Analysis of Infant Formula for Steroid Hormones by Gas Chromatography–Tandem Mass Spectrometry Using Microwave-Assisted Extraction and Gel Permeation Chromatography Clean Up

A new method was developed for effective separation and simultaneous determination of estrogens, gestagens, and androgens, including estrone, 17β-estradiol, testosterone, progesterone, and estriol, in infant formula. The samples were enzymatically digested with β-glucuronidase/arylsulfatase prior to microwave-assisted extraction. After the extract was cleaned up by gel permeation chromatography the hormones were derivatived with 50 μL BSTFA containing 1 % TMCS. The derivatived hormones were measured with GC–MS/MS using electron impact ionization source in the positive multi-reaction monitoring mode. The calibration curves showed good linearity with correlation coefficient (r) of >0.999. The limit of quantification of five hormones ranged from 0.094 to 0.265 μg kg^?1, which is below the minimum required performance limits established by the European Community. The intra- and inter-day precision (as RSD) for six determinations of five analytes at 40 μg kg^?1 spiked level was in range of 3.4–5.4 % and 3.5–6.8 %, respectively. The recovery of five analytes was obtained to be 84.5–104 %, with relative standard deviations (RSD, n?=?6) of 1.7–5.5 %. This method has been successfully used for the qualitatively and quantitatively determination of estrone, 17β-estradiol, testosterone, progesterone, and estriol in infant formula.     

Gas Chromatography–Mass Spectrometry Analysis and Chemical Composition of the Bamboo-Carbonized Liquid

Bamboo plant is native to Asia and a popular ingredient in Asian dishes. Bamboo distillate solution has mild acidic pH of 3.0. GC–MS analysis has been done, and 43 compounds have been identified. The percentage composition of phenolic compounds, aromatic hydrocarbons, and other ingredients are identified in the acidic bamboo distillate by ether extraction method.     

Quantitative Determination and Confirmation of Five Synthetic Glucocorticoid Residues in Milk Powder by Gel Permeation Chromatography–Liquid Chromatography–Tandem Mass Spectrometry

A new method for multi-residue determination of five synthetic glucocorticoids (betamethasone, dexamethasone, prednisone, prednisolone, and hydrocortisone) in milk powder is developed. The glucocorticoids in the samples were extracted with tert-butyl methyl ether under ultrasonication incubation, and then cleaned up through gel permeation chromatography. After C18 LC gradient elution separation using acetonitrile with 0.1% formic acid as a mobile phase, the eluents were determined by liquid chromatography–tandem mass spectrometry with multiple reaction monitoring and positive ionization modes. The effective separation for the five glucocorticoids was achieved. The limit of quantification of the method for testing five glucocorticoids in milk powder was in the range from 0.2 to 0.5 μg kg⁻¹, which was lower than the maximum residue limits established by European Union for glucocorticoids in foods. Experiments on spiked samples of milk powder showed that the mean recoveries at addition level of 1.0, 3.0, and 5.0 μg kg⁻¹ were in the range of 71.2% and 103%, and the relative standard deviation ranged from 4.7% to 16.8%. The calibration curves for these drugs between 1.0 and 100 μg l⁻¹ showed good linearity, with correlation coefficient (r) more than 0.999. The real sample test showed that this method is sensitive and accurate. It can be used for qualitative and quantitative determination of studied glucocorticoid residues in milk powder samples.     

Gas Chromatography Analysis of Resin and Fatty Acids from Laboratory Generated Bleach Plant Effluents

Laboratory generated spent bleached liquor from the chlorination, caustic extraction stage of mixed wood kraft pulp processing has been analyzed both qualitatively and quantitatively for various resin & fatty acids by using GC. A number of resin acids, saturated and unsaturated fatty acids, chloro fatty and resin acid have been detected and their concentrations are estimated. The results are compared with results on different agriculture residue/hardwood pulps, which were reported earlier. The concentrations of various compounds detected have also been compared with their reported LC50 values.     

Investigation of Levels and Fate of Pyridalyl in Fruit and Vegetable Samples by Fast Gas Chromatography–Mass Spectrometry

The search on pyridalyl residues, the novel insecticide, in strawberries and spring onions was evaluated. The QuEChERS technique was used for sample preparation. A fast gas chromatography–mass spectrometry (GC–MS) method was developed and validated for the analysis of pyridalyl in both matrices. Fast GC–MS was performed with a narrow-bore capillary column and a quadrupole mass detector with electron ionization and negative chemical ionization, both operating in selected ion monitoring mode. Fortification studies at 1, 5, 10, and 250 μg/kg for fruit and vegetable matrices were performed. Recoveries for all fortification levels, two ionization modes ranged from 72 to 114 %. Matrix effects were discussed. Limits of quantification were established at 1 μg/kg. Field experiments to investigate the pre-harvest interval were carried out. The proposed method was applied successfully to the determination of pyridalyl residues in samples available on Slovak market, and none of the samples contained detectable amounts of pesticides. The developed method is simple, efficient, and easy to adopt in laboratories engaged in pesticide residue analysis method.     

Optimized Dispersive Liquid–Liquid Microextraction and Determination of Sorbic Acid and Benzoic Acid in Beverage Samples by Gas Chromatography

A new rapid method for direct determination of trace levels of sorbic and benzoic acids was developed by dispersive liquid–liquid microextraction and gas chromatography with flame ionization detection. In the proposed approach, the separation procedure of sorbic and benzoic acids was performed on a general chromatographic column without any prior derivatization processes. Some effective parameters on the microextraction recovery were studied and optimized utilizing multilevel factorial and central composite experimental designs. The best concurrent extraction efficiency acquired using ethanol and chloroform as dispersive and extraction solvents. Central composite design (CCD) resulted in the optimized values of microextraction parameters as follows: 1.0 mL of dispersive and 0.1 mL of extraction solvents, ionic salt concentration of 50 g?L^?1 at pH 4. Under optimum conditions, the calibration curve was linear over the range 0.5–20 mg L^?1. Relative standard deviation was 11% and 13% for five repeated determinations for sorbic and benzoic acids, respectively. Limits of detection were acquired as 0.2 mg L^?1 for sorbic acid and 0.5 mg L^?1 for benzoic acid. The average recoveries were 31% and 39% for sorbic and benzoic acids, respectively. The method was successfully applied to the determination of sorbic and benzoic acids as preservatives in beverage samples.     

Analysis of Peanut Using Near-Infrared Spectroscopy and Gas Chromatography–Mass Spectrometry: Correlation of Chemical Components and Volatile Compounds

Peanut contains protein, oil, oleic acid, and linoleic acid its flavor is largely determined by pyrazine and aldehyde compounds. Both nutritional value and flavor are standards for measuring peanut quality. In this report, the contents of protein, oil, oleic acid, and linoleic acid were determined using near-infrared reflectance spectroscopy, and flavor compounds were identified using headspace solid-phase microextraction combined with gas chromatography–mass spectrometry in 12 different peanut cultivars. Our results showed that the content of oleic acid in raw peanut ranged from 35.69 to 82.79 g/100 g oil and the linoleic acid content ranged from 2.92 to 44.19 g/100 g oil, with high coefficients of variation. The coefficients of variation of protein and oil were lower, with content of 26.97–33.07 g/100 g raw materials and 45.53–55.53 g/100 g raw materials, respectively. Overall, 14 volatile components were isolated and identified, among which pyrazine and aldehyde compounds were the major aroma components in 12 different peanut cultivars.. Based on these results, peanuts with high protein content have high linoleic oil levels but low oleic oil levels, and roasted peanuts have a high content of pyrazines but low content of aldehydes. The results of this study will enable manufacturers to develop simple tests that predict the flavor of roasted peanuts based on their composition.     

Liquid Chromatography–Tandem Mass Spectrometry Multiclass Method for 46 Antibiotics Residues in Milk and Meat: Development and Validation

A screening method for analysis of 46 antibiotics residues, belonging to different classes, such as tetracyclines, sulfonamides, fluoroquinolones, β-lactams, cephalosporins, macrolides and other minority groups was developed and validated for application in bovine milk and bovine, swine, poultry, equine, fish and shrimp meat samples. Sample preparation consists in solvent extraction followed by clean up with C18 bulk and low temperature purification. Instrumental analysis was performed using liquid chromatography coupled to tandem mass spectrometry system. Chromatographic separation was achieved using a C18 column. Mobile phase was composed by methanol and water. The method was validated according to Commission Decision 2002/657/EC criteria. Validation parameters such as specificity and detection capability (CCβ) were determined and considered suitable to the established criteria. Values of CCβ ranged from 1.0 to 50.0 μg L^?1 or μg Kg^?1, depending on the compound and the matrix. The proposed method has been applied into Brazilian National Residue Control Plan since 2013 for the determination of antibiotic residues. A total of 3833 samples were analyzed until the current date and 13 samples showed positive results with concentrations above the permitted. The method is fast, easy and adequate for high throughput analysis in routine laboratories.     

Simultaneous Determination of Triclabendazole and its Metabolites in Bovine and Goat Fat Tissues by Liquid Chromatography–Tandem Mass Spectrometry

A sensitive and reliable method for the simultaneous determination of triclabendazole, its main metabolites (triclabendazole sulfone and triclabendazole sulfoxide) and a marker residue (ketotriclabendazole) in edible ruminant fat tissues is developed and validated. Analytes are extracted from fat tissues with acetonitrile, and crude extracts are subjected to liquid?Cliquid extraction with n-hexane. Chromatographic separation is performed on a C₁₈ reversed-phase column with gradient elution. Analytes are detected by tandem quadrupole mass spectrometry after positive electrospray ionization by multiple reaction monitoring. Relative recoveries from spiked samples range from 86.1% to 114.3%, with relative standard deviations generally below 13.8%. Limits of detection and quantification for analytes are within 0.125?C1.25???g/kg and 0.5?C5???g/kg, respectively. The method proposed in this study was successfully applied to real sample testing.     

Identification of Acacia Honey Adulteration with Rape Honey Using Liquid Chromatography–Electrochemical Detection and Chemometrics

The adulteration of honey is generally a concern of consumers and management departments of safety and quality. Adding low-price honey to high-price honey is often seen in the market. In this study, a reliable and simple method of liquid chromatography–electrochemical detection (LC-ECD) was presented to detect the adulteration of acacia honey which was added with rape honey at different levels (5–50 %, w/w). Chromatographic separation was carried out with a reversed phase column, and the mobile phase was methanol/2 % (v/v) aqueous acetic acid. Fingerprints of authentic honeys showed that the contents of chlorogenic acid were higher in acacia honey (1.738 mg kg^?1), while those of ellagic acid were much lower (0.274 mg kg^?1) in rape honey, so the chlorogenic acid and ellagic acid could be considered as possible markers of acacia and rape honeys, respectively. Samples were classified by cluster analysis and principal component analysis (PCA) according to the contents of phenolic acids. The results of PCA showed that chlorogenic acid and ellagic acid were the major variables, and no adulterated sample was identified as authentic honey. The results of cluster analysis (CA) indicated that the samples were appropriately divided into three main clusters, and adulterated samples were identified. Therefore, acacia honey adulteration with rape honey could be undoubtedly detected by LC-ECD combined with chemometric methods down to the level of 5 %.     

Determination of 103 Pesticides and Their Main Metabolites in Animal Origin Food by QuEChERS and Liquid Chromatography–Tandem Mass Spectrometry

A rapid and sensitive analytical multiresidue method has been developed for the simultaneous determination of 103 pesticides (herbicides, insecticides, and fungicides) and 18 metabolites in foods of animal origin using liquid chromatography-tandem with triple quadrupole in dynamic multiple reaction monitoring (DMRM) mode. A modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) sample preparation technique was established, and the efficiency of the dispersive solid-phase extraction (d-SPE) cleanup step was evaluated by comparing the effects of different d-SPE sorbent combinations (primary secondary amine (PSA) + graphitized carbon black (GCB), PSA + C18, C18, and C18 + GCB). The limits of quantification (LOQs) ranged from 1 to 10 μg/kg, and the coefficient of determination (R ²) was ≥0.995 within the calibration linearity range of 0–250 μg/L for all pesticides. The combination of C18 + GCB was validated at two spiking levels (10 and 50 μg/kg) in chicken, fish, pork, and rabbit. Satisfactory recoveries (70–119%) and RSDs ≤17% were achieved for all analytes, except for naptalam (60–69%), pyrimethanil (40–49%), and thiabendazole (62–66%) at 10 μg/kg spiking level. The validated method was successfully applied to the analysis of real samples of food of animal origin.     

Determination of Benzalkonium Homologues and Didecyldimethylammonium in Powdered and Liquid Milk for Infants by Hydrophilic Interaction Liquid Chromatography–Mass Spectrometry

In this study, a hydrophilic interaction liquid chromatography–mass spectrometry (HILIC-MS/MS) method for the determination of benzalkonium (BAC) homologues and didecyldimethylammonium (DDAC) was developed. A satisfactory chromatographic separation of BAC homologues and DDAC was achieved using, as mobile phase, acetonitrile–aqueous 50 mM ammonium formate (pH 3.2) (93?+?7 v/v) at 0.3 mL min^?1. The elution order of BAC homologues was from benzyldimethylhexadecylammonium chloride (C₁₆-BAC) to benzyldimethyldecylammonium chloride (C₁₀-BAC), the exact opposite with respect to separation using reversed liquid chromatography. The instrumental method was successfully applied to powdered and liquid milk for infants (about 50 samples). From powdered milk samples, BAC and DDAC were extracted using 5 % formic acid in methanol for 60 min at 60 °C in an ultrasonic bath; after dilution with water and 5 % NH₄OH solution, a purification step using a weak cationic exchange column was performed. Satisfactory limit of detections (LODs) were achieved, below 1.0 μg kg^?1 and 0.05 μg L^?1 for powdered and liquid milk for infants, respectively. No sample was free of BAC homologues and DDAC, and in one powdered milk sample, the contamination level exceeded 500 μg kg^?1, the maximum level recommended by the Standing Committee on the Food Chain and Animal Health for food and feed.     

Supercritical Fluid Chromatography × Ultra-High Pressure Liquid Chromatography for Red Chilli Pepper Fingerprinting by Photodiode Array,Quadrupole-Time-of-Flight and Ion Mobility Mass Spectrometry (SFC × RP-UHPLC-PDA-Q-ToF MS-IMS)

The coupling of normal phase and reversed phase liquid chromatography (NP-LC × RP-LC) is one of the most effective ways to increase orthogonality in two-dimensional comprehensive separations, being the two retention mechanisms truly independent. However, such coupling is not straightforward to implement, due to immiscibility of the mobile phases, poor peak focusing at the head of the secondary column (²D), signal interferences and peak deterioration. In this research, supercritical fluid chromatography (SFC) was used in the first dimension (¹D), coupled to ultra high pressure LC (UHPLC), to alleviate incompatibility issues and provide a number of advantages related to the use of supercritical CO₂. An on-line SFC × RP-UHPLC system was implemented in an automated fashion, around two 2-position, six-port switching valves equipped with octadecyl silica cartridges for effective trapping and focusing of the analytes eluted from ¹D. A water make-up flow added to the SFC effluent permitted to efficiently focus the solutes on the sorbent material and to reduce interferences of the expanded CO₂ on the ²D separation. In addition to photodiode array and quadrupole-time-of-flight mass spectrometry detection, ion mobility separation based on analyte mass, shape and size added a fourth separation dimension for carotenoid fingerprinting in a red chilli pepper sample.     

Determination of Chlorothalonil Residue in Cabbage by a Modified QuEChERS-Based Extraction and Gas Chromatography–Mass Spectrometry

Being susceptible to any matrix with pH >5, taking cabbage as an example, the low recovery of chlorothalonil residues adsorbed onto the cabbage matrix was almost completely improved by extracting with 1/1 (v/v) acetonitrile (containing 5 % acetic acid)/toluene. Under the optimized conditions, the recoveries of chlorothalonil in cabbage fortified at three concentrations of 0.5 to 10 mg kg^?1 were 71–93 % with relative standard deviations (RSDs) lower than 6 %. The limit of detection (LOD) and the limit of quantification (LOQ) of the gas chromatography–mass spectrometry (GC–MS) method for chlorothalonil were 0.05 and 0.5 mg kg^?1, respectively, which were much lower than the maximum residue limits (MRLs). The proposed analytical method demonstrated a potential for its application to monitor for chlorothalonil and to help assure food safety, especially base-sensitive-pesticide analysis.     

Application and Optimization of Microwave-Assisted Extraction and Dispersive Liquid–Liquid Microextraction Followed by High-Performance Liquid Chromatography for the Determination of Oleuropein and Hydroxytyrosol in Olive Pomace

In the present study, a new method based on microwave-assisted extraction and dispersive liquid–liquid microextraction (MAE–DLLME) followed by high-performance liquid chromatography (HPLC) was proposed for the separation and determination of oleuropein (Ole) and hydroxytyrosol (HyT) from olive pomace samples. The effective factors in the MAE–DLLME process such as microwave power, extraction time, the type and volume of extraction, and dispersive solvents were studied and optimized with the aid of response surface methodology (RSM) based on a central composite design (CCD) to obtain the best condition for Ole and HyT extraction. At the optimized conditions, parameter values were 220 W microwave power, 12 min extraction time, 60 μL extracting solvent, and 500 μL dispersive solvent. The calibration graphs of the proposed method were linear in the range of 10–500,000 μg L^?1, with the coefficient of determination (R²) higher than 0.99 for Ole and HyT. Repeatability of the method, described as the relative standard deviation (RSD), was 4.12–5.63% (n?=?6). The limits of detection were 35 and 20 μg L^?1 for Ole and HyT, respectively. The recoveries of these compounds in the spiked olive pomace sample were from 93 to 98%. The proposed method, MAE–DLLME–HPLC–UV, was an accurate, rapid, and reliable method when compared with previous methods.     

Analysis of Pesticides in Tomato Combining QuEChERS and Dispersive Liquid–Liquid Microextraction Followed by High-Performance Liquid Chromatography

A new sample preparation procedure combining QuEChERS and dispersive liquid–liquid microextraction (DLLME) was optimized for the determination at trace levels of 13 pesticides from different chemical families (i.e. 2,4-D, acetamiprid, bentazone, cymoxanil, deltamethrin, dicamba, diuron, foramsulfuron, mesotrione, metalaxyl-M, methomyl, pyraclostrobin and tembotrione) in tomato by high-performance liquid chromatography with diode array detection. Target pesticides from tomato samples were isolated by liquid partitioning with acetonitrile and salts and cleaned up by dispersive solid-phase extraction (d-SPE); the analytes were concentrated in trichloromethane by the DLLME procedure. The disperser solvent from DLLME was used at the same time as carrier of analytes form extraction in QuEChERS method. The main factors affecting sample cleanup by d-SPE in QuEChERS and DLLME yield were optimized by means of an experimental design. Under the optimum conditions, good linearity was obtained, the recoveries of pesticides in tomato samples at spiking levels between 0.01 and 1.00 mg/kg ranged from 86 to 116 % (for foramsulfuron and cymoxanil, respectively). Precision was within 15.0 % (RSD) except at the LQ for tembotrione, which was 17.4 %. Limits of quantification achieved (ranging from 0.0058 to 0.15 mg/kg) were below the maximum residue limits established by the European Union.     

Biogenic Amines in Wines and Pomegranate Molasses—A Non-Ionic Micellar Electrokinetic Chromatography Assay with Laser-Induced Fluorescence Detection

Biogenic amines in wine samples and pomegranate molasses were detected and quantified by a nonionic micellar electrokinetic chromatography method coupled to laser-induced fluorescence detection. The method provides a satisfactory and fast separation of seven biogenic amines and matrix peaks in food samples in less than 9 min. Detection limits are between 0.42 and 1.26 nM, and precisions were lower than 3% RSD for peak areas. The recovery values were between 93% and 104%, depending on the food matrix. The method is sensitive and rapid and widely applicable for the determination of biogenic amines in wine samples and fruit molasses.     

Simultaneous Determination of Trimethoprim and Diaveridine in Tissues of Chicken, Porcine, and Fish by Hydrophilic Interaction Liquid Chromatography–Tandem Mass Spectrometry

A sensitive liquid chromatography–tandem mass spectrometry method for simultaneous determination of trimethoprim and diaveridine in edible tissue samples (chicken and porcine muscle; liver, kidney, and fat tissues as well as fish muscle) was developed and validated in this study. Trimethoprim, diaveridine, and the internal standard trimethoprim-D₃ were extracted from samples using acetonitrile. The Oasis MCX Solid-Phase Extraction Cartridge was selected for cleaning up the extracts. Chromatographic separation was performed on a hydrophilic interaction liquid chromatography column with gradient elution. The analytes were determined using triple–quadrupole mass spectrometry in positive electrospray ionization and multiple reaction monitoring mode. The relative recoveries from spiked samples ranged from 82.5 to 117.2 %, with the relative standard deviations generally being below 15.4 %. Limits of detection and quantification for analytes were within 0.3–1 and 1–2 μg kg^?1, respectively. The proposed method was successfully applied to detect trimethoprim and diaveridine in real samples.     

Simultaneous Determination of Squalene, α-Tocopherol and β-Carotene in Table Olives by Solid Phase Extraction and High-Performance Liquid Chromatography with Diode Array Detection

Olives, the fruit of the Olea europaea tree, are highly appreciated in olive oil and table olives (20 % of crops) not only for their flavor but also for their nutritional properties, especially for antioxidant compounds such as squalling (SQ), α-tocopherol (TH) and β-carotene (BC). This paper presents a new analytical method for simultaneously determining SQ, TH and BC in table olives by using solid phase extraction (SPE) and high performance-liquid chromatography with diode array detection (HPLC-DAD), avoiding the classic saponification process. The correlation coefficients of calibration curves of the analyzed compounds ranged from 0.998 to 0.999, and the recoveries were in the range of 89.4–99.6 %. The validated method was used to analyze 30 table olive samples from Italy for their content of SQ (537–1,583 mg kg^?1), TH (21–90 mg kg^?1) and BC (0.4–2.6 mg kg^?1). Finally, experiments with HPLC-MS were conducted to compare this novel method with the classic saponification procedure.     

Determination of 23 Dyes in Chili Powder and Paste by High-Performance Liquid Chromatography–Electrospray Ionization Tandem Mass Spectrometry

A sensitive and comprehensive method was developed to determine 23 prohibited dyes in chili powder and paste by high-performance liquid chromatography–electrospray ionization tandem mass spectrometry. Target compounds were simultaneously extracted from chili samples with acetonitrile and purified using freezing-lipid filtration. Chromatographic separation was achieved on a Waters UPLC BEH C18 column (100× 2.1 mm, 1.7 μm) with gradient elution. Detection and quantification were performed using mass spectrometry in multiple reaction monitoring mode. The method was validated for selectivity, linearity, recovery, precision, and limit of quantification (LOQ), using spiked chili powder and paste samples. The average recoveries of analytes were 58.6–122.1%, with relative standard deviations between 1.0% and 18.9%. The LOQs ranged from 0.2 to 50 μg/kg. This method was successfully applied to chili powder and paste obtained from local markets. Chrysoidine, Rhodamine B, Orange II, and Sudan I and IV were detected in several samples.