Development and validation of a multiresidue method for the analysis of 151 pesticide residues in strawberry by gas chromatography coupled to a triple quadrupole mass analyzer

A new method was developed and validated for the simultaneous determination of 151 pesticide residues in strawberry by gas chromatography coupled to a triple quadrupole mass analyzer (GC/QqQ-MS/MS), mainly using the selected reaction monitoring (SRM) mode. The list of target compounds included various classes of pesticides such as organochlorine (OCPs), organophosphorus (OPPs), carbamates, pyrethroids, triazoles and dicarboximides. A single extraction of 10 g of sample with acetonitrile followed by liquid-liquid partition formed by the addition of 4 g of MgSO4 and 1 g of NaCl was applied in sample preparation. Cleanup of the extracts was carried out by applying dispersive solid-phase extraction (D-SPE) with primary secondary amine (PSA). The analysis time was 21 min. The method was subjected to a thorough validation procedure. The recovery data were obtained by spiking blank samples at two concentration levels (11.5 and 50 microg/kg), yielding recoveries in the range 70-110%. Precision values expressed as relative standard deviation (RSD) were lower than 18% and 22% for the intraday and interday precision, respectively. Linearity was studied in the range 10-200 microg/kg and determination coefficients (R(2)) were higher than 0.98% for all compounds. Limits of detection (LODs) and limits of quantification (LOQs) were established as 4 and 10 microg/kg, respectively. The overall uncertainty of the method was estimated at two different concentrations (11.5 and 50 microg/kg), being lower than 25% in both cases. According to the validation data and performance characteristics as well as the high sample throughput and low cost, the proposed method is suitable for routine application.     

Validation of a gas chromatography/triple quadrupole mass spectrometry based method for the quantification of pesticides in food commodities

A new multiresidue method has been validated in cucumber matrix for the routine analysis of 130 multiclass pesticide residues by gas chromatography/triple quadrupole mass spectrometry. The pesticides were extracted with ethyl acetate. A first identification of the pesticides was based on a tandem mass spectrometric (MS/MS) screening method, which monitors a single transition for each target compound, in less than 12 min. After that, potentially non-negative samples were analyzed again by the MS/MS confirmation/quantification method, which monitors two or three MS/MS transitions for each compound, also in less than 12 min. Performance characteristics, such as trueness, precision, linear range, detection limit (LOD) and quantification limit (LOQ), for each pesticide were calculated. The average recoveries obtained ranged between 70 and 120% at three different fortification levels (25, 200 and 500 microg/kg) with precision, expressed as relative standard deviation (RSD), values lower than 15%. The calculated LOD and LOQ were typically <3.2 and 9.6 microg/kg, respectively. Such limits were much lower than the maximum residue levels (MRLs) established by European legislation. The proposed methodology was applied to the determination of pesticides in real vegetable samples from Almería (Spain).     

Application of gas chromatography-triple quadrupole mass spectrometry in the quantification-confirmation of pesticides and polychlorinated biphenyls in eggs at trace levels

A new multiresidue method has been developed and validated for the simultaneous analysis of 57 compounds, including organochlorine and organophosphorus pesticide residues (OCPs and OPPs) and polychlorinated biphenyls (PCBs), in eggs at trace levels by gas chromatography coupled to triple quadrupole mass spectrometry (GC-QqQ-MS/MS). Egg samples were extracted by a simple and fast matrix solid phase dispersion (MSPD) procedure using C18 as sorbent, and ethyl acetate and acetonitrile saturated in n-hexane (85:15, v/v) as elution solvent with a simultaneous clean up with Florisil in-line. The QqQ analyzer acquired data in selected reaction monitoring (SRM) mode, permitting both quantification and confirmation in a single injection with a running time reduced up to 17.70 min. Recovery was in the range of 70-110% and 70-106% at 15 and 50 microg/kg, respectively. Precision values expressed as relative standard deviation (RSD) were lower than 20%. Linearity in the range of 10-150 microg/kg provided determination coefficients (R(2)) higher than 0.98 for all compounds. Limits of detection (LODs) for pesticides were < or =2.25 microg/kg and limits of quantification (LOQs) ranged from 0.02 to 7.78 microg/kg. LODs for PCBs were < or =0.41 microg/kg and LOQ were < or =0.71 microg/kg. The method was applied to real samples. Endosulfan sulphate and p,p'-DDE were found in two samples at concentrations below the first calibration level.     

Comparison of four mass analyzers for determining carbosulfan and its metabolites in citrus by liquid chromatography/mass spectrometry

Four liquid chromatography/mass spectrometry (LC/MS) systems, equipped with single quadrupole, triple quadrupole (QqQ), quadrupole ion trap (QIT) and quadrupole time-of-flight (QqTOF) mass analyzers, were evaluated for the analysis of carbosulfan and its main transformation products. The comparison of quantitative aspects (sensitivity, precision and accuracy) was emphasized. Results showed that the triple quadrupole instrument reaches at least 20-fold higher sensitivity (LOD from 0.04 to 0.4 microg kg(-1)) compared to the single quadrupole (4-70 microg kg(-1)), the QIT (4-25 microg kg(-1)) and the QqTOF (4-23 microg kg(-1)) instruments. Recoveries were over 70% for all the analytes, except dibutylamine and 7-phenolcarbofuran. Repeatabilities (within-day) were slightly better by the single quadrupole (5-10%) and the QqQ (5-9%) than by the QIT (12-16%) and the QqTOF (9-16%). Both the QqTOF and QIT offer a linear dynamic range of two orders of magnitude whereas the single quadrupole and QqQ of, at least, three orders of magnitude. The method was applied to analyze carbosulfan field-treated orange samples, in which carbosulfan, carbofuran, 3-hydroxycarbofuran, and dibutylamine were found. As an example, the mean carbosulfan concentration was 20 +/- 0.6 microg kg(-1) measured by the QqQ, 22 +/- 1.2 microg kg(-1) by the single quadrupole, 25 +/- 2.8 microg kg(-1) by the QIT, and 20 +/- 1.8 microg kg(-1) by the QqTOF. Although the QqQ is more sensitive and precise, the mean values obtained by the four instruments are acceptable and comparable. The potential of each technique for the verification of the identity of residues detected in oranges is discussed using the concept of identification points.     

气相色谱-三重四极杆串联质谱法测定蔓越橘提取物中的88种农药残留

采用改进的快速,简单、便宜、有效、稳定和可靠的前处理方法(quick,easy,cheap,effective,rugged,safe,即QuEChERS法),结合气相色谱-三重四极杆串联质谱(GC-MS/MS)检测技术,建立了蔓越橘提取物中88种农药残留的分析方法.样品由含1％乙酸的丙酮-正己烷(1∶1,v/v)溶剂...     

Identification of unknown pesticides in fruits using ultra-performance liquid chromatography-quadrupole time-of-flight mass spectrometry. Imazalil as a case study of quantification

Ultra-high-performance liquid chromatography-quadrupole time-of-flight mass spectrometry (UPLC-QqTOF-MS) is an emerging technique offering more rapid and efficient separation, as well as the possibility to obtain accurate mass measurement and tandem mass spectrometry (MS/MS). This paper deals with the use of UPLC-QqTOF-MS to identify the pesticide residues present in complex pear extracts. Carbendazim, imazalil, and ethoxyquin were successfully identified because of the accurate mass determination of their protonated molecule and their major fragments in the product ion mass spectra. A few plastic and latex additives were also found, most of them probably coming from the packaging transfer to the fruits. The potential of the UPLC-QqTOF-MS and UPLC-QqTOF-MS/MS techniques as a quantification tool is also discussed taking imazalil as example. For quantification, calibration curves were linear over a dynamic range of 2 orders of magnitude, whereas higher calibration ranges are better adjusted to polynomial curves of second and third order. Quantification using different mass windows was also assessed. Accurate quantification required mass windows as wide as 20 mDa, narrower mass windows of 5 mDa provided erroneous quantification, probably because the low ion abundance. The mean recoveries and percentage relative standard deviation (RSD) of 35 determinations for imazalil were 76% (13% RSD) by MS and 77% (14% RSD) by MS/MS. The theoretical limit of detection was 0.4 microg kg(-1), with a validated limit of quantification of 2 microg kg(-1). The quantitative data obtained using UPLC-QqTOF-MS were compared with those obtained using conventional liquid chromatography (LC)-MS/MS with a triple quadrupole (QqQ). It was concluded that UPLC-QqTOF-MS might become a powerful analytical tool for both, unknown's identification and quantification of target pesticides.     

Determination of multiresidue quinolones regulated by the European Union in pig liver samples. High-resolution time-of-flight mass spectrometry versus tandem mass spectrometry detection

The use of liquid chromatography coupled to orthogonal acceleration time-of-flight mass spectrometry (LC-ToF-MS) provides an attractive alternative to liquid chromatography coupled to quadrupole (LC-MS) or triple quadrupole mass spectrometry (LC-MS/MS) in multiresidue analysis. ToF-MS provides accurate mass information and a significantly higher mass resolution than quadrupole analyzers. In this work, the influential parameters in time-of-flight detection using an electrospray ionization (ESI) source were studied using a central composite design to obtain the main effects and their two-factor interactions. The method developed uses LC-ESI-ToF-MS to determine and characterize quinolones regulated by the EU in pig liver samples below the maximum residue limits (MRLs). Linearity, decision limit, detection capability, detection and quantification limits, precision and recoveries were determined and adequate results were obtained, with quantification limits between 1.5 and 6 microg kg(-1) and recoveries higher than 60% for all quinolones. Limits of detection are lower than 2 microg kg(-1). Results obtained using LC-ESI-ToF-MS were compared with those obtained using LC coupled to a quadrupole and to triple quadrupole mass spectrometer. The work described in this paper illustrates the suitability and excellent confirmatory potential of LC-ToF-MS for multiresidue analysis in food samples.     

凝胶渗透色谱净化-气相色谱/串联质谱分析蘑菇中的36种农药残留

建立了用凝胶渗透色谱净化-气相色谱/串联质谱分析蘑菇中36种农药残留的方法。蘑菇中的待测农药组分在30 ℃条件下用乙酸乙酯提取,高速匀浆后通过凝胶渗透色谱净化;选用填料为中性多孔的聚苯乙烯二乙烯基苯微球体的S-X3玻璃柱(22 g,19 cm×2 cm)作为凝胶渗透色谱净化柱,流动相为乙酸乙酯-环己烷(体积比为1∶1)溶液,流速5 mL/min;收集第7~15 min流出的液体用气相色谱-三重四极杆串联质谱仪测定。在0.01~1.0 mg/L的质量浓度范围内,各种农药标准溶液的线性相关系数均大于0.99。在样品中添加36种农药(添加水平为0.01,0.05,0.10 mg/kg)的混合标准溶液,平均回收率为72.6%~117.1%,相对标准偏差为2.0%~10.8%(n=5),最低检出限为 0.1~0.7 μg/kg,最低定量限为 0.2~2 μg/kg。     

Multiresidue analysis of pesticides in animal liver by gas chromatography using triple quadrupole tandem mass spectrometry

Two methods for extracting organochlorine (OCs) and organophosphorus (OPs) pesticides from animal liver have been developed. The determination was carried out by gas chromatography with electron impact ionization tandem mass spectrometry (GC-(EI-)MS/MS) using a triple quadrupole (QqQ) analyzer. First, a liquid-solid extraction performed with a high-speed homogenizer (Polytron) using ethyl acetate as solvent, and a subsequent clean-up by gel permeation chromatography (GPC) was applied, determining 34 pesticides. Secondly, a matrix solid phase dispersion (MSPD) extraction with octadecylsilyl (C(18)) sorbent combined with a Florisil clean-up and ethyl acetate elution was performed, analyzing 25 compounds. These methodologies have been tested and compared in the sample pre-treatment due to the fatty nature of the matrix. The GPC method was finally selected and validated, yielding recoveries in the range 70-115%, with precision values expressed as relative standard deviation (RSD) lower or equal to 20%, at the spiking levels of 25 and 50 microg kg(-1), and limits of quantification (LOQs) lower than the maximum residue levels (MRLs) set by the European Union in animal products, except for isofenphos. Linearity was also studied ranging between 5 and 300 microg kg(-1) for most of pesticides. This method was applied to the analysis of real liver samples of chicken, pork and lamb.     

固相萃取-三重串联四极杆气相色谱/质谱联用分析蔬菜中43种农药残留留

建立了气相色谱/三重四极杆串联质谱同时分析蔬菜中43种农药残留的方法。采用乙腈提取样品中待测组分,经固相萃取法(SPE)净化后采用气相色谱/三重四极杆串联质谱在多反应监测(MRM)模式下进行外标法定量测定。分别对青菜进行3个水平(10、80、200 μg/kg)的加标回收试验,其回收率为62.2%～170.0%,其中36种农药的回收率为70.0%～120.0%。方法的相对标准偏差(RSD)小于18%,定量限(LOQ)为0.3～4.4 μg/kg。该分析方法背景干扰低,灵敏度高,适合蔬菜中多种农药及杀虫剂残留的测定。     

Simultaneous determination of betamethasone and dexamethasone residues in bovine liver by liquid chromatography/tandem mass spectrometry

In this study a new method for the simultaneous confirmation of betamethasone and dexamethasone residues in bovine liver is presented. A Quattro LCZ triple quadrupole mass spectrometer, equipped with an atmospheric pressure ionization (API) source, was coupled to a high performance liquid chromatograph (HPLC) system. Spiked liver samples were first extracted with acetonitrile, and the extracts were purified on C-18 columns. LC separations were performed on a Hypercarb column, with acetonitrile/water (90:10, v/v, +0.3% formic acid) as the mobile phase. Retention times for dexa- and betamethasone were 6.60 and 8.50 min, respectively. Fluorometholone had a retention time of 6.70 min and was used as the internal standard. The detection of the analytes was performed in the multiple reaction monitoring (MRM) mode. The assay was linear over the range of 0.5 to 8 microg/kg for both analytes. The estimated determination limits were 0.2 microg/kg for both beta- and dexamethasone and the quantification limits were 0.4 microg/kg for dexamethasone and 0.3 microg/kg for betamethasone. Analysis precision at 1, 2 and 4 microg/kg was lower than 6.1% (relative standard deviation, RSD) and accuracy was at least 97.5%. Recoveries at 1, 2 and 4 microg/kg ranged between 56 and 69%.     

Analysis of fumonisins B(1), B(2) and B(3) in corn-based baby food by pressurized liquid extraction and liquid chromatography/tandem mass spectrometry

A sensitive and reliable method using pressurized liquid extraction (PLE) and liquid chromatography (LC)/electrospray ionization (ESI) tandem mass spectrometry with a triple quadrupole (QqQ) analyzer has been developed for the analysis of fumonisin B(1) (FB(1)), fumonisin B(2) (FB(2)) and fumonisin B(3) (FB(3)) in corn-based baby foods. Influence of several extraction parameters that affect PLE efficiency such as temperature, pressure, solvent extraction, number of cycles and dispersant/clean-up agents were studied. The selected PLE operating method was: 3g of sample was packed into 11 ml stainless-steel cell and fumonisins were extracted with methanol at 40 degrees C, 34 atm in one cycle of 5 min at 60% flush. The analytes were ionized in ESI operating with positive ion mode and identified by selecting two monitoring transitions, permitting quantification and confirmation in a single injection. Recoveries ranged from 68% to 83% at fortification levels of 200 microg kg(-1) with relative standard deviation (RSD) from 4% to 12%. The limits of quantification were from 2 microg kg(-1) for FB(1) and FB(2), and 5 microg kg(-1) for FB(3), which are below the maximum residue level established by the European Union legislation in infant formulas. The proposed method was successfully applied to the analysis of twenty seven samples of baby food products collected from different markets, and one positive sample with a content of 15.9 microg kg(-1) for FB(1), 9.2 microg kg(-1)for FB(2) and 5.8 microg kg(-1) for FB(3) was obtained. Given the simplicity and potential of the proposed procedure, its application for safety control is recommended.     

Quantification of 8-α-hydroxy-mutilin as marker residue for tiamulin in rabbit tissues by high-performance liquid chromatography-mass spectrometry

For the first time, a sensitive and specific method was developed and fully validated for the quantification of the EU marker residue of tiamulin, 8-α-hydroxy-mutilin, in rabbit muscle and liver tissues using liquid chromatography combined with positive heated electrospray ionization triple quadrupole mass spectrometry. The mass spectrometer was operated in the selected reaction monitoring (SRM) mode with selection of the [M + H]⁺ ion in both quadrupoles 1 and 3, resulting in the SRM transition m/z 337.25?>?337.25 for quantification. Chromatography was performed using a Hypersil Gold C18 column using a gradient elution program with water and methanol as mobile phases. The sample preparation procedure for the analysis of 8-α-hydroxy-mutilin in liver and muscle samples consisted of three main steps: (1) extraction of the tissue matrix using 0.1 N hydrochloric acid/acetone (50/50, v/v), (2) hydrolysis of tiamulin and metabolites to 8-α-hydroxy-mutilin in alkaline medium at 45 °C, and (3) liquid–liquid extraction in acidic medium using ethyl acetate. This is the first method presenting fully validated results, encompassing a linearity of 50 to 2,000 μg/kg, within-run and between-run accuracy and precision, limit of quantification (50 μg/kg for both muscle and liver tissues), limit of detection (muscle, 11.9 μg/kg; liver, 20.6 μg/kg), extraction recovery (muscle, 66.2 %; liver, 75.5 %), signal suppression and enhancement (muscle, 51.7 %; liver, 43.3 %), carryover, applicability and practicability, and stability during storage and analysis. This novel method is therefore sensitive enough to be used for residue depletion studies of tiamulin in rabbits and for food safety monitoring with respect to MRL compliance of residues.     

微热助吹扫捕集-超高压液相色谱-串联质谱法快速测定蔬菜中12种半挥发性农药残留

将微热助吹扫捕集技术与超高压液相色谱-串联质谱(UHPLC-MS/MS)结合,建立了蔬菜中12种半挥发性农药残留的快速分析方法。系统优化了前处理条件,在10 min内即可完成样品前处理过程。12种半挥发性农药残留在各自范围内线性关系良好,相关系数(R²)为0.991 8～0.999 7;检出限为0.3～1.3μg/kg,定量限为1.0～4.3μg/kg。实际样品的加标回收率为80.0%～120.0%,日内和日间精密度均小于10%。该方法具有基质净化效果好、前处理过程简单和分析速度快等优点,可用于蔬菜中多种半挥发农药残留的同时快速分析。     

Analytical procedure to simultaneously measure trace amounts of trenbolone acetate and beta-trenbolone residues in porcine muscle using HPLC-UVD and MS

The current study was undertaken to validate the performance for the determination of both TBA and beta-trenbolone (beta-TB) residues in porcine muscle at concentrations required to monitor compliance with the maximum residue limit (MRL). The method involves a one phase liquid-liquid extraction, cleanup with low-temperature fat precipitation, separation of the respective compounds by HPLC on a Capcell pak C(18) column, use of a methanol-water isocratic system as an eluent, and measurement by UV absorbance detection at 340 nm. Both compounds were confirmed using LC-MS/MS with electrospray interface (ESI) and a triple quadrupole (QqQ) analyzer. The method was found to be precise and accurate, with a linearity range of 1-10 microg/kg (r(2) >0.973). The intra- and interday precision showed good reproducibility with RSDs < or =13.25%. The LODs were 0.12 and 0.22 microg/kg, and the LOQs were 0.37 and 0.66 microg/kg, for TBA and beta-TB, respectively. The applicability of the method was demonstrated by analyzing real samples collected from major cities in the Republic of Korea. No residues of the selected compounds were detected in any of the samples. The advantages of our method are that it is: selective, sensitive, requires a short time for analysis (13 min), and performs simple sample extraction and clean-up procedure with low-temperature fat precipitation as compared to the previously published methods.     

气相色谱-质谱/质谱法检测蔬菜中的毒死蜱及其代谢物

建立了蔬菜中毒死蜱及其代谢物3,5,6-三氯-2-羟基吡啶（3,5,6-trichloro-2-pyridinol,TCP)的气相色谱-质谱/质谱分析方法。蔬菜样品采用丙酮提取,浓缩后TCP用N-甲基-N-叔丁基二甲基硅基三氟乙酰胺(MTBSTFA)衍生,再经氟罗里硅土固相萃取柱净化。采用三重四极杆质谱电子轰击多反应监测(MRM)模式测定。采用内标法对毒死蜱定量,方法的检出限为1 μg/kg,加标回收率为75.57%～106.41%,相对标准偏差(RSD)为8.33%～17.58%。采用外标法对TCP定量,方法的检出限为0.5 μg/kg,加标回收率为69.11%～108.43%,RSD为5.20%～19.42%。在2～100 μg/L范围内,两种被测物的线性关系良好（r＞0.99）。该方法可用于蔬菜中毒死蜱及其代谢物的检测。     

气相色谱-串联质谱双内标法测定茶叶中53种农药残留

建立了气相色谱-串联质谱（GC-MS/MS）动态多反应离子监测（dMRM）模式,结合串联双色谱柱检测茶叶中53种农药残留量的分析方法。样品中加入QuEChERS缓冲盐,用乙腈提取,采用石墨化炭黑/氨基柱（ENVI-Carb/NH₂）净化。为减少农药在GC-MS/MS分析中基质效应的影响,在标准溶液中加入古洛糖酸内酯和山梨醇作为保护剂,用蒽醌-D8和磷酸三苯酯作双内标定量。结果表明,除了氯氰菊酯的线性范围是40~1000 μg/L外,其他52种农药的线性范围均为20~500 μg/L,线性关系良好,相关系数均大于0.99;有28种农药的定量限（LOQ）小于10 μg/kg,其余25种农药的定量限为10~20 μg/kg;加标回收率为72.5%~130.9%;相对标准偏差（RSD）为0.4%~19.4%。该方法能有效地减少茶叶在GC-MS/MS上的基质效应,操作简单快速,灵敏度和选择性高,适用于农药残留的日常检测。     

Streamlining sample preparation and gas chromatography–tandem mass spectrometry analysis of multiple pesticide residues in tea

In this work, a new rapid method for the determination of 135 pesticide residues in green and black dry tea leaves and stalks employing gas chromatography coupled to tandem mass spectrometry (GC–MS/MS) with a triple quadrupole was developed and validated. A substantial simplification of sample processing prior to the quantification step was achieved: after addition of water to a homogenised sample, transfer of analytes into an acetonitrile layer was aided by the addition of inorganic salts. Bulk co-extracts, contained in the crude organic extract obtained by partition, were subsequently removed by liquid–liquid extraction using hexane with the assistance of added 20% (w/w) aqueous NaCl solution. The importance of matrix hydration prior to the extraction for achieving good recoveries was demonstrated on tea samples with incurred pesticide residues. For most of the analytes, recoveries in the acceptable range of 70–120% and repeatabilities (relative standard deviations, RSDs) ≤20% were achieved for both matrices at spiking levels of 0.01, 0.1 and 1 mg kg⁻¹. Under optimised GC–MS/MS conditions, most of the analytes gave lowest calibration level ≤0.01 mg kg⁻¹, permitting the control at the maximum residue levels (MRLs) laid down in Regulation (EC) No 396/2005. The developed method was successfully applied to the determination of pesticide residues in real tea samples.     

超高效液相色谱-电喷雾串联质谱法测定饲料中残留的三聚氰胺

饲料样品经1%三氯乙酸-二甲基亚砜提取,Waters Oasis MCX柱净化,超高效液相色谱分离,最终采用电喷雾串联四极杆质谱进行检测。结果表明,三聚氰胺在饲料中的含量范围为10～5000 μg/kg时,线性关系良好(r＞0.99)。在10～100 μg/kg 的添加水平范围内的平均回收率为83%～94%,相对标准偏差为4.2%～6.5%。该方法的检出限为10 μg/kg。     

Multi-residue analysis of pesticide residues in mangoes using solid-phase microextraction coupled to liquid chromatography and UV-Vis detection

A sensitive and efficient solid‐phase microextraction method, based on liquid chromatography and UV–Vis detection, was developed and validated as an alternative method for sample screening prior to LC‐MS analysis. It enables the simultaneous determination of ten pesticides in mango fruits. The fiber used was polydimethylsiloxane while optimum SPME conditions employed have been developed and optimized in a previous work. The desorption process was performed in static mode, using acetonitrile as a solvent. The results indicate that the DI‐SPME/HPLC/UV–Vis procedure resulted in good linear range, accuracy, precision and sensibility and is adequate for analyzing pesticide residues in mango fruits. The limits of detection (0.6–3.3 μg/kg) and quantification (2.0–10.0 μg/kg) were achieved with values lower than the maximum residue levels (MRLs) established by Brazilian legislation for all pesticides in this study. The average recovery rates obtained for each pesticide ranged from 71.6 to 104.3% at three fortification levels, with the relative standard deviation ranging from 4.3 to 18.6%. The proposed method was applied for the determination of the aforementioned compounds in commercial mango samples and residues of azoxystrobin, fenthion, permethrin, abamectin and bifenthrin were detected in the mango samples, although below the MRLs established by Brazilian legislation.