Graphitized Carbon Black Sorbents Research Articles

Multi-analyte gas chromatography-mass spectrometry method to monitor bisphenols, musk fragrances, ultraviolet filters, and pesticide residues in seafood

A gas chromatography-mass spectrometry method for the analysis of thirty-six anthropogenic contaminants in the edible portion of four distinct seafood items is reported. Considering the heterogeneous composition of algae, mussels, and lean/fatty fish muscles, a generic sample preparation based on the QuEChERS procedure combined with dispersive liquid-liquid microextraction (DLLME) with in situ acetylation was successfully applied for quantification of pesticide residues, bisphenols, musk fragrances and UV-filters. Matrix effects were influenced by the type of seafood, with the lowest effects being observed with EMR-lipid and graphitized carbon black sorbents in dispersive solid-phase extraction cleanup step. Method performance features were successful evaluated in the different seafood samples – algae, mussel, lean and fatty fish muscles, following the criteria established by SANTE/12682/2019 for analytical methods for pesticide residues analysis. The detection and quantification of bisphenol F, musk fragrances (galaxolide and tonalide), UV-filters (2-ethylhexyl salicylate, 2-ethylhexyl 4-methoxycinnamate, and isoamyl 4-methoxycinnamate), and residues of permethrin in commercial samples of algae, mussel and fish collected in a Portuguese estuary support the suitability of the proposed method for future seafood monitoring by food safety authorities.

Simultaneous determination of isoxaflutole and its two metabolites in corn under field conditions by LC-MS/MS.

An improved QuEChERS method was established and verified for simultaneous determination of isoxaflutole and its metabolites diketonitrile and benzoic acid analogue residues in corn and plants. This method was mainly used to study the digestion rule and final residue level of isoxaflutole and its metabolites in corn and plants. It was hoped that the safe use of isoxaflutole in corn can be achieved eventually. The method was completed by means of ultra-performance liquid chromatography with triple quadrupole mass spectrometry. The extraction of the target substance was through acetonitrile solution containing 1% acetic acid, and the purification was through primary secondary amine, octadecylsilane and graphitized carbon black sorbent. In the method, the quantitative limits and detection limits of the three analytes were 0.005-0.01 and 0.001-0.003 mg kg-1 respectively. The half-life of isoxaflutole in the plants in Shandong and Anhui was 36.4 and 42.1 days respectively, and the digestion dynamics all conformed to the first-order kinetics. The final residues of isoxaflutole in green corn and mature corn were less than 0.02 mg kg-1 of the maximum residue limit set by the Codex Alimentarius Commission. The residual amount of isoxaflutole in corn and plants at harvest time was acceptable when isoxaflutole was applied once at a dose of 121.5g a.i. ha-1 . © 2021 Society of Chemical Industry.

Analysis of 22 free amino acids in honey from Eastern Europe and Central Asia using LC-MS/MS technique without derivatization step

This study aimed to investigate the presence of 22 free amino acids (FAAs) in six honey types from Belarus (BY), Kazakhstan (KZ) and Poland (PL), for the first time. A short sample preparation step based on extraction by formic acid/water/methanol system and a relatively simple and easy clean-up stage with graphitized carbon black sorbent were performed. Using a HILIC (hydrophilic interaction liquid chromatography) column, the separation of 22 FAAs was successfully carried out. Liquid chromatography coupled with mass spectrometry detectors (LC–MS/MS) were used in 22 FAAs analysis without a derivatization step. Eighty one samples of honey from 6 types and 3 origins with 13 combinations: honeydew (16), multifloral (18), rape (16), linden (8), buckwheat (9) and dandelion (5) contained FAAs from 127.7 mg/kg (dandelion, PL) to 1523.2 mg/kg (multifloral herbs, KZ). Proline ranged from 70.8 to 461.4 mg/kg, tyrosine was characteristic for KZ honey (429 mg/kg), and cystine was present only in PL linden honey (0.1 mg/kg). Summarized results confirm presence and the diversity of FAAs in honey of different types and origin. Honey samples were classified using chemometric methods based on the amino acid concentration. Amino acid profiling of honey is useful, additional tool, expanding standard quality and melissopalynological analysis.

Analytical Methodologies for Lipidomics in Hemp Plant.

The chemical composition of Cannabis sativa L. has been extensively studied for tens of years, but little is known about its lipidome. This chapter describes an analytical workflow for polar lipid determination in hemp. After extraction, lipids are enriched and isolated by graphitized carbon black sorbent, and the isolated lipid is analyzed by liquid chromatography (LC) coupled with high resolution mass spectrometry, leading to identification of many lipid species. We have developed a semi-automated platform using commercially available Lipostar software for lipid identification. Our approach affords the identification of 189 polar lipids in hemp extract, including sulfolipids and phospholipids. The number of the identified lipid species is by far the highest ever reported for Cannabis sativa.

Identification and Antimicrobial Activity of Medium-Sized and Short Peptides from Yellowfin Tuna (Thunnus albacares) Simulated Gastrointestinal Digestion.

Due to the rapidly increasing resistance to conventional antibiotics, antimicrobial peptides are emerging as promising novel drug candidates. In this study, peptide fragments were obtained from yellowfin tuna muscle by simulated gastrointestinal digestion, and their antimicrobial activity towards Gram-positive and Gram-negative bacteria was investigated. In particular, the antimicrobial activity of both medium- and short-sized peptides was investigated by using two dedicated approaches. Medium-sized peptides were purified by solid phase extraction on C18, while short peptides were purified thanks to a graphitized carbon black sorbent. For medium-sized peptide characterization, a peptidomic strategy based on shotgun proteomics analysis was employed, and identification was achieved by matching protein sequence database by homology, as yellowfin tuna is a non-model organism, leading to the identification of 403 peptides. As for short peptide sequences, an untargeted suspect screening approach was carried out by means of an inclusion list presenting the exact mass to charge ratios (m/z) values for all di-, tri- and tetrapeptides. In total, 572 short sequences were identified thanks to a customized workflow dedicated to short peptide analysis implemented on Compound Discoverer software.

Dissipation kinetics, dietary and ecological risk assessment of chlorantraniliprole residue in/on tomato and soil using GC-MS.

An alternate single quadrupole gas chromatography coupled with electron ionization mass spectrometry (GC-EI-MS) method was developed and validated for the determination chlorantraniliprole residue in tomato and soil. The target analyte was extracted from selected matrices with acetonitrile followed by dispersive solid-phase extraction clean up with primary secondary amine and graphitized carbon black sorbent to remove co-extractives prior to analysis. Limit of quantification of the method was 0.01μg/g and the recovery of chlorantraniliprole was in the range of 92-99% with RSD of less than 3%. The dissipation kinetics of chlorantraniliprole in tomato and soil followed first-order kinetics with the half-life of 1.26 and 1.77days, respectively. A safe waiting period of 1day suggested for safe consumption of tomato fruits considering the FSSAI maximum residue limit of 0.6μg/g. The residue concentrations were reduced in the range of 13 to 64% from tomato fruit using simple household approaches. The present study suggested that the use of chlorantraniliprole in tomato does not seem to pose any dietary risk to consumers. The ecological risk quotient (RQ) values indicated that the chlorantraniliprole residues in the soil may pose a medium level of risk to earthworms and arthropods during this period.

A clean-up strategy for identification of circulating endogenous short peptides in human plasma by zwitterionic hydrophilic liquid chromatography and untargeted peptidomics identification

Short peptides, namely di- tri- and tetra peptides, have been proven to play an important diagnostic role in several diseases. Therefore, the development of an analytical approach for their detection and identification is nowadays an important research goal. This paper describes an analytical procedure able to overcome the issues of short peptide isolation, clean-up and identification in plasma samples. Four different protocols were compared and tested to maximize both recovery and total number of identifications of short circulating plasma endogenous peptides. The purified peptides, coming from the four different tested protocols, were separated by zwitterionic hydrophilic liquid chromatography coupled to high-resolution mass spectrometry with the purpose of accomplishing an untargeted investigation based on suspect screening for short peptides in plasma. In particular, the use of Phree™ Phospholipid removal cartridge in combination with a purification step by solid phase extraction on a graphitized carbon black sorbent allowed the identification of the largest number of amino acid sequences (91 short peptides). The clean-up procedure allowed to tackle the issue of the low abundance of such peptides and their suppression during mass-spectrometric analysis. The results indicated that sample preparation is therefore fundamental for short peptide analysis in plasma samples.

Recovery and reactivity of polycyclic aromatic hydrocarbons collected on selected sorbent tubes and analyzed by thermal desorption-gas chromatography/mass spectrometry

This article describes the optimization of methodology for extending the measurement of volatile organic compounds (VOCs) to increasingly heavier polycyclic aromatic hydrocarbons (PAHs) with a detailed focus on recent sorbent tube technology. Although PAHs have lower volatility than compounds such as benzene, toluene, ethylbenzene and xylenes, these semi-volatile compounds can be detected in air and breath samples. For this work, PAHs were captured on sorbent tubes and subsequently analyzed using automated thermal desorption gas chromatography – mass spectrometry (ATD-GC/MS). While many different sorbent tubes are commercially available, optimization for airborne PAH sampling using sorbent tubes has not been previously considered. Herein, several commercially available sorbent tubes, including Carbograph 2 TD/1TD, Tenax TA, XRO-440, and inert-coated PAH tubes are compared to determine the relative recovery for eight PAHs commonly found in the environment. Certain types of sorbent materials were found to be better suited for PAH recovery during thermal desorption, and PAH reaction products were observed on several types of sorbent tubes, including graphitized carbon black sorbents with stainless steel tube materials. As such, selection of sorbent tube media should be carefully considered prior to embarking on a PAH study.

Determination of Dufulin Residue in Vegetables, Rice, and Tobacco Using Liquid Chromatography with Tandem Mass Spectrometry.

A rapid and accurate LC/MS/MS method using positive electrospray ionization was established for the determination of residues of the novel plant antiviral agent dufulin in samples of tobacco leaf (dry), tomato, cucumber, and rice. Samples were extracted with acetonitrile; cleaned up by dispersive SPE using primary secondary amine, C18, and graphitized carbon black sorbents; separated on a C18 column; and confirmed by multiple reaction monitoring mode MS with a matrix effect of -21.5-19.6%. The method showed satisfactory linearity (R2≥0.9912) for the target compound. The LOD and the LOQ were 0.05 and 0.15 μg/kg, respectively. The mean recoveries from four matrixes varied from 71.9 to 93.6% with intraday RSD in the range of 2.9 to 9.0% and interday RSD 6.9 to 15.2%. The method was successfully applied for analysis of dufulin in actual trial samples.

Dispersive Cleanup of Acetonitrile Extracts of Tea Samples by Mixed Multiwalled Carbon Nanotubes, Primary Secondary Amine, and Graphitized Carbon Black Sorbents

A method for analysis of 37 pesticide residues in tea samples was developed and validated and was based on reversed-dispersive solid-phase extraction (r-DSPE) cleanup in acetonitrile solution, followed by liquid chromatography-electrospray tandem mass spectrometry determination. Green tea, oolong tea, and puer tea were selected as matrixes and represent the majority of tea types. Acetonitrile was used as the extraction solvent, with sodium chloride and magnesium sulfate enhancing partitioning of analytes into the organic phase. The extract was then cleaned up by r-DSPE using a mixture of multiwalled carbon nanotubes, primary secondary amine, and graphitized carbon black as sorbents to absorb interferences. Further optimization of sample preparation and determination allowed recoveries of between 70% and 111% for all 37 pesticides with relative standard deviations lower than 14% at two concentration levels of 10 and 100 μg kg(-1). Limits of quantification ranged from 5 to 20 μg kg(-1) for all pesticides. The developed method was successfully applied to the determination of pesticide residues in market tea samples.

Multiresidue Pesticide Analysis of Wines by Dispersive Solid-Phase Extraction and Ultrahigh-Performance Liquid Chromatography−Tandem Mass Spectrometry

A multiresidue pesticide method is described for the determination of 72 pesticides in wines. Pesticides were extracted using acetonitrile saturated with magnesium sulfate and sodium chloride, followed by solid-phase dispersive cleanup using primary-secondary amine and graphitized carbon black sorbents. Analysis is performed by ultraperformance liquid chromatography-electrospray ionization-tandem mass spectrometry (UPLC-MS/MS). The limits of quantitation (LOQs) for most of the pesticides ranged from 0.3 to 3.3 μg/L with the exception of cyromazine, fenhexamid, and acibenzolar S-methyl (LOQ > 10 μg/L), and quantitation was determined from calibration curves of standards containing 5.0-2500 μg/L with r(2) > 0.99. Recovery studies were performed by fortifying wine samples with the pesticides to concentrations of 10, 100, and 1000 μg/L, resulting in recoveries of >80% for most of the pesticides. Lower (<70%) and higher (>120%) recoveries were most likely from complications of pesticide lability or volatility, matrix interference, or inefficient desorption from the solid-phase sorbents. The method was used to analyze 10 wines collected from a market basket survey, and 19 different pesticides, primarily fungicides, were present at concentrations ranging from <1.0 to 1000 μg/L.

Analysis of polycyclic aromatic hydrocarbons (PAHs) in airborne particles by direct sample introduction thermal desorption GC/MS

The technique of thermal desorption (TD)–GC/MS was evaluated for measuring airborne, 4–6 ring polycyclic aromatic hydrocarbons (PAHs) collected onto quartz filters. TD provides a more readily automated and sensitive alternative to traditional solvent extraction, decreasing the time/cost of analysis and reducing the risk of analyte loss or sample contamination. The developed method was successfully applied to the analysis of PAH standard solutions loaded on sorbent tubes packed with quartz wool and the graphitized carbon black sorbent Carbograph2. The optimized method showed high desorption efficiency over the whole range of target PAHs with good precision, linearity and sensitivity. The proposed method was verified on an urban dust Standard Reference Material (SRM 1649a); the experimentally determined concentrations agreed with the certified ranges (95% confidence limit) for all target compounds except benzo[a]anthracene, which fell just outside the narrow certified range. The desorption efficiency and the reproducibility of the method was evaluated by analysing pieces of real sample filters sampled from urban air for a period of 24 h. The results confirmed the homogeneity of the filter and showed high recovery efficiencies for all target PAHs.

Solid-phase extraction cleanup of tomato samples for the determination of pesticide residues by gas chromatography-electron capture detection

Extracts of tomato samples, obtained using acetone solvent followed by liquid–liquid partition with a mixture of dichloromethane and light petroleum (40–60°C), were subjected to cleanup with solid-phase extraction (SPE) columns for the simultaneous multiclass determination of 12 pesticides with different physicochemical properties (log P ow = 0.7 to > 6). Silica, aminopropyl (NH2), graphitized carbon black (GCB), octadecyl (C-18) with GCB and the mixed-mode SAX/PSA (SPE) columns were evaluated. The sample cleanup provided by these columns was evaluated using gas chromatography with electron capture detection. The mixed-mode SAX/PSA columns were found to provide the most effective cleanup, along with the (NH2) columns, removing the greatest number of sample matrix interferences. The GCB sorbents also remove pigments but do not remove noticeable chromatographic interferents. The silica columns did little to eliminate the matrix effect for the compound dimethoate. Likewise, the C-18 in combination with the GCB sorbents did little to eliminate matrix interferences.

Comparison of biodegradation of poly(ethylene glycol)s and poly(propylene glycol)s

The biodegradation of poly(ethylene glycol)s (PEGs) and poly(propylene glycol)s (PPGs), both being major by-products of non-ionic surfactants biodegradation, was studied under the conditions of the River Water Die-Away Test. PEGs were isolated from a water matrix using solid-phase extraction with graphitized carbon black sorbent, then derivatized with phenyl isocyanate and determined by HPLC with UV detection. PPGs were isolated from a water matrix by liquid–liquid extraction with chloroform, then derivatized with naphthyl isocyanate and determined by HPLC with fluorescence detection. The primary biodegradation of both PEGs and PPGs reached approximately 99% during the test. The tests show different biodegradation pathways of PEG and PPG. During PEG biodegradation, their chains are shortened leading to the formation of ethylene glycol and diethylene glycol. During PPG biodegradation, no short-chained biodegradation products were found.