 h varied in intensity and between replicates, most notably a transient sensory defect being detectable after 0.25 h exposure, but these changes did not correspond to any volatile organic compound (VOC) generation detected by PTR-MS. After 24 h, several compounds showed enhanced release profiles. Principal components analysis related these VOCs to changes in the sensory properties of the milk, described as oxidised/rancid/hay-like.     

通过式SPE-UPLC-MS/MS测定植物油中的9 种酚类抗氧化剂

建立采用通过式固相萃取柱净化，超高效液相色谱-串联质谱法同时检测植物油中9 种酚类抗氧化剂的方法。油样品中酚类抗氧化剂用酸化乙腈提取，正己烷除脂，上清液经Oasis? PRIME HLB通过式固相萃取柱净化，C18色谱柱分离，采用乙腈-水流动相进行梯度洗脱，三重四极杆质谱电喷雾多反应监测模式检测，外标法定量。结果表明：采用本实验建立的方法，没食子酸丙酯、2,4,5-三羟基苯丁酮、叔丁基对苯二酚、去甲二氢愈创木酸、叔丁基对羟基茴香醚、2,6-二叔丁基-4-羟甲基苯酚、没食子酸辛酯、2,6-二叔丁基对甲基苯酚及没食子酸十二酯9 种抗氧化剂在各自质量浓度范围内线性关系良好，相关系数（R2）大于0.994。其中9 种抗氧化剂的方法检出限（RSN=3）在0.003～0.02 mg/kg范围，定量限（RSN=10）在0.01～0.05 mg/kg范围。在0.05、5.0、50.0 mg/kg三个添加水平下，9 种抗氧化剂平均加标回收率在82.2%～115.2%之间，相对标准偏差均小于9.3%。该方法简单、高效、灵敏度高，适用于植物油中抗氧化剂的快速定性、定量分析。