Effects of temperature and purity of magnesium sulfate during extraction of pesticides residues using the QuEChERS method

USDA-ARS?s Scientific Manuscript database

Despite its many documented advantages, the QuEChERS (quick, easy, cheap, effective, rugged and safe) sample preparation approach has problems with a few unstable pesticides, partly due to the exothermic reaction generated by the use of anhydrous magnesium sulfate during extraction. These pesticide...

Comparison of accelerated solvent extraction and quick, easy, cheap, effective, rugged and safe method for extraction and determination of pharmaceuticals in vegetables.

PubMed

Chuang, Ya-Hui; Zhang, Yingjie; Zhang, Wei; Boyd, Stephen A; Li, Hui

2015-07-24

Land application of biosolids and irrigation with reclaimed water in agricultural production could result in accumulation of pharmaceuticals in vegetable produce. To better assess the potential human health impact from long-term consumption of pharmaceutical-contaminated vegetables, it is important to accurately quantify the amount of pharmaceuticals accumulated in vegetables. In this study, a quick, easy, cheap, effective, rugged and safe (QuEChERS) method was developed and optimized to extract multiple classes of pharmaceuticals from vegetables, which were subsequently quantified by liquid chromatography coupled to tandem mass spectrometry. For the eleven target pharmaceuticals in celery and lettuce, the extraction recovery of the QuEChERS method ranged from 70.1 to 118.6% with relative standard deviation <20%, and the method detection limit was achieved at the levels of nanograms of pharmaceuticals per gram of vegetables. The results revealed that the performance of the QuEChERS method was comparable to, or better than that of accelerated solvent extraction (ASE) method for extraction of pharmaceuticals from plants. The two optimized extraction methods were applied to quantify the uptake of pharmaceuticals by celery and lettuce growing hydroponically. The results showed that all the eleven target pharmaceuticals could be absorbed by the vegetables from water. Compared to the ASE method, the QuEChERS method offers the advantages of short time and reduced costs of sample preparation, and less amount of organic solvents used. The established QuEChERS method could be used to determine the accumulation of multiple classes of pharmaceutical residues in vegetables and other plants, which is needed to evaluate the quality and safety of agricultural produce consumed by humans. Copyright © 2015 Elsevier B.V. All rights reserved.

Validation of an Analytical Method for Determination of Benzo[a]pyrene Bread using QuEChERS Method by GC-MS

PubMed Central

Eslamizad, Samira; Yazdanpanah, Hassan; Javidnia, Katayon; Sadeghi, Ramezan; Bayat, Mitra; Shahabipour, Sara; Khalighian, Najmeh; Kobarfard, Farzad

2016-01-01

A fast and simple modified QuEChERS (quick, easy, cheap, rugged and safe) extraction method based on spiked calibration curves and direct sample introduction was developed for determination of Benzo [a] pyrene (BaP) in bread by gas chromatography-mass spectrometry single quadrupole selected ion monitoring (GC/MS-SQ-SIM). Sample preparation includes: extraction of BaP into acetone followed by cleanup with dispersive solid phase extraction. The use of spiked samples for constructing the calibration curve substantially reduced adverse matrix-related effects. The average recovery of BaP at 6 concentration levels was in range of 95-120%. The method was proved to be reproducible with relative standard deviation less than 14.5% for all of the concentration levels. The limit of detection and limit of quantification were 0.3 ng/g and 0.5 ng/g, respectively. Correlation coefficient of 0.997 was obtained for spiked calibration standards over the concentration range of 0.5-20 ng/g. To the best of our knowledge, this is the first time that a QuEChERS method is used for the analysis of BaP in breads. The developed method was used for determination of BaP in 29 traditional (Sangak) and industrial (Senan) bread samples collected from Tehran in 2014. These results showed that two Sangak samples were contaminated with BaP. Therefore, a comprehensive survey for monitoring of BaP in Sangak bread samples seems to be needed. This is the first report concerning contamination of bread samples with BaP in Iran. PMID:27642317

Residue analysis of sixty pesticides in red swamp crayfish using QuEChERS with high-performance liquid chromatography-tandem mass spectrometry

USDA-ARS?s Scientific Manuscript database

In this study, a multi-residue analytical method using QuEChERS extraction and dispersive solid-phase extraction (d-SPE) cleanup followed by high-performance liquid chromatography–tandem mass spectrometry (HPLC-MS/MS) was developed for rapid determination of 60 pesticide residues in whole crayfish a...

Comparison of micellar extraction combined with ionic liquid based vortex-assisted liquid-liquid microextraction and modified quick, easy, cheap, effective, rugged, and safe method for the determination of difenoconazole in cowpea.

PubMed

Chen, Xiaochu; Bian, Yanli; Liu, Fengmao; Teng, Peipei; Sun, Pan

2017-10-06

Two simple sample pretreatment for the determination of difenoconazole in cowpea was developed including micellar extraction combined with ionic liquid based vortex-assisted liquid-liquid microextraction (ME-IL-VALLME) prior to high performance liquid chromatography (HPLC), and modified quick, easy, cheap, effective, rugged, and safe method (QuEChERS) coupled with HPLC-MS/MS. In ME-IL-VALLME method, the target analyte was extracted by surfactant Tween 20 micellar solution, then the supernatant was diluted with 3mL water to decrease the solubility of micellar solution. Subsequently, the vortex-assisted liquid-liquid microextraction (VALLME) procedure was performed in the diluted extraction solution by using the ionic liquid of 1-hexyl-3-methylimidazolium hexafluorophosphate ([HMIM]PF 6 ) as the extraction solvent and Tween 20 as an emulsifier to enhance the dispersion of the water-immiscible ionic liquid into the aqueous phase. Parameters that affect the extraction have been investigated in both methods Under the optimum conditions, the limits of quantitation were 0.10 and 0.05mgkg -1 , respectively. And good linearity was achieved with the correlation coefficient higher than 0.9941. The relative recoveries ranged from 78.6 to 94.8% and 92.0 to 118.0% with the relative standard deviations (RSD) of 7.9-9.6% and 1.2-3.2%, respectively. Both methods were quick, simple and inexpensive. However, the ME-IL-VALLME method provides higher enrichment factor compared with conventional QuEChERS method. The ME-IL-VALLME method has a strong potential for the determination of difenoconazole in complex vegetable matrices with HPLC. Copyright © 2017 Elsevier B.V. All rights reserved.

Pesticide Multiresidue Analysis in Cereal Grains Using Modified QuEChERS Method Combined with Automated Direct Sample Introduction GC-TOFMS and UPLC-MS/MS Techniques

USDA-ARS?s Scientific Manuscript database

The QuEChERS (quick, easy, cheap, effective, rugged, and safe) sample preparation method was modified to accommodate various cereal grain matrices (corn, oat, rice and wheat) and provide good analytical results (recoveries in the range of 70-120% and RSDs <20%) for the majority of the target pestici...

Pesticide analysis in teas and chamomile by liquid chromatography and gas chromatography tandem mass spectrometry using a modified QuEChERS method: validation and pilot survey in real samples.

PubMed

Lozano, Ana; Rajski, Łukasz; Belmonte-Valles, Noelia; Uclés, Ana; Uclés, Samanta; Mezcua, Milagros; Fernández-Alba, Amadeo R

2012-12-14

This paper presents the validation of a modified QuEChERS method in four matrices - green tea, red tea, black tea and chamomile. The experiments were carried out using blank samples spiked with a solution of 86 pesticides (insecticides, fungicides and herbicides) at four levels - 10, 25, 50 and 100 μg/kg. The samples were extracted according to the citrate QuEChERS protocol; however, to reduce the amount of coextracted matrix compounds, calcium chloride was employed instead of magnesium sulphate in the clean-up step. The samples were analysed by LC-MS/MS and GC-MS/MS. Included in the scope of validation were: recovery, linearity, matrix effects, limits of detection and quantitation as well as intra-day and inter-day precision. The validated method was used in a real sample survey carried out on 75 samples purchased in ten different countries. In all matrices, recoveries of the majority of compounds were in the 70-120% range and were characterised by precision lower than 20%. In 85% of pesticide/matrix combinations the analytes can be detected quantitatively by the proposed method at the European Union Maximum Residue Level. The analysis of the real samples revealed that large number of teas and chamomiles sold in the European Union contain pesticides whose usage is not approved and also pesticides in concentrations above the EU MRLs. Copyright © 2012 Elsevier B.V. All rights reserved.

Multifamily determination of pesticide residues in soya-based nutraceutical products by GC/MS-MS.

PubMed

Páleníková, Agneša; Martínez-Domínguez, Gerardo; Arrebola, Francisco Javier; Romero-González, Roberto; Hrouzková, Svetlana; Frenich, Antonia Garrido

2015-04-15

An analytical method based on a modified QuEChERS extraction coupled with gas chromatography-tandem mass spectrometry (GC-MS/MS) was evaluated for the determination of 177 pesticides in soya-based nutraceutical products. The QuEChERS method was optimised and different extraction solvents and clean-up approaches were tested, obtaining the most efficient conditions with a mixture of sorbents (PSA, C18, GBC and Zr-Sep(+)). Recoveries were evaluated at 10, 50 and 100 μg/kg and ranged between 70% and 120%. Precision was expressed as relative standard deviation (RSD), and it was evaluated for more than 160 pesticides as intra and inter-day precision, with values always below 20% and 25%, respectively. Limits of detection (LODs) ranged from 0.1 to 10 μg/kg, whereas limits of quantification (LOQs) from 0.5 to 20 μg/kg. The applicability of the method was proved by analysing soya-based nutraceuticals. Two pesticides were found in these samples, malathion and pyriproxyfen, at 11.1 and 1.5 μg/kg respectively. Copyright © 2014 Elsevier Ltd. All rights reserved.

Food safety traits of mussels and clams: distribution of PCBs, PBDEs, OCPs, PAHs and PFASs in sample from different areas using HRMS-Orbitrap® and modified QuEChERS extraction followed by GC-MS/MS.

PubMed

Chiesa, Luca Maria; Nobile, Maria; Malandra, Renato; Pessina, Davide; Panseri, Sara; Labella, Giuseppe Federico; Arioli, Francesco

2018-05-01

Reviewing the presence of contaminant residues is important both for food safety and for monitoring of environmental pollution. Here, the occurrence of 6 polychlorinated biphenyls (PCBs), 15 organochlorine pesticides (OCPs), 7 polybrominated diphenyl ethers (PBDEs), 4 polycyclic aromatic hydrocarbons (PAHs) and 17 perfluoroalkyl substances (PFASs) was evaluated in mussels and clams. A liquid chromatography-high resolution mass spectrometry (HPLC-HRMS) and an innovative QuEChERS extraction followed by gas chromatography-tandem mass spectrometry (GC-MS/MS) methods were developed, validated and applied. We demonstrate good linearity, repeatability and accuracy of these methods, confirming that they are suitable for the analyses of mollusc samples. The prevalence of PCBs, OCPs and PAHs was higher in mussels than in clams. For PFASs, contamination was higher in clams than in mussels. The samples were all compliant with the regulations, and, for the compounds without legislative limits, a risk assessment confirmed that the values were lower than the tolerable intakes.

Validation of QuEChERS based method for determination of fenitrothion residues in tomatoes by gas chromatography-flame photometric detector: Decline pattern and risk assessment.

PubMed

Malhat, Farag; Boulangé, Julien; Abdelraheem, Ehab; Abd Allah, Osama; Abd El-Hamid, Rania; Abd El-Salam, Shokr

2017-08-15

A simple and rapid gas chromatography with flame photometric detector (GC-FPD) determination method was developed to detect residue levels and investigate the dissipation pattern and safe use of fenitrothion in tomatoes. A modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) using an ethyl acetate-based extraction, followed by a dispersive solid-phase extraction (d-SPE) with primary-secondary amine (PSA) and graphite carbon black (GCB) for clean up, was applied prior to GC-FPD analysis. The method showed satisfactory linearity, recovery and precision. The limits of detection (LOD) and quantification (LOQ) were 0.005 and 0.01mg/kg, respectively. The residue levels of fenitrothion were best described by first order kinetics with a half-life of 2.2days in tomatoes. The potential health risks posed by fenitrothion were not significant, based on supervised residue trial data. The current findings could provide guidance for safe and reasonable use of fenitrothion in tomatoes and prevent health problems to consumers. Copyright © 2017 Elsevier Ltd. All rights reserved.

A High Throughput Method for Measuring Polycyclic Aromatic Hydrocarbons in Seafood Using QuEChERS Extraction and SBSE.

PubMed

Pfannkoch, Edward A; Stuff, John R; Whitecavage, Jacqueline A; Blevins, John M; Seely, Kathryn A; Moran, Jeffery H

2015-01-01

National Oceanic and Atmospheric Administration (NOAA) Method NMFS-NWFSC-59 2004 is currently used to quantitatively analyze seafood for polycyclic aromatic hydrocarbon (PAH) contamination, especially following events such as the Deepwater Horizon oil rig explosion that released millions of barrels of crude oil into the Gulf of Mexico. This method has limited throughput capacity; hence, alternative methods are necessary to meet analytical demands after such events. Stir bar sorptive extraction (SBSE) is an effective technique to extract trace PAHs in water and the quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction strategy effectively extracts PAHs from complex food matrices. This study uses SBSE to concentrate PAHs and eliminate matrix interference from QuEChERS extracts of seafood, specifically oysters, fish, and shrimp. This method provides acceptable recovery (65-138%) linear calibrations and is sensitive (LOD = 0.02 ppb, LOQ = 0.06 ppb) while providing higher throughput and maintaining equivalency between NOAA 2004 as determined by analysis of NIST SRM 1974b mussel tissue.

Comparison of QuEChERS sample preparation methods for the analysis of pesticide residues in canned and fresh peach.

PubMed

Costa, Fabiane Pinho; Caldas, Sergiane Souza; Primel, Ednei Gilberto

2014-12-15

Original, citrate and acetate QuEChERS methods were studied in order to evaluate the extraction efficiency and the matrix effect in the extraction of pesticides from canned peach samples. Determinations were performed by gas chromatography coupled to mass spectrometry (GC-MS). The proposed method with extraction using the original QuEChERS method and determination by GC-MS was validated. LOQs ranged between 1 and 10 μg kg(-1) and all analytical curves showed r values higher than 0.99. Recovery values varied from 69% to 125% with RSDs less than 20%. The matrix effect was evaluated and most compounds showed signal enrichment. Robustness was demonstrated using fresh peaches, which provided recovery values within acceptable limits. The applicability of the method was verified and residues of tebuconazole and dimethoate were found in the samples. Copyright © 2014 Elsevier Ltd. All rights reserved.

Detecting a wide range of environmental contaminants in human blood samples--combining QuEChERS with LC-MS and GC-MS methods.

PubMed

Plassmann, Merle M; Schmidt, Magdalena; Brack, Werner; Krauss, Martin

2015-09-01

Exposure to environmental pollution and consumer products may result in an uptake of chemicals into human tissues. Several studies have reported the presence of diverse environmental contaminants in human blood samples. However, previously developed multi-target methods for the analysis of human blood include a fairly limited amount of compounds stemming from one or two related compound groups. Thus, the sample preparation method QuEChERS (quick easy cheap effective rugged and safe) was tested for the extraction of 64 analytes covering a broad compound domain followed by detection using liquid and gas chromatography coupled to mass spectrometry (LC- and GC-MS). Forty-seven analytes showed absolute recoveries above 70% in the first QuEChERS step, being a simple liquid-liquid extraction (LLE) using acetonitrile and salt. The second QuEChERS step, being a dispersive solid phase extraction, did not result in an overall improvement of recoveries or removal of background signals. Using solely the LLE step, eight analytes could subsequently be detected in human blood samples from the German Environmental Specimen Bank. Using a LC-multiple reaction monitoring (MRM) method with a triple quadrupole instrument, better recoveries were achieved than with an older LC-high-resolution (HR) MS full scan orbitrap instrument, which required a higher concentration factor of the extracts. However, the application of HRMS full scan methods could be used for the detection of additional compounds retrospectively.

Development of a modified QuEChERS method for the determination of veterinary antibiotics in swine manure by liquid chromatography tandem mass spectrometry.

PubMed

Guo, Chunna; Wang, Mingru; Xiao, Hui; Huai, Binbin; Wang, Feng; Pan, Guangfang; Liao, Xiaoping; Liu, Yahong

2016-08-01

A QuEChERS (quick, easy, cheap, effective, rugged and safe) based methodology was developed for the rapid, simultaneous quantification and identification of 26 veterinary drugs in swine manure by liquid chromatography tandem mass spectrometry. The selected antibiotics included tetracyclines, sulfonamides, macrolides, fluoroquinolones, lincosamides and pleuromutilins. This is the first study to determine pleuromutilin levels in manure. The QuEChERS process involved two simple steps. First, sample extraction with methanol: acetonitrile: 0.1M EDTA-McIlvaine buffer followed by phase separation with MgSO4: NaCl addition. The supernatant was then extracted and cleaned by dispersive solid-phase extraction using a primary-secondary amine (PSA) and octadecylsilane (C18) support. The proposed method provides a linearity in the range of 1-500ngmL-1 and linear regression coefficients (r) were greater than 0.996. MDL and MQL ranged between 0.01-1.86μgkg(-1) and 0.05-5.91μgkg(-1), respectively. Recoveries ranged from 61.39 to 105.65% with the exception of sulfaquinoxaline (55.7-56.8%) and valnemulin (33.7-37.7%). This method resulted in good precision (repeatability and reproducibility) and relative standard deviations less than 17% within the same day, and lower than 20% between days. The method was then applied to study the swine manure samples collected from Guangdong, China. Chlortetracycline, tetracycline, doxycycline, sulfadimidine and tilmicosin were detected in all samples indicating high residuals in manure. In fact tilmicosin was detected at 14400μgkg(-1) suggesting that prudent treatment of manure should be conducted to prevent environmental contamination. In conclusion, this workflow can provide a simpler and more cost-effective alternative to conventional methods and is compatible with processing large sample numbers over a short time period. Copyright © 2016 Elsevier B.V. All rights reserved.

Analysis of organo-chlorine pesticides residue in raw coffee with a modified "quick easy cheap effective rugged and safe" extraction/clean up procedure for reducing the impact of caffeine on the gas chromatography-mass spectrometry measurement.

PubMed

Bresin, Bruno; Piol, Maria; Fabbro, Denis; Mancini, Maria Antonietta; Casetta, Bruno; Del Bianco, Clorinda

2015-01-09

The control of pesticide residues on raw coffee is a task of great importance due to high consumption of this beverage in Italy and in many other countries. High caffeine content can hamper extraction and measurement of any pesticide residue. A tandem extraction protocol has been devised by exploiting the quick easy cheap effective rugged and safe (QuEChERS) scheme for extraction, coupled to a dispersive liquid-liquid micro-extraction (DLLME) in order to drastically reduce caffeine content in the final extract. Gas chromatography-mass spectrometry (GC-MS) has been used for quantification of organo-chlorine pesticides in single ion monitoring (SIM) mode. Method has been validated and performances meet the criteria prescribed by European Union regulations. Copyright © 2014 Elsevier B.V. All rights reserved.

Modified QuEChERS combined with ultra high performance liquid chromatography tandem mass spectrometry to determine seven biogenic amines in Chinese traditional condiment soy sauce.

PubMed

Dong, Hao; Xiao, Kaijun

2017-08-15

A rapid and sensitive UHPLC-MS/MS method followed by modified QuEChERS was developed for the simultaneous determination of seven biogenic amines in soy sauce. Samples were firstly diluted by water and pH values of which were adjusted using ammonia water. Modified QuEChERS method was adopted for the purification and 1, 7-heptyldiamine was used as the internal standard. Analysis of seven biogenic amines was within 4min. Under the optimized conditions, linear relations were favorable over the selected concentration ranges of 3.0-600μg/L with correlationcoefficients greater than 0.999. The average accuracy was between 84% and 115%. Intra- and inter- assay precisions for six replicates ranged from 2.2% to 8.8% or below 12%, respectively. The method limits of detection and the method limits of quantitation were 4-8μg/kg and 15-30μg/kg, respectively. The method was successfully applied to determine the concentrations of seven biogenic amines in soy sauces. Copyright © 2017 Elsevier Ltd. All rights reserved.

Comparison of two extraction methods for the determination of 135 pesticides in Corydalis Rhizoma, Chuanxiong Rhizoma and Angelicae Sinensis Radix by liquid chromatography-triple quadrupole-mass spectrometry. Application to the roots and rhizomes of Chinese herbal medicines.

PubMed

Liu, Jie; Tong, Ling; Li, Dongxiang; Meng, Wenting; Sun, Wanyang; Zhao, Yunli; Yu, Zhiguo

2016-04-01

In this study, two simple pretreatment methods were comprehensively evaluated for the determination of 135 pesticide residues in roots and rhizomes of Chinese herbal medicines (CHMs). The studied methodologies are (a) solid-phase extraction (SPE) and (b) Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS). For SPE, extraction solvents, SPE cartridges and types and volume of eluent were accessed and optimized. For QuEChERS, different versions, acetic acid concentration and dispersive solid-phase extraction (dSPE) sorbent materials were tested. SPE and QuEChERS were estimated in recovery range, the number of pesticides that were recovered ranging from 90% to 110% and expenses in Corydalis Rhizoma, Chuanxiong Rhizoma and Angelicae Sinensis Radix. QuEChERS method showed better performance than SPE. The method showed good linearity over the range assayed 0.9986-0.9999 (1-80ng/mL for 124 pesticides, 1-50ng/mL for 10 pesticides, 1-20ng/mL for satisfar). The matrix effect was compensated by matrix-based calibration curves with internal standard. The average recoveries of all pesticides were ranging from 70% to 120% at three levels of 10, 50 and 100ng/g with relative standard deviations less than 20%. The limits of quantification of the 135 pesticides in three matrices were 1-5ng/g, which were below the maximum residue levels (MRLs) established by the European Union. The verified QuEChERS method was successfully applied to the analysis of 65 actual samples from eight different types of roots and rhizomes of CHMs. Angelicae Sinensis Radix was the most susceptible to pesticides among these samples, and the most frequently detected pesticide was carbendazim with levels below MRLs. Metalaxyl, phorate, atrazine, diniconazole, coumaphos and paclobutrazol were also detected in some samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Simultaneous determination of UV-filters and estrogens in aquatic invertebrates by modified quick, easy, cheap, effective, rugged, and safe extraction and liquid chromatography tandem mass spectrometry.

PubMed

He, Ke; Timm, Anne; Blaney, Lee

2017-08-04

Ultraviolet-filters (UV-filters) and estrogens have attracted increased attention as contaminants of emerging concern (CECs) due to their widespread occurrence in the environment. Most of these CECs are hydrophobic and have the potential to accumulate in aquatic organisms. To date, co-analysis of UV-filters and estrogens has not been reported due, in part, to the complex environmental matrices. Here, a multi-residue method has been developed for simultaneous determination of five UV-filters and three estrogens in tissue from aquatic and marine organisms. The procedure involved a modified Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) extraction with a novel reverse-solid-phase extraction (reverse-SPE) cleanup in place of dispersive-SPE, followed by liquid chromatography tandem mass spectrometry (LC-MS/MS) analysis. The tissue mass, acetonitrile content, and salt conditions for QuEChERS extraction, along with the reverse-SPE cartridge material and elution conditions, were thoroughly investigated and optimized. Five UV-filters (i.e., 3-(4-methylbenzylidene) camphor, benzophenone-3, ethylhexylmethoxycinnamate, homosalate, and octocrylene) and three estrogens (i.e., estrone, 17β-estradiol, and 17α-ethinylestradiol) were simultaneously analyzed by taking advantage of wrong-way-round ionization in LC-MS/MS. The optimized analytical protocol exhibited good recoveries (>80%) for target compounds and enabled their detection at concentrations as low as 0.2ng/g in 50mg tissue samples. The method was applied to determine concentrations of target analytes in four invertebrates (i.e., Orconectes virilis, Procambarus clarkii, Crassostrea virginica, and Ischadium recurvum). All eight target analytes were detected at least once in the tissue samples, with the highest concentration being 399ng/g of homosalate in O. virilis. These results highlight the ubiquitous bioaccumulation of CECs in aquatic and marine invertebrates. Copyright © 2017 Elsevier B.V. All rights reserved.

Determination of mycotoxins in plant-based beverages using QuEChERS and liquid chromatography-tandem mass spectrometry.

PubMed

Miró-Abella, Eugènia; Herrero, Pol; Canela, Núria; Arola, Lluís; Borrull, Francesc; Ras, Rosa; Fontanals, Núria

2017-08-15

A method was developed for the simultaneous determination of 11 mycotoxins in plant-based beverage matrices, using a QuEChERS extraction followed by ultra-high performance liquid chromatography coupled to tandem mass spectrometry detection (UHPLC-(ESI)MS/MS). This multi-mycotoxin method was applied to analyse plant-based beverages such as soy, oat and rice. QuEChERS extraction was applied obtaining suitable extraction recoveries between 80 and 91%, and good repeatability and reproducibility values. Method Quantification Limits were between 0.05μgL -1 (for aflatoxin G 1 and aflatoxin B 1 ) and 15μgL -1 (for deoxynivalenol and fumonisin B 2 ). This is the first time that plant-based beverages have been analysed, and certain mycotoxins, such as deoxynivalenol, aflatoxin B 1 , aflatoxin B 2 , aflatoxin G 1 , aflatoxin G 2 , ochratoxin A, T-2 toxin and zearalenone, were found in the analysed samples, and some of them quantified between 0.1μgL -1 and 19μgL -1 . Copyright © 2017 Elsevier Ltd. All rights reserved.

Accelerated solvent extraction by using an 'in-line' clean-up approach for multiresidue analysis of pesticides in organic honey.

PubMed

Chiesa, Luca Maria; Labella, Giuseppe Federico; Panseri, Sara; Britti, Domenico; Galbiati, Fabrizio; Villa, Roberto; Arioli, Francesco

2017-05-01

The worldwide loss of honeybee colonies may be due to their exposure to several contaminants (i.e., pesticides); such contamination may also have impacts on consumers' health. Therefore, it is essential to develop quick and new methods to detect several pesticide residues in honey samples. In this study, the effectiveness of accelerated solvent extraction (ASE) was compared with QuEChERS methods for the analysis of 53 pesticides in organic honey by gas chromatography-triple quadrupole mass spectrometry. Two simple and rapid ASE methods with 'in-line' clean-up were optimised and then compared with QuEChERS. Hexane-ethyl acetate (Hex:EtAc) and Florisil were chosen as extraction solvent and retainer for the first ASE method respectively; acetonitrile and a primary-secondary amine phase (ACN-PSA) were selected for the second ASE method. The methods were validated according to the European Union SANTE/11945/2015 guidelines. The validation parameters showed that QuEChERS and ASE with PSA as retainer had better repeatability than ASE with Hex:EtAc and Florisil. In particular, QuEChERS and ASE (ACN-PSA) showed good recovery, according to the SANTE criteria, for the majority of investigated pesticides. Conversely, when ASE with Hex:EtAc and Florisil was used as the retainer, several compounds showed recoveries lower than the acceptable value of 70%. The ASE in-line method was finally applied to evaluate pesticide concentration in organic honey samples.

Rapid Modified QuEChERS Method for Pesticides Detection in Honey by High-Performance Liquid Chromatography UV-visible

PubMed Central

Ceci, Edmondo; Montemurro, Nicola; Tantillo, Giuseppina; Di Pinto, Angela; Celano, Gaetano Vitale; Bozzo, Giancarlo

2014-01-01

The extensive use of pesticides in agriculture plays an important role in bees die-off and allows the presence of residues in hive products, particularly in honey. An accurate and reliable analytical method, based on QuEChERS extractive technique, has been developed for the quantitative determination by high-performance liquid chromatography UV-visible detector of 5 pesticides (Deltamethrin, Dimethoate, Imidacloprid, Acetamiprid, Chlorfenvinphos) in honey. The method, according to Commission Directive 2002/63/EC and Regulation 882/2004/EC, provided excellent results with respect to linearity (correlation coefficient up to 0.993), limits of detection and quantification (0.005 and 0.01 µg/mL for Dimethoate, Deltamethrin and Chlorfenvinphos; 0.02 and 0.05 µg/mL for Acetamiprid and Imidacloprid), recovery values (86.4 to 96.3%), precision and relative expanded uncertainty of a measurement, demonstrating the conformity of the this method with the European directives. The proposed method was applied to 23 samples of Apulian honey. None of the investigated pesticides was detected in these samples. PMID:27800334

Multiresidue method for detection of pesticides in beef meat using liquid chromatography coupled to mass spectrometry detection (LC-MS) after QuEChERS extraction.

PubMed

Oliveira, Fabiano Aurélio da Silva; Pereira, Elba Nathália Corrêa; Gobbi, Jennifer Mattedi; Soto-Blanco, Benito; Melo, Marília Martins

2018-01-01

Beef meat is an important food that can be contaminated by pesticides. This study aimed to optimize a multiresidue method for identification and quantification of pesticides in beef meat by liquid chromatography coupled to mass spectrometry detection (LC-MS). The extraction and clean-up procedures were adapted from the QuECHERS method. From the 188 analytes tested, the method was validated as qualitative method for 19 compounds and as quantitative method for 152 compounds. The results were satisfactory, yielding coefficients of variation of less than 20% and recoveries ranging from 70% to 120% and expanded uncertainty of less than 50%. The quantification limit was typically 10 µg kg -1 (but 25 µg kg -1 for 12 of the compounds) and the detection limit was 5.0 µg kg -1 . Thirty-two real samples of commercialized beef meat were analyzed without any residual pesticide being found. Thus, the results showed that the multiresidue method for detecting 171 pesticides, using adapted QuECHERS for extraction and LC-MS for detection, is suitable for analyzing beef meat.

Chemometric-assisted QuEChERS extraction method for post-harvest pesticide determination in fruits and vegetables

NASA Astrophysics Data System (ADS)

Li, Minmin; Dai, Chao; Wang, Fengzhong; Kong, Zhiqiang; He, Yan; Huang, Ya Tao; Fan, Bei

2017-02-01

An effective analysis method was developed based on a chemometric tool for the simultaneous quantification of five different post-harvest pesticides (2,4-dichlorophenoxyacetic acid (2,4-D), carbendazim, thiabendazole, iprodione, and prochloraz) in fruits and vegetables. In the modified QuEChERS (quick, easy, cheap, effective, rugged and safe) method, the factors and responses for optimization of the extraction and cleanup analyses were compared using the Plackett-Burman (P-B) screening design. Furthermore, the significant factors (toluene percentage, hydrochloric acid (HCl) percentage, and graphitized carbon black (GCB) amount) were optimized using a central composite design (CCD) combined with Derringer’s desirability function (DF). The limits of quantification (LOQs) were estimated to be 1.0 μg/kg for 2,4-D, carbendazim, thiabendazole, and prochloraz, and 1.5 μg/kg for iprodione in food matrices. The mean recoveries were in the range of 70.4-113.9% with relative standard deviations (RSDs) of less than 16.9% at three spiking levels. The measurement uncertainty of the analytical method was determined using the bottom-up approach, which yielded an average value of 7.6%. Carbendazim was most frequently found in real samples analyzed using the developed method. Consequently, the analytical method can serve as an advantageous and rapid tool for determination of five preservative pesticides in fruits and vegetables.

Chemometric-assisted QuEChERS extraction method for post-harvest pesticide determination in fruits and vegetables

PubMed Central

Li, Minmin; Dai, Chao; Wang, Fengzhong; Kong, Zhiqiang; He, Yan; Huang, Ya Tao; Fan, Bei

2017-01-01

An effective analysis method was developed based on a chemometric tool for the simultaneous quantification of five different post-harvest pesticides (2,4-dichlorophenoxyacetic acid (2,4-D), carbendazim, thiabendazole, iprodione, and prochloraz) in fruits and vegetables. In the modified QuEChERS (quick, easy, cheap, effective, rugged and safe) method, the factors and responses for optimization of the extraction and cleanup analyses were compared using the Plackett–Burman (P–B) screening design. Furthermore, the significant factors (toluene percentage, hydrochloric acid (HCl) percentage, and graphitized carbon black (GCB) amount) were optimized using a central composite design (CCD) combined with Derringer’s desirability function (DF). The limits of quantification (LOQs) were estimated to be 1.0 μg/kg for 2,4-D, carbendazim, thiabendazole, and prochloraz, and 1.5 μg/kg for iprodione in food matrices. The mean recoveries were in the range of 70.4–113.9% with relative standard deviations (RSDs) of less than 16.9% at three spiking levels. The measurement uncertainty of the analytical method was determined using the bottom-up approach, which yielded an average value of 7.6%. Carbendazim was most frequently found in real samples analyzed using the developed method. Consequently, the analytical method can serve as an advantageous and rapid tool for determination of five preservative pesticides in fruits and vegetables. PMID:28225030

Chemometric-assisted QuEChERS extraction method for post-harvest pesticide determination in fruits and vegetables.

PubMed

Li, Minmin; Dai, Chao; Wang, Fengzhong; Kong, Zhiqiang; He, Yan; Huang, Ya Tao; Fan, Bei

2017-02-22

An effective analysis method was developed based on a chemometric tool for the simultaneous quantification of five different post-harvest pesticides (2,4-dichlorophenoxyacetic acid (2,4-D), carbendazim, thiabendazole, iprodione, and prochloraz) in fruits and vegetables. In the modified QuEChERS (quick, easy, cheap, effective, rugged and safe) method, the factors and responses for optimization of the extraction and cleanup analyses were compared using the Plackett-Burman (P-B) screening design. Furthermore, the significant factors (toluene percentage, hydrochloric acid (HCl) percentage, and graphitized carbon black (GCB) amount) were optimized using a central composite design (CCD) combined with Derringer's desirability function (DF). The limits of quantification (LOQs) were estimated to be 1.0 μg/kg for 2,4-D, carbendazim, thiabendazole, and prochloraz, and 1.5 μg/kg for iprodione in food matrices. The mean recoveries were in the range of 70.4-113.9% with relative standard deviations (RSDs) of less than 16.9% at three spiking levels. The measurement uncertainty of the analytical method was determined using the bottom-up approach, which yielded an average value of 7.6%. Carbendazim was most frequently found in real samples analyzed using the developed method. Consequently, the analytical method can serve as an advantageous and rapid tool for determination of five preservative pesticides in fruits and vegetables.

Use of ammonium formate in QuEChERS for high-throughput analysis of pesticides in food by fast, low-pressure gas chromatography and liquid chromatography tandem mass spectrometry.

PubMed

González-Curbelo, Miguel Ángel; Lehotay, Steven J; Hernández-Borges, Javier; Rodríguez-Delgado, Miguel Ángel

2014-09-05

The "quick, easy, cheap, effective, rugged, and safe" (QuEChERS) approach to sample preparation is widely applied in pesticide residue analysis, but the use of magnesium sulfate and other nonvolatile compounds for salting out in the method is not ideal for mass spectrometry. In this study, we developed and evaluated three new different versions of the QuEChERS method using more volatile salts (ammonium chloride and ammonium formate and acetate buffers) to induce phase separation and extraction of 43 representative pesticide analytes of different classes. Fast low-pressure gas chromatography tandem mass spectrometry (LPGC-MS/MS) and liquid chromatography (LC)-MS/MS were used for analysis. The QuEChERS AOAC Official Method 2007.01 was also tested for comparison purposes. Of the studied methods, formate buffering using 7.5g of ammonium formate and 15mL of 5% (v/v) formic acid in acetonitrile for the extraction of 15g of sample (5g for wheat grain) provided the best performance and practical considerations. Method validation was carried out with and without the use of dispersive solid-phase extraction for cleanup, and no significant differences were observed for the majority of pesticides. The method was demonstrated in quantitative analysis for GC- and LC-amenable pesticides in 4 representative food matrices (apple, lemon, lettuce, and wheat grain). With the typical exceptions of certain pH-dependent and labile pesticides, 90-110% recoveries and <10% RSD were obtained. Detection limits were mostly <5ng/g, which met the general need to determine pesticide concentrations as low as 10ng/g for monitoring purposes in food applications. Published by Elsevier B.V.

Determination of acetamiprid, imidacloprid, and spirotetramat and their relevant metabolites in pistachio using modified QuEChERS combined with liquid chromatography-tandem mass spectrometry.

PubMed

Faraji, Mohammad; Noorbakhsh, Roya; Shafieyan, Hooshang; Ramezani, Mohammadkazem

2018-02-01

A QuEChERS based methodology was developed for the simultaneous identification and quantification of acetamiprid, imidacloprid, and spirotetramat and their relevant metabolites in pistachio by liquid chromatography-tandem mass spectrometry for the first time. First, sample extraction was done with MeCN:citrate buffer:NaHCO 3 followed by phase separation with the addition of MgSO 4 :NaCl. The supernatant was then cleaned by a primary-secondary amine (PSA), GCB, and MgSO 4 . The proposed method provides a linearity in the range of 5-200µgL -1 , and the linear regression coefficients were higher than 0.99. LOD and LOQ were obtained to be 2 and 5µgkg -1 for the studied insecticides, respectively, with the exception of imidacloprid-olefin (5 and 10µgkg -1 ). Acceptable recoveries (91-110%) were obtained for all the analytes with good intra- and inter-precisions (0.4≥RSD ≤11.0). The method was then used for the pistachio samples collected from a field trial to estimate the maximum residue limits (MRLs) in next step. Copyright © 2017 Elsevier Ltd. All rights reserved.

Validation of QuEChERS method for the determination of 36 pesticide residues in fruits and vegetables from Ghana, using gas chromatography with electron capture and pulsed flame photometric detectors.

PubMed

Donkor, Augustine; Osei-Fosu, Paul; Nyarko, Stephen; Kingsford-Adaboh, Robert; Dubey, Brajesh; Asante, Isaac

2015-01-01

In this study, "Quick, Easy, Cheap, Effective, Rugged and Safe" 'QuEChERS' method was modified for the determination of 36 pesticides fortified at (0.01-1.0) mg kg(-1) in three vegetables and a fruit (lettuce, carrot, tomatoes and pineapples respectively) from Ghana. The method involved extraction with acetonitrile, phase separation with primary secondary amine and magnesium sulfate; the final injection solution was reconstituted in ethyl acetate. Organochlorine and synthetic pyrethroids residues were detected with electron capture detector whereas organophosphorus, pulsed flame photometric detector was used. The recoveries at different concentration levels (0.01, 0.1 and 1.0 mg kg(-1)) were in the range of 83% and 93% with relative standard deviation ranging from 2% to 10% (n = 5) and the coefficient of determination (R(2)) was greater than 0.99 for all the 36 pesticides. The method was successfully tested on 120 real samples from Accra markets and this proved to be useful for monitoring purposes particularly in laboratories that have no gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry.

Multiresidue method for the determination of 227 pesticides in hot pepper (Capsicum annuum L.) by liquid chromatography with tandem mass spectrometry.

PubMed

Zhu, Yong-Zhe; Zhao, Mei-Ai; Nan Feng, Ya; Han Kim, Jeong

2014-10-01

A high-throughput, rapid, and efficient modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) method with a simple cleanup procedure has been developed for simultaneously determining 227 pesticides in pepper samples by liquid chromatography with tandem mass spectrometry (running time: 10 min). Pesticide residues were extracted/partitioned with an acetonitrile/DisQuE QuEChERS pouch, and the resulting samples were cleaned up with different methods: dispersive solid-phase extraction with primary secondary amines or multiwalled carbon nanotubes and graphitized carbon solid mini cartridge column. The results indicated that multiwalled carbon nanotubes dispersive sorbents achieved the best recoveries and had less matrix interference. The numbers of pesticides with a recovery in the range of 70-120% were 199 at a spiked level of 40 μg/kg. The correlation coefficients (r(2)) for 227 pesticides were above 0.99, while the limits of quantitation of pesticides in pepper samples ranged from 0.13 to 13.51 μg/kg (S/N = 10), and the limits of detection ranged from 0.04 to 4.05 μg/kg (S/N = 3). The relative standard deviations of approximately 197 pesticides were below 20% at spiked levels of 40 μg/kg. Based on these results, the proposed method was chosen as the most suitable cleanup procedure for the determination of multiresidue pesticides in pepper samples. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rapid analysis of diclofenac and some of its transformation products in the three-spined stickleback, Gasterosteus aculeatus, by liquid chromatography-tandem mass spectrometry.

PubMed

Daniele, Gaëlle; Fieu, Maëva; Joachim, Sandrine; Bado-Nilles, Anne; Baudoin, Patrick; Turies, Cyril; Porcher, Jean-Marc; Andres, Sandrine; Vulliet, Emmanuelle

2016-06-01

Pharmaceuticals are emerging organic contaminants ubiquitously present in the environment due to incessant input into the aquatic compartment mainly resulting from incomplete removal in wastewater treatment plants. One of the major preoccupations concerning pharmaceuticals released into surface waters is their potential for bioaccumulation in biota, possibly leading to deleterious effects on ecosystems especially as they could affect a broad variety of organisms living in or depending on the aquatic environment. Thus, the development of accurate and sensitive methods is necessary to detect these compounds in aquatic ecosystems. Considering this need, this study deals with the analytical development of a methodology to quantify traces of diclofenac together with some of its biotic and abiotic transformation products in whole-body tissue of three-spined stickleback. A simple and reliable extraction method based on a modified QuEChERS extraction is implemented on 200 mg of fish. The detection and quantification of the ten target compounds are performed using liquid chromatography-tandem mass spectrometry. The whole process was successfully validated regarding linearity, recovery, repeatability, and reproducibility. The method limits of detection and quantification do not exceed 1 ng/g. To reproduce environmental conditions, we measured the concentration of DCF and its transformation products in three-spined sticklebacks after a 6-month exposure in mesocosms at several levels of DCF ranging from 0.05 to 4.1 μg/L. The phase I metabolite 4'-hydroxydiclofenac was detected in fish samples exposed at the highest DCF concentration. Graphical abstract Analysis of diclofenac and some of its transformation products in the three-spined stickleback, Gasterosteus aculeatus, by QuEChERS extraction followed by LC-MS/MS.

Cold-induced aqueous acetonitrile phase separation: A salt-free way to begin quick, easy, cheap, effective, rugged, safe.

PubMed

Shao, Gang; Agar, Jeffrey; Giese, Roger W

2017-07-14

Cooling a 1:1 (v/v) solution of acetonitrile and water at -16° C is known to result in two clear phases. We will refer to this event as "cold-induced aqueous acetonitrile phase separation (CIPS)". On a molar basis, acetonitrile is 71.7% and 13.6% in the upper and lower phases, respectively, in our study. The phase separation proceeds as a descending cloud of microdroplets. At the convenient temperature (typical freezer) employed here the lower phase is rather resistant to solidification, although it emerges from the freezer as a solid if various insoluble matter is present at the outset. In a preliminary way, we replaced the initial (salting-out) step of a representative QuEChERS procedure with CIPS, applying this modified procedure ("CIPS-QuEChERS") to a homogenate of salmon (and partly to beef). Three phases resulted, where only the upper, acetonitrile-rich phase is a liquid (that is completely clear). The middle phase comprises ice and precipitated lipids, while the lower phase is the residual matrix of undissolved salmon or meat. Treating the upper phase from salmon, after isolation, with anhydrous MgSO 4 and C18-Si (typical QuEChERS dispersive solid phase extraction sorbents), and injecting into a GC-MS in a nontargeted mode, gives two-fold more preliminary hits for chemicals, and also number of spiked pesticides recovered, relative to that from a comparable QuEChERS method. In part, this is because of much higher background signals in the latter case. Further study of CIPS-QuEChERS is encouraged, including taking advantage of other QuERChERS conditions. Copyright © 2017 Elsevier B.V. All rights reserved.

Evaluation of various QuEChERS based methods for the analysis of herbicides and other commonly used pesticides in polished rice by LC-MS/MS.

PubMed

Pareja, Lucía; Cesio, Verónica; Heinzen, Horacio; Fernández-Alba, Amadeo R

2011-02-15

Four different extraction and clean-up protocols based on the QuEChERS method were compared for the development of an optimized sample preparation procedure for the multiresidue analysis of 16 commonly applied herbicides in rice crops using LC-QqQ/MS. Additionally the methods were evaluated for the analysis of 26 insecticides and fungicides currently used in rice crops. The methods comprise, in general, the hydratation of the sample with water followed by the extraction with acetonitrile, phase separation with the addition of different salts and finally a clean-up step with various sorbents. Matrix effects were evaluated for the 4 studied methods using LC-QqQ/MS. Additionally LC-TOF/MS was used to compare the co-extractants obtained with the four assayed methodologies. Thirty-six pesticides presented good performance with recoveries in the range 70-120% and relative standard deviations below 20% using 7.5 g of milled polished rice and the buffered acetate QuEChERS method without clean-up at both fortification levels: 10 and 300 μg kg(-1). The other six pesticides presented low recovery rates, nevertheless all these analytes could be analyzed with at least one of the other three studied procedures. Copyright © 2010. Published by Elsevier B.V.

Large-scale pesticide testing in olives by liquid chromatography-electrospray tandem mass spectrometry using two sample preparation methods based on matrix solid-phase dispersion and QuEChERS.

PubMed

Gilbert-López, Bienvenida; García-Reyes, Juan F; Lozano, Ana; Fernández-Alba, Amadeo R; Molina-Díaz, Antonio

2010-09-24

In this work we have evaluated the performance of two sample preparation methodologies for the large-scale multiresidue analysis of pesticides in olives using liquid chromatography-electrospray tandem mass spectrometry (LC-MS/MS). The tested sample treatment methodologies were: (1) liquid-liquid partitioning with acetonitrile followed by dispersive solid-phase extraction clean-up using GCB, PSA and C18 sorbents (QuEChERS method - modified for fatty vegetables) and (2) matrix solid-phase dispersion (MSPD) using aminopropyl as sorbent material and a final clean-up performed in the elution step using Florisil. An LC-MS/MS method covering 104 multiclass pesticides was developed to examine the performance of these two protocols. The separation of the compounds from the olive extracts was achieved using a short C18 column (50 mm x 4.6 mm i.d.) with 1.8 microm particle size. The identification and confirmation of the compounds was based on retention time matching along with the presence (and ratio) of two typical MRM transitions. Limits of detection obtained were lower than 10 microgkg(-1) for 89% analytes using both sample treatment protocols. Recoveries studies performed on olives samples spiked at two concentration levels (10 and 100 microgkg(-1)) yielded average recoveries in the range 70-120% for most analytes when QuEChERS procedure is employed. When MSPD was the choice for sample extraction, recoveries obtained were in the range 50-70% for most of target compounds. The proposed methods were successfully applied to the analysis of real olives samples, revealing the presence of some of the target species in the microgkg(-1) range. Besides the evaluation of the sample preparation approaches, we also discuss the use of advanced software features associated to MRM method development that overcome several limitations and drawbacks associated to MS/MS methods (time segments boundaries, tedious method development/manual scheduling and acquisition limitations). This software feature recently offered by different vendors is based on an algorithm that associates retention time data for each individual MS/MS transition, so that the number of simultaneously traced transitions throughout the entire chromatographic run (dwell times and sensitivity) is maximized. Copyright 2010 Elsevier B.V. All rights reserved.

Trace analysis of parabens preservatives in drinking water treatment sludge, treated, and mineral water samples.

PubMed

Marta-Sanchez, Ana Victoria; Caldas, Sergiane Souza; Schneider, Antunielle; Cardoso, Sónia Maria Vaz Sanches; Primel, Ednei Gilberto

2018-05-01

Parabens have been widely used as antimicrobial agents, mainly in food products, pharmaceuticals, and cosmetics. Although they are known as safe preservatives, they also cause some harm to human health, which has been discussed lately. Therefore, the aim of this study was to evaluate the occurrence of nine parabens (including isomers) in mineral and drinking waters, besides in drinking water treatment sludge (DWTS) samples with determination by liquid chromatography tandem mass spectrometry (LC-MS/MS). Both methods solid phase extraction (SPE) and QuEChERS were validated. Calibration curves showed a correlation coefficient of 0.99 for all compounds. LOQ values ranged from 0.04 to 4 μg L -1 in aqueous matrices and from 5 to 500 ng g -1 in DWTS. Recoveries between 70 and 115% were reached with RSD below 20% for all compounds in SPE whereas recoveries between 62 and 119% were found with RSD below 20% for almost all compounds in QuEChERS. Matrix effect had low values (< 20%); it was only above 20% for methylparaben in the SPE and for pentylparaben in the QuEChERS. Using a quick and simple extraction procedures with SPE, QuEChERS, and LC-MS/MS analyses, these methods proved to be selective and sensitive. They were successfully applied to real samples (treated water, mineral water, and sludge), and methylparaben was detected at concentration levels below 0.242 μg L -1 in mineral and treated water samples and 10 ng g -1 in DWTS samples.

Simultaneous determination of 24 personal care products in fish muscle and liver tissues using QuEChERS extraction coupled with ultra pressure liquid chromatography-tandem mass spectrometry and gas chromatography-mass spectrometer analyses.

PubMed

Yao, Li; Zhao, Jian-Liang; Liu, You-Sheng; Yang, Yuan-Yuan; Liu, Wang-Rong; Ying, Guang-Guo

2016-11-01

A sensitive and selective quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction combined with dispersive solid-phase extraction (d-SPE) cleanup method was developed to simultaneously extract a wide range of personal care products (16 biocides, 4 synthetic musks, and 4 benzotriazoles) in fish muscle and liver tissues. In order to get satisfactory recoveries, different extraction parameters were optimized, including extraction salts and d-SPE materials, extraction solvents and acetic acid contents in organic phase, and the ratios of solvent and water. Ultra pressure liquid chromatography-tandem mass spectrometry and gas chromatography-mass spectrometry were used to analyze the target compounds in the extracts. Among the 24 personal care products, the recoveries in the range of 70-120 % were obtained for 20, 19, and 12 analytes in fish muscle at the spiking concentrations of 10, 5, and 1 ng/g ww, respectively, and for 13, 12, and 11 analytes in liver at the spiking concentrations of 40, 20, and 4 ng/g ww, respectively. Method quantification limits (MQLs) of all analytes were 0.02-2.12 ng/g ww for fish muscle and 0.22-12.2 ng/g ww for fish liver tissues. The method was successfully applied to wild fish samples collected from Dongjiang River, south China. Twenty-one and 17 of the analytes were found in fish muscle and liver samples, respectively, in at least one site of the river with the concentrations between below MQLs and 119 ng/g ww, respectively. Graphical abstract Achieved satisfactory recoveries, high precision, and low method quantification limits (MQLs) for PCPs in wild fish tissues by QuEChERS procedure optimization combined with UPLC-MS/MS and GC-MS analyses.

Determination of pesticides in sewage sludge from an agro-food industry using QuEChERS extraction followed by analysis with liquid chromatography-tandem mass spectrometry.

PubMed

Ponce-Robles, Laura; Rivas, Gracia; Esteban, Belen; Oller, Isabel; Malato, Sixto; Agüera, Ana

2017-10-01

An analytical method was developed and validated for the determination of ten pesticides in sewage sludge coming from an agro-food industry. The method was based on the application of Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) extraction for solid sewage sludge and SPE extraction for sludge aqueous phase, followed by liquid chromatography (LC) coupled to hybrid quadrupole/linear ion trap mass spectrometry (QqLIT-MS). The QuEChERS method was reported 14 years ago and nowadays is mainly applied to the analysis of pesticides in food. More recent applications have been reported in other matrices as sewage sludge, but the complexity of the matrix makes necessary the optimization of the cleanup step to improve the efficiency of the analysis. With this aim, several dispersive solid-phase extraction cleanup sorbents were tested, choosing C18 + PSA as a d-SPE sorbent. The proposed method was satisfactorily validated for most compounds investigated, showing recoveries higher than 80% in most cases, with the only exception of prochloraz (71%) at low concentration level. Limits of quantification were lower than 40 ng l -1 in the aqueous phase and below 40 ng g -1 in the solid phase for the majority of the analytes. The method was applied to solid sludge and the sludge aqueous phase coming from an agro-food industry which processes fruits and vegetables. Graphical abstract Application of LC/MS/MS advanced analytical techniques for determination of pesticides contained in sewage sludge.

Automated mini-column solid-phase extraction cleanup for high-throughput analysis of chemical contaminants in foods by low-pressure gas chromatography – tandem mass spectrometry

USDA-ARS?s Scientific Manuscript database

This study demonstrated the application of an automated high-throughput mini-cartridge solid-phase extraction (mini-SPE) cleanup for the rapid low-pressure gas chromatography – tandem mass spectrometry (LPGC-MS/MS) analysis of pesticides and environmental contaminants in QuEChERS extracts of foods. ...

Streamlined sample cleanup using combined dispersive solid-phase extraction and in-vial filtration for analysis of pesticides and environmental pollutants in shrimp

USDA-ARS?s Scientific Manuscript database

A new method of sample preparation was developed and is reported for the first time. The approach combines in-vial filtration with dispersive solid-phase extraction (d-SPE) in a fast and convenient cleanup of QuEChERS (quick, easy, cheap, effective, rugged, and safe) extracts. The method was appli...

Evaluation of a new carbon/zirconia-based sorbent for the cleanup of food extracts in multiclass analysis of pesticides and environmental contaminants

USDA-ARS?s Scientific Manuscript database

A novel carbon/zirconia based material, SupelTM QuE Verde (Verde), was evaluated in a filter-vial dispersive solid phase extraction (d-SPE) cleanup of QuEChERS extracts of pork, salmon, kale, and avocado for residual analysis of pesticides and environmental contaminants. Low pressure (LP) GC-MS/MS w...

QuEChERS Purification Combined with Ultrahigh-Performance Liquid Chromatography Tandem Mass Spectrometry for Simultaneous Quantification of 25 Mycotoxins in Cereals.

PubMed

Sun, Juan; Li, Weixi; Zhang, Yan; Hu, Xuexu; Wu, Li; Wang, Bujun

2016-12-15

A method based on the QuEChERS (quick, easy, cheap, effective, rugged, and safe) purification combined with ultrahigh performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS), was optimized for the simultaneous quantification of 25 mycotoxins in cereals. Samples were extracted with a solution containing 80% acetonitrile and 0.1% formic acid, and purified with QuEChERS before being separated by a C18 column. The mass spectrometry was conducted by using positive electrospray ionization (ESI+) and multiple reaction monitoring (MRM) models. The method gave good linear relations with regression coefficients ranging from 0.9950 to 0.9999. The detection limits ranged from 0.03 to 15.0 µg·kg -1 , and the average recovery at three different concentrations ranged from 60.2% to 115.8%, with relative standard deviations (RSD%) varying from 0.7% to 19.6% for the 25 mycotoxins. The method is simple, rapid, accurate, and an improvement compared with the existing methods published so far.

Enantioselective determination of triazole fungicide simeconazole in vegetables, fruits, and cereals using modified QuEChERS (quick, easy, cheap, effective, rugged and safe) coupled to gas chromatography/tandem mass spectrometry.

PubMed

Li, Jing; Dong, Fengshou; Xu, Jun; Liu, Xingang; Li, Yuanbo; Shan, Weili; Zheng, Yongquan

2011-09-19

A rapid and effective method for enantioselective determination of simeconazole enantiomers in food products (cucumber, tomato, apple, pear, wheat and rice) has been developed. The enantiomers were resolved by capillary gas chromatography (GC) using a commercial chiral column (BGB-172) and a temperature program from 150°C (held for 1 min) and then raised at 10°C min(-1) to 240°C (held for 10 min). This enantioselective gas chromatographic separation was combined with a clean-up/enrichment procedure based on the modification of QuEChERS (quick, easy, cheap, effective, rugged and safe) method. Co-extractives were removed with graphitized carbon black/primary secondary amine (GCB/PSA) solid-phase extraction (SPE) cartridges using acetonitrile:toluene (3:1, v/v) as eluent. Gas chromatography/ion trap mass spectrometry (GC-ITMS) with electron ionization (EI) was then used for qualitative and quantitative determination of the simeconazole enantiomers. Two precursor-to-product ion transitions (m/z 121-101 and 195-153) with the best signal intensity were chosen to build the multiple-reaction monitoring (MRM) acquisition method. The limits of detection for each enantiomer of simeconazole in six food products ranged between 0.4 and 0.9 μg kg(-1), which were much lower than maximum residue levels (MRLs) established by Japan. The methodology was successfully applied for the enantioselective analysis of simeconazole enantiomers in real samples, indicating its efficacy in investigating the environmental stereochemistry of simeconazole in food matrix. Copyright © 2011 Elsevier B.V. All rights reserved.

New Trends in Pesticide Residue Analysis in Cereals, Nutraceuticals, Baby Foods, and Related Processed Consumer Products.

PubMed

Raina-Fulton, Renata

2015-01-01

Pesticide residue methods have been developed for a wide variety of food products including cereal-based foods, nutraceuticals and related plant products, and baby foods. These cereal, fruit, vegetable, and plant-based products provide the basis for many processed consumer products. For cereal and nutraceuticals, which are dry sample products, a modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) method has been used with additional steps to allow wetting of the dry sample matrix and subsequent cleanup using dispersive or cartridge format SPE to reduce matrix effects. More processed foods may have lower pesticide concentrations but higher co-extracts that can lead to signal suppression or enhancement with MS detection. For complex matrixes, GC/MS/MS or LC/electrospray ionization (positive or negative ion)-MS/MS is more frequently used. The extraction and cleanup methods vary with different sample types particularly for cereal-based products, and these different approaches are discussed in this review. General instrument considerations are also discussed.

Quantification of VX Nerve Agent in Various Food Matrices by Solid-Phase Extraction Ultra-Performance Liquid ChromatographyTime-of-Flight Mass Spectrometry

DTIC Science & Technology

2016-04-01

QUANTIFICATION OF VX NERVE AGENT IN VARIOUS FOOD MATRICES BY SOLID-PHASE EXTRACTION ULTRA-PERFORMANCE...TITLE AND SUBTITLE Quantification of VX Nerve Agent in Various Food Matrices by Solid-Phase Extraction Ultra-Performance Liquid Chromatography... food matrices. The mixed-mode cation exchange (MCX) sorbent and Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) methods were used for

Simultaneous determination of spirotetramat and its four metabolites in fruits and vegetables using a modified quick, easy, cheap, effective, rugged, and safe method and liquid chromatography/tandem mass spectrometry.

PubMed

Zhu, Yulong; Liu, Xingang; Xu, Jun; Dong, Fengshou; Liang, Xuyang; Li, Minmin; Duan, Lifang; Zheng, Yongquan

2013-07-19

A modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) method for the simultaneous determination of spirotetramat and its four metabolites in fruits (apple, peach) and vegetables (cabbage, tomato, potato, cucumber), based on the use of liquid extraction/partition and dispersive solid phase extraction (dispersive-SPE) followed by ultrahigh-performance chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS), was established. Acidified acetonitrile (containing 1% (v/v) acetic acid) as the extraction solvent and simultaneous liquid-liquid partitioning formed by adding anhydrous magnesium sulfate (MgSO4) and anhydrous sodium acetate (NaOAc). The extract was then cleaned up by dispersive-SPE using graphitized carbon black (GCB) as selective sorbent. Further optimization of sample preparation and determination achieved recoveries of between 82 and 110% for all analytes with RSD values lower than 14% in apple, peach, cabbage, tomato, potato and cucumber at three levels (10, 100 and 1000μg/kg). The method showed excellent linearity (R(2)≥0.9895) for all studied analytes. The determination of the target compounds was achieved in less than 6.0min using an electrospray ionization source in positive mode (ESI+). The method is demonstrated to be convenient and reliable for the routine monitoring of spirotetramat and its metabolites in fruits and vegetables. Copyright © 2013 Elsevier B.V. All rights reserved.

Development and validation of modified QuEChERS method coupled with LC-MS/MS for simultaneous determination of cymiazole, fipronil, coumaphos, fluvalinate, amitraz, and its metabolite in various types of honey and royal jelly.

PubMed

Zheng, Weijia; Park, Jin-A; Abd El-Aty, A M; Kim, Seong-Kwan; Cho, Sang-Hyun; Choi, Jeong-Min; Yi, Hee; Cho, Soo-Min; Ramadan, Amer; Jeong, Ji Hoon; Shim, Jae-Han; Shin, Ho-Chul

2018-01-01

Over the past few decades, honey products have been polluted by different contaminants, such as pesticides, which are widely applied in agriculture. In this work, a modified EN - quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction method was developed for the simultaneous quantification of pesticide residues, including cymiazole, fipronil, coumaphos, fluvalinate, amitraz, and its metabolite 2,4-dimethylaniline (2,4-DMA), in four types of honey (acacia, wild, chestnut, and manuka) and royal jelly. Samples were buffered with 0.2M dibasic sodium phosphate (pH 9), and subsequently, acetonitrile was employed as the extraction solvent. A combination of primary secondary amine (PSA) and C18 sorbents was used for purification prior to liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI + /MS-MS) analysis. The estimated linearity measured at six concentration levels presented good correlation coefficients (R 2 )≥0.99. The recovery, calculated from three different spiking levels, was 62.06-108.79% in honey and 67.58-106.34% in royal jelly, with an RSD<12% for all the tested compounds. The matrix effect was also evaluated, and most of the analytes presented signal enhancement. The limits of quantification (LOQ) ranged between 0.001 and 0.005mg/kg in various samples. These are considerably lower than the maximum residue limits (MRL) set by various regulatory authorities. A total of 43 market (domestic and imported) samples were assayed for method application. Among the tested samples, three samples were tested positive (i.e. detected and quantified) only for cymiazole residues. The residues in the rest of the samples were detected but not quantified. We concluded that the protocol developed in this work is simple and versatile for the routine quantification of cymiazole, 2,4-DMA, fipronil, coumaphos, amitraz, and fluvalinate in various types of honey and royal jelly. Copyright © 2017 Elsevier B.V. All rights reserved.

Validation of QuEChERS method for the determination of some pesticide residues in two apple varieties.

PubMed

Tiryaki, Osman

2016-10-02

This study was undertaken to validate the "quick, easy, cheap, effective, rugged and safe" (QuEChERS) method using Golden Delicious and Starking Delicious apple matrices spiked at 0.1 maximum residue limit (MRL), 1.0 MRL and 10 MRL levels of the four pesticides (chlorpyrifos, dimethoate, indoxacarb and imidacloprid). For the extraction and cleanup, original QuEChERS method was followed, then the samples were subjected to liquid chromatography-triple quadrupole mass spectrometry (LC-MS/MS) for chromatographic analyses. According to t test, matrix effect was not significant for chlorpyrifos in both sample matrices, but it was significant for dimethoate, indoxacarb and imidacloprid in both sample matrices. Thus, matrix-matched calibration (MC) was used to compensate matrix effect and quantifications were carried out by using MC. The overall recovery of the method was 90.15% with a relative standard deviation of 13.27% (n = 330). Estimated method detection limit of analytes blew the MRLs. Some other parameters of the method validation, such as recovery, precision, accuracy and linearity were found to be within the required ranges.

QuEChERS Purification Combined with Ultrahigh-Performance Liquid Chromatography Tandem Mass Spectrometry for Simultaneous Quantification of 25 Mycotoxins in Cereals

PubMed Central

Sun, Juan; Li, Weixi; Zhang, Yan; Hu, Xuexu; Wu, Li; Wang, Bujun

2016-01-01

A method based on the QuEChERS (quick, easy, cheap, effective, rugged, and safe) purification combined with ultrahigh performance liquid chromatography tandem mass spectrometry (UPLC–MS/MS), was optimized for the simultaneous quantification of 25 mycotoxins in cereals. Samples were extracted with a solution containing 80% acetonitrile and 0.1% formic acid, and purified with QuEChERS before being separated by a C18 column. The mass spectrometry was conducted by using positive electrospray ionization (ESI+) and multiple reaction monitoring (MRM) models. The method gave good linear relations with regression coefficients ranging from 0.9950 to 0.9999. The detection limits ranged from 0.03 to 15.0 µg·kg−1, and the average recovery at three different concentrations ranged from 60.2% to 115.8%, with relative standard deviations (RSD%) varying from 0.7% to 19.6% for the 25 mycotoxins. The method is simple, rapid, accurate, and an improvement compared with the existing methods published so far. PMID:27983693

Evaluation of a new modified QuEChERS method for the monitoring of carbamate residues in high-fat cheeses by using UHPLC-MS/MS.

PubMed

Hamed, Ahmed M; Moreno-González, David; Gámiz-Gracia, Laura; García-Campaña, Ana M

2017-01-01

A simple and efficient method for the determination of 28 carbamates in high-fat cheeses is proposed. The methodology is based on a modified quick, easy, cheap, effective, rugged, and safe procedure as sample treatment using a new sorbent (Z-Sep + ) followed by ultra-high performance liquid chromatography with tandem mass spectrometry determination. The method has been validated in different kinds of cheese (Gorgonzola, Roquefort, and Camembert), achieving recoveries of 70-115%, relative standard deviations lower than 13% and limits of quantification lower than 5.4 μg/kg, below the maximum residue levels tolerated for these compounds by the European legislation. The matrix effect was lower than ±30% for all the studied pesticides. The combination of ultra-high performance liquid chromatography and tandem mass spectrometry with this modified quick, easy, cheap, effective, rugged, and safe procedure using Z-Sep + allowed a high sample throughput and an efficient cleaning of extracts for the control of these residues in cheeses with a high fat content. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evaluation of zirconium dioxide-based sorbents to decrease the matrix effect in avocado and almond multiresidue pesticide analysis followed by gas chromatography tandem mass spectrometry.

PubMed

Lozano, Ana; Rajski, Łukasz; Uclés, Samanta; Belmonte-Valles, Noelia; Mezcua, Milagros; Fernández-Alba, Amadeo R

2014-01-01

Two sorbents containing ZrO₂ (Z-Sep and Z-Sep+) were tested as a d-SPE clean-up in combination with the QuEChERS and ethyl acetate multiresidue method in the pesticide residues extraction in avocado. All extracts were analysed using gas chromatography coupled with a triple quadrupole mass spectrometer working in multi-reaction monitoring mode. GC QToF was used to compare the amount of matrix compounds present in the final extracts, prepared according to different protocols. The highest number of pesticides with acceptable recoveries and the lowest amount of coextracted matrix compounds were provided by QuEChERS with Z-Sep. Subsequently, this method was fully validated in avocado and almonds. Validation studies were carried out according to DG Sanco guidelines including: the evaluation of recoveries at two levels (10 and 50 μg/kg), limit of quantitation, linearity, matrix effects, as well as interday and intraday precision. In avocado, 166 pesticides were fully validated compared to 119 in almonds. The method was operated satisfactorily in routine analysis and was applied to real samples. © 2013 Published by Elsevier B.V.

New analytical method for the determination of musks in personal care products by Quick, Easy, Cheap, Effective, Rugged, and Safe extraction followed by GC-MS.

PubMed

Homem, Vera; Silva, José Avelino; Cunha, Carina; Alves, Arminda; Santos, Lúcia

2013-07-01

Synthetic musks are organic compounds used as fragrance additives and fixative compounds in a diversity of personal care products. A new method based on quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction followed by GC-MS for the analysis of 12 musks in personal care products was developed and validated. Some experimental parameters, such as total QuEChERS mass, sample mass/solvent volume ratio, type of extraction solvent, as well as salts and sorbents amount were investigated and optimized. The final method involves the musks extraction using acetonitrile, followed by the addition of anhydrous magnesium sulphate and sodium acetate. The clean-up step was performed using dispersive SPE with primary and secondary amine and octadecyl-silica sorbents. This extraction procedure is fast (about 10 min) when compared to other traditional approaches. The method was robust for the matrices studied and shows a high precision (%RSD < 15%) and accuracy (average recovery of 85%), allowing the detection of musks in minimum concentrations between 0.01 ng/g (galaxolide) and 15.80 ng/g (musk xylene). The developed method was applied to the analysis of 12 samples, which revealed musks concentrations ranging from 2 ng/g (toothpaste) to 882,340 ng/g (perfumed body lotion). © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multi-residue pesticide analysis (gas chromatography-tandem mass spectrometry detection)-Improvement of the quick, easy, cheap, effective, rugged, and safe method for dried fruits and fat-rich cereals-Benefit and limit of a standardized apple purée calibration (screening).

PubMed

Rasche, Claudia; Fournes, Britta; Dirks, Uwe; Speer, Karl

2015-07-17

Some steps of the QuEChERS method for the analysis of pesticides with GC-MS/MS in cereals and dried fruits were improved or simplified. For the latter, a mixing vessel with stator-rotor-system proved to be advantageous. The extraction procedure of dried fruits is much easier and safer than the Ultra Turrax and results in excellent validation data at a concentration level of 0.01mg/kg (116 of 118 analytes with recoveries in the range of 70-120%, 117 of 118 analytes with RSD <20%). After qualifying problematic lipophilic pesticides in fat-rich cereals (fat content >7%), predominantly organochlorines showed recoveries of <70% in quantification when the standard QuEChERS method with water was used. A second extraction was carried out analogous to the QuEChERS method, however, without the addition of water. With this simple modification, the problematic lipophilic pesticides, which had been strongly affected by the fat content of the commodities, could be determined with recoveries above 70% even at a concentration level of 0.01mg/kg. Moreover, a GC-MS/MS screening method for 120 pesticides at a concentration level of 0.01mg/kg was established by employing analyte protectants (ethylglycerol, gulonolactone, and sorbitol). The use of only one standardized calibration, made of an apple purée extract in combination with analyte protectants, allowed for a qualitative and quantitative analysis of 120 pesticides in different matrix extracts (tomato, red pepper, sour cherries, dried apples, black currant powder, raisins, wheat flour, rolled oats, wheat germ). The analyte protectants leveled the differences in the matrix-induced protection effect of the analyzed extracts over a wide range. The majority of the pesticides were analyzed with good analytical results (recoveries in the range of 70-120% and RSD <20%). Copyright © 2015 Elsevier B.V. All rights reserved.

New Method for Analysis of Multiple Anthelmintic Residues in Animal Tissue

USDA-ARS?s Scientific Manuscript database

For the first time, 39 of the major anthelmintics can be detected in one rapid and sensitive LC-MS/MS method, including the flukicides, which have been generally overlooked in surveillance programs. Utilizing the QuEChERS approach, residues were extracted from liver and milk using acetonitrile, sod...

Matrix Effect Evaluation and Method Validation of Azoxystrobin and Difenoconazole Residues in Red Flesh Dragon Fruit (Hylocereus polyrhizus) Matrices Using QuEChERS Sample Preparation Methods Followed by LC-MS/MS Determination.

PubMed

Noegrohati, Sri; Hernadi, Elan; Asviastuti, Syanti

2018-06-01

Production of red flesh dragon fruit (Hylocereus polyrhizus) was hampered by Colletotrichum sp. Pre-harvest application of azoxystrobin and difenoconazole mixture is recommended, therefore, a selective and sensitive multi residues analytical method is required in monitoring and evaluating the commodity's safety. LC-MS/MS is a well-established analytical technique for qualitative and quantitative determination in complex matrices. However, this method is hurdled by co-eluted coextractives interferences. This work evaluated the pH effect of acetate buffered and citrate buffered QuEChERS sample preparation in their effectiveness of matrix effect reduction. Citrate buffered QuEChERS proved to produce clean final extract with relative matrix effect 0.4%-0.7%. Method validation of the selected sample preparation followed by LC-MS/MS for whole dragon fruit, flesh and peel matrices fortified at 0.005, 0.01, 0.1 and 1 g/g showed recoveries 75%-119%, intermediate repeatability 2%-14%. The expanded uncertainties were 7%-48%. Based on the international acceptance criteria, this method is valid.

Enantioselective determination of metconazole in multi matrices by high-performance liquid chromatography.

PubMed

He, Rujian; Fan, Jun; Tan, Qi; Lai, Yecai; Chen, Xiaodong; Wang, Tai; Jiang, Ying; Zhang, Yaomou; Zhang, Weiguang

2018-02-01

A reliable and effective HPLC analytical method has been developed to stereoselectively quantify metconazole in soil and flour matrices. Effects of polysaccharide chiral stationary phase, type and content of alcoholic modifier on separation of racemic metconazole have been discussed in detail. Resolution and quantitative determination of metconazole stereoisomers were performed by using an Enantiopak OD column, with the n-hexane-ethanol mixture (97:3, v/v) at the flow rate of 1.0mL/min. Then, extraction and cleanup procedures followed by the modified QuEChERS (quick, easy, cheap, effective, rugged and safe) method were used for metconazole racemate in soil and flour matrices. The residual analysis method was validated. Good linearity (R 2 ≥ 0.9997) and recoveries (94.98-104.89%, RSD ≤ 2.0%) for four metconazole stereoisomers were obtained. In brief, this proposed method showed good accuracy and precision, which might be applied in enantioselective determination, residual quantitative analysis, and degradation of metconazole in food and environmental matrices. Copyright © 2017 Elsevier B.V. All rights reserved.

Multi-residue determination of 171 pesticides in cowpea using modified QuEChERS method with multi-walled carbon nanotubes as reversed-dispersive solid-phase extraction materials.

PubMed

Han, Yongtao; Song, Le; Zou, Nan; Chen, Ronghua; Qin, Yuhong; Pan, Canping

2016-09-15

A rapid and sensitive method for the determination of 171 pesticides in cowpea was developed using multi-walled carbon nanotubes (MWCNTs) as reversed-dispersive solid-phase (r-DSPE) extraction materials. The clean-up performance of MWCNTs was proved to be obviously superior to PSA and GCB. This method was validated on cowpea spiked at 0.01 and 0.1mgkg(-1) with five replicates. The mean recoveries for 169 pesticides ranged from 74% to 129% with relative standard deviations (RSDs) (n=5) lower than 16.4%, except diflufenican and quizalofop-ethyl. Good linearity for all pesticides was obtained with the calibration curve coefficients (R(2)) larger than 0.9970. The limit of detection (LODs) and limit of quantification (LOQs) for the 171 pesticides ranged from 0.001 to 0.003mgkg(-1) and from 0.002 to 0.009mgkg(-1), respectively. The method was demonstrated to be reliable and sensitive for the routine monitoring of the 171 pesticides in cowpea samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Extension of the QuEChERS method for pesticide residues in cereals to flaxseeds, peanuts, and doughs.

PubMed

Koesukwiwat, Urairat; Lehotay, Steven J; Mastovska, Katerina; Dorweiler, Kelly J; Leepipatpiboon, Natchanun

2010-05-26

A simple method was evaluated for the determination of pesticide residues in flaxseeds, doughs, and peanuts using gas chromatography-time-of-flight mass spectrometry (GC-TOF) for analysis. A modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) method, which was previously optimized for cereal grain samples, was evaluated in these fatty matrices. This extraction method involves first mixing the sample with 1:1 water/acetonitrile for an hour to swell the matrix and permit the salt-out liquid-liquid partitioning step using anhydrous MgSO(4) and NaCl. After shaking and centrifugation, cleanup is done by dispersive solid-phase extraction (d-SPE) using 150 mg of anhydrous MgSO(4), 150 mg of PSA, and 50 mg of C-18 per milliliter of extract. This method gave efficient separation of pesticides from fat and removal of coextracted substances better than gel permeation chromatography or use of a freeze-out step, which involved excessive use of solvent and/or time. The optimized analytical conditions were evaluated in terms of recoveries, reproducibilities, limits of detection, and matrix effects for 34 representative pesticides using different types of flaxseeds, peanuts, and doughs. Use of matrix-matched standards provided acceptable results for most pesticides with overall average recoveries between 70 and 120% and consistent RSDs <20% for semipolar pesticides and <26% for lipophilic pesticides. The recoveries of these latter types of pesticides depended on the fat content in the matrices and partitioning factor between the lipids and acetonitrile. We believe that the consistency of the pesticide recoveries for different samples in multiple experiments and the physicochemical partitioning explanation for <70% recoveries of lipophilic pesticides justify compensation of results for the empirically determined recovery values. In any case, this method still meets 10 ng/g detection limit needs for lipophilic pesticides and may be used for qualitative screening applications, in which any identified pesticides can be quantified and confirmed by a more intensive method that achieves >70% recoveries for lipophilic pesticides.

Determination of 17 Organophosphate Pesticide Residues in Mango by Modified QuEChERS Extraction Method Using GC-NPD/GC-MS and Hazard Index Estimation in Lucknow, India

PubMed Central

Srivastava, Ashutosh K.; Rai, Satyajeet; Srivastava, M. K.; Lohani, M.; Mudiam, M. K. R.; Srivastava, L. P.

2014-01-01

A total of 162 samples of different varieties of mango: Deshehari, Langra, Safeda in three growing stages (Pre-mature, Unripe and Ripe) were collected from Lucknow, India, and analyzed for the presence of seventeen organophosphate pesticide residues. The QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method of extraction coupled with gas chromatography was validated for pesticides and qualitatively confirmed by gas chromatography- mass spectrometry. The method was validated with different concentrations of mixture of seventeen organophosphate pesticides (0.05, 0.10, 0.50 mg kg−1) in mango. The average recovery varied from 70.20% to 95.25% with less than 10% relative standard deviation. The limit of quantification of different pesticides ranged from 0.007 to 0.033 mg kg−1. Out of seventeen organophosphate pesticides only malathion and chlorpyriphos were detected. Approximately 20% of the mango samples have shown the presence of these two pesticides. The malathion residues ranged from ND-1.407 mg kg−1 and chlorpyriphos ND-0.313 mg kg−1 which is well below the maximum residues limit (PFA-1954). In three varieties of mango at different stages from unpeeled to peeled sample reduction of malathion and chlorpyriphos ranged from 35.48%–100% and 46.66%–100% respectively. The estimated daily intake of malathion ranged from 0.032 to 0.121 µg kg−1 and chlorpyriphos ranged from zero to 0.022 µg kg−1 body weight from three different stages of mango. The hazard indices ranged from 0.0015 to 0.0060 for malathion and zero to 0.0022 for chlorpyriphos. It is therefore indicated that seasonal consumption of these three varieties of mango may not pose any health hazards for the population of Lucknow, city, India because the hazard indices for malathion and chlorpyriphos residues were below to one. PMID:24809911

Multiclass screening method based on solvent extraction and liquid chromatography-tandem mass spectrometry for the determination of antimicrobials and mycotoxins in egg.

PubMed

Capriotti, Anna Laura; Cavaliere, Chiara; Piovesana, Susy; Samperi, Roberto; Laganà, Aldo

2012-12-14

A QuEChERS (Quick Easy Cheap Effective Rugged Safe)-like extraction method was developed for the simultaneous analysis of veterinary drugs and mycotoxins in hen eggs by liquid chromatography-tandem mass spectrometry (LC-MS/MS) with electrospray (ESI) source. Various classes of antimicrobials (tetracyclines, ionophores, coccidiostats, penicillins, cephalosporins, fluoroquinolones, sulfonamides) and mycotoxins (enniatins, beauvericin, ochratoxins, aflatoxins) were considered for the development of this method. Particular attention was devoted to extraction optimization: different solvents (acetone, acetonitrile and methanol), different pH values and different sample to extracting volume ratios were tested and evaluated in terms of recovery, relative standard deviation (RSD) and ESI signal suppression due to matrix effect. Chromatographic and mass spectrometric conditions were optimized to obtain the best instrumental performances for most of the analytes. Quantitative analysis was performed by means of matrix-matched calibration, in a range that varied depending on the analyte and its established maximum limit, when there was one. Recoveries at 100 μg kg(-1) spiking level were >62% (3

Measurement of pyrethroids and their environmental degradation products in fresh fruits and vegetables using a modification of the quick easy cheap effective rugged safe (QuEChERS) method.

PubMed

Li, Weiwei; Morgan, Marsha K; Graham, Stephen E; Starr, James M

2016-05-01

Pyrethroid insecticides are used extensively in agriculture, and they, as well as their environmental degradates, may remain as residues on foods such as fruits and vegetables. Since pyrethroid degradates can be identical to the urinary markers used in human biomonitoring, it is important to understand the contribution of these degradates when studying sources of human pyrethroid exposure. We modified the widely used Quick Easy Cheap Effective Rugged Safe (QuEChERS) method to measure several current-use pyrethroids (cis/trans-permethrin, cypermethrin, deltamethrin, esfenvalerate, bifenthrin, cyfluthrin, and cyhalothrin) and their environmental degradation products (3-PBA, cis/trans-DCCA, 4-F-3-PBA, DBCA, and MPA) in selected fresh fruits and vegetables. Using fortified samples, we determined extraction efficiencies from: tomatoes, oranges (whole, peeled, and rind), grapes, apples, bananas (peeled and rind only), onions, lettuce, green peppers, carrots and broccoli. For a subset of these food items (apples, grapes, tomatoes, lettuce and banana peel), we also established limits of detection (MDLs) and quantitation (MQLs). Each sample was homogenized (1kg) then spiked with the target pyrethroids and their degradation products. Sub-samples (15g) were extracted with acetonitrile, then salted out and partitioned with NaCl and MgSO4. The extract was divided and further cleaned using solid phase extraction (SPE) cartridges containing either graphitized non-porous carbon (pyrethroids) or C18 (degradation products). Sample analysis was via liquid chromatography/tandem mass spectrometry (LC-MS/MS). Considering the mean recoveries each of the 14 analytes in all 13 matrices: 42% of the recoveries were ≥90%, 70% were ≥80%, and 90% were ≥70%. All MDL's were less than 100ng/kg, except 3-PBA (132ng/kg, tomato), MPA (129ng/kg, tomato), and trans-permethrin (141ng/kg, banana peel). We then applied the method to non-spiked samples (subset of 5 for which the MDLs/MQLs had been determined) collected weekly for four weeks from local supermarkets. At least one pyrethroid was present in measureable concentrations in all matrices except banana peels. In contrast, the only degradation products detected were cis/trans-DCCA, in one lettuce sample. Published by Elsevier B.V.

Evaluation and prevention of the negative matrix effect of terpenoids on pesticides in apples quantification by gas chromatography-tandem mass spectrometry.

PubMed

Giacinti, Géraldine; Raynaud, Christine; Capblancq, Sophie; Simon, Valérie

2016-12-21

The sample matrix can enhance the gas chromatography signal of pesticide residues relative to that obtained with the same concentration of pesticide in solvent. This paper is related to negative matrix effects observed in coupled gas chromatography-mass spectrometry ion trap (GC/MS 2 ) quantification of pesticides in concentrated extracts of apple peel prepared by the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) method. It is focused on the pesticides most frequently used on the apple varieties studied, throughout the crop cycle, right up to harvest, to combat pests and diseases and to improve fruit storage properties. Extracts from the fleshy receptacle (flesh), the epiderm (peel) and fruit of three apple varieties were studied by high-performance thin-layer chromatography hyphenated with UV-vis light detection (HPTLC/UV visible). The peel extracts had high concentrations of triterpenic acids (oleanolic and ursolic acids), reaching 25mgkg -1 , whereas these compounds were not detected in the flesh extracts (<0.05mgkg -1 ). A significant relationship has been found between the levels of these molecules and negative matrix effects in GC/MS 2 . The differences in the behavior of pesticides with respect to matrix effects can be accounted for by the physicochemical characteristics of the molecules (lone pairs, labile hydrogen, conjugation). The HPTLC/UV visible method developed here for the characterization of QuEChERS extracts acts as a complementary clean-up method, aimed to decrease the negative matrix effects of such extracts. Copyright © 2016 Elsevier B.V. All rights reserved.

Evaluation and prevention of the negative matrix effect of terpenoids on pesticides in apples quantification by gas chromatography-tandem mass spectrometry.

PubMed

Giacinti, Géraldine; Raynaud, Christine; Capblancq, Sophie; Simon, Valérie

2017-02-03

The sample matrix can enhance the gas chromatography signal of pesticide residues relative to that obtained with the same concentration of pesticide in solvent. This paper is related to negative matrix effects observed in coupled gas chromatography-mass spectrometry ion trap (GC/MS 2 ) quantification of pesticides in concentrated extracts of apple peel prepared by the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) method. It is focused on the pesticides most frequently used on the apple varieties studied, throughout the crop cycle, right up to harvest, to combat pests and diseases and to improve fruit storage properties. Extracts from the fleshy receptacle (flesh), the epiderm (peel) and fruit of three apple varieties were studied by high-performance thin-layer chromatography hyphenated with UV-vis light detection (HPTLC/UV visible). The peel extracts had high concentrations of triterpenic acids (oleanolic and ursolic acids), reaching 25mgkg -1 , whereas these compounds were not detected in the flesh extracts (<0.05mgkg -1 ). A significant relationship has been found between the levels of these molecules and negative matrix effects in GC/MS 2 . The differences in the behavior of pesticides with respect to matrix effects can be accounted for by the physicochemical characteristics of the molecules (lone pairs, labile hydrogen, conjugation). The HPTLC/UV visible method developed here for the characterization of QuEChERS extracts acts as a complementary clean-up method, aimed to decrease the negative matrix effects of such extracts. Copyright © 2016 Elsevier B.V. All rights reserved.

Determination of pesticides in coconut (Cocos nucifera Linn.) water and pulp using modified QuEChERS and LC-MS/MS.

PubMed

Ferreira, Jordana Alves; Ferreira, Joana Maria Santos; Talamini, Viviane; Facco, Janice de Fátima; Rizzetti, Tiele Medianeira; Prestes, Osmar Damian; Adaime, Martha Bohrer; Zanella, Renato; Bottoli, Carla Beatriz Grespan

2016-12-15

The use of pesticides is directly linked to improvements in productivity and to the preservation of coconut palms. However pesticide analysis is necessary to determine whether pesticide residues in the food products containing coconut are within the maximum residue limits (MRLs), ensuring the quality of these products. This work aimed to develop a method for multiresidue determination of ten pesticides in coconut water and pulp using QuEChERS and LC-MS/MS. The method was effective in terms of selectivity, linearity, matrix effect, accuracy and precision, providing LOD of 3μgkg(-1), LOQ of 10μgkg(-1) and recoveries between 70 and 120% with RSD lower than 20%. The developed method was applied to 36 samples in which residues of carbendazim, carbofuran, cyproconazole and thiabendazole were found below the LOQ in coconut water and pulp. Copyright © 2016 Elsevier Ltd. All rights reserved.

Pesticide residue evaluation in major staple food items of Ethiopia using the QuEChERS method: a case study from the Jimma Zone.

PubMed

Mekonen, Seblework; Ambelu, Argaw; Spanoghe, Pieter

2014-06-01

Samples of maize, teff, red pepper, and coffee (green bean and coffee bean with pulp) were collected from a local market in the Jimma Zone, Ethiopia. Samples were analyzed for the occurrence of cypermethrin, permethrin, deltamethrin, chlorpyrifos ethyl, DTT and its metabolites, and endosulfan (α, β). In the analytical procedure, the QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) extraction methodology with dispersive solid phase extraction clean up (d-SPE) technique was applied. Validation of the QuEChERS method was satisfactory. Recovery percentages of most pesticides were in the range of 70% to 120%, with good repeatability (%relative standard deviation < 20). The limit of detection and limit of quantification varied between 0.001 µg/g and 0.092 µg/g and between 0.002 µg/g and 0.307 µg/g, respectively. The main pesticides detected were DDT, endosulfan, cypermethrin, and permethrin. All of the pesticides analyzed were detected in red pepper and green coffee bean. Residues of DDT in coffee pulp significantly differed (p < 0.01) from other food items except for red pepper. The concentration of pesticides in the food items varied from 0.011 mg/kg to 1.115 mg/kg. All food items contained 1 or more pesticides. Two-thirds of the samples had residues below corresponding maximum residue limits, and the remaining one-third of samples were above the maximum residue limits. These results indicate the need for a good pesticide monitoring program to evaluate consumer risk for the Ethiopian people. © 2014 SETAC.

Development and Validation of a Multiresidue Method for the Determination of Pesticides in Dry Samples (Rice and Wheat Flour) Using Liquid Chromatography/Triple Quadrupole Tandem Mass Spectrometry.

PubMed

Grande-Martínez, Ángel; Arrebola, Francisco Javier; Moreno, Laura Díaz; Vidal, José Luis Martínez; Frenich, Antonia Garrido

2015-01-01

A rapid and sensitive multiresidue method was developed and validated for the determination of around 100 pesticides in dry samples (rice and wheat flour) by ultra-performance LC coupled to a triple quadrupole mass analyzer working in tandem mode (UPLC/QqQ-MS/MS). The sample preparation step was optimized for both matrixes. Pesticides were extracted from rice samples using aqueous ethyl acetate, while aqueous acetonitrile extraction [modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) method] was used for wheat flour matrixes. In both cases the extracts were then cleaned up by dispersive solid phase extraction with MgSO4 and primary secondary amine+C18 sorbents. A further cleanup step with Florisil was necessary to remove fat in wheat flour. The method was validated at two concentration levels (3.6 and 40 μg/kg for most compounds), obtaining recoveries ranging from 70 to 120%, intraday and interday precision values≤20% expressed as RSDs, and expanded uncertainty values≤50%. The LOQ values ranged between 3.6 and 20 μg/kg, although it was set at 3.6 μg/kg for the majority of the pesticides. The method was applied to the analysis of 20 real samples, and no pesticides were detected.

Matrix effects in pesticide multi-residue analysis by liquid chromatography-mass spectrometry.

PubMed

Kruve, Anneli; Künnapas, Allan; Herodes, Koit; Leito, Ivo

2008-04-11

Three sample preparation methods: Luke method (AOAC 985.22), QuEChERS (quick, easy, cheap, effective, rugged and safe) and matrix solid-phase dispersion (MSPD) were applied to different fruits and vegetables for analysis of 14 pesticide residues by high-performance liquid chromatography with electrospray ionization-mass spectrometry (HPLC/ESI/MS). Matrix effect, recovery and process efficiency of the sample preparation methods applied to different fruits and vegetables were compared. The Luke method was found to produce least matrix effect. On an average the best recoveries were obtained with the QuEChERS method. MSPD gave unsatisfactory recoveries for some basic pesticide residues. Comparison of matrix effects for different apple varieties showed high variability for some residues. It was demonstrated that the amount of co-extracting compounds that cause ionization suppression of aldicarb depends on the apple variety as well as on the sample preparation method employed.

Evaluation of the QuEChERS sample preparation approach for the analysis of pesticide residues in olives.

PubMed

Cunha, Sara C; Lehotay, Steven J; Mastovska, Katerina; Fernandes, José O; Beatriz, Maria; Oliveira, P P

2007-03-01

This paper describes the use of a quick, easy, cheap, effective, rugged, and safe (QuEChERS) method for extraction and cleanup of 16 pesticide residues of interest in olives and olive oil. These products contain a high lipid content, which can adversely affect pesticide recoveries and harm traditional chromatographic systems. For extraction, the main factors (oil and water content) were studied and optimized in experiments to maximize pesticide recoveries. Dispersive SPE with different sorbents was also investigated to minimize matrix coextractives and interferences. For analysis, a new automated DSI device was tested in GC-MS to avoid nonvolatile coextractives from contaminating the instrument. LC-MS/MS with positive ESI was used for those pesticides that were difficult to detect by GC-MS. The final method was validated for olives in terms of recoveries, repeatabilities, and reproducibilities using both detection techniques. The results demonstrated that the method achieved acceptable quantitative recoveries of 70-109% with RSDs < 20% for DSI-GC-MS and 88-130% with RSDs < 10% for LC-MS/MS, and LOQ at or below the regulatory maximum residue limits for the pesticides were achieved.

Graphene oxide-SiO2 nanocomposite as the adsorbent for extraction and preconcentration of plant hormones for HPLC analysis.

PubMed

Zhang, Xiaona; Niu, Jiahua; Zhang, Xiaoting; Xiao, Rui; Lu, Minghua; Cai, Zongwei

2017-03-01

In this research, a modified Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) method based on graphene oxide@SiO 2 (SiO 2 @GO) nanocomposite as adsorbent of dispersive solid-phase extraction (dSPE) combined with high performance liquid chromatography (HPLC) for the analysis of four plant hormones in different plants was established. The as-prepared SiO 2 @GO was characterized by scanning electron microscopy, transmission electron microscopy and infrared spectroscopy. The experimental conditions for dSPE, including the ratio of material to liquid, pH of sample, adsorption and desorption time, desorption temperature as well as desorption solution, were investigated. The detection limits for the analysis of indole-3-acetic acid, indole-3-butyric acid, 1-naphthylacetic acid and abscisic acid were achieved below 0.05μgmL -1 . The established method was applied to the analysis of the plant hormones in fruits, vegetables and other food samples. The obtained results indicated that the method was sensitive, accurate, convenient and quick, which provided an alternative analytical approach for plant hormones in complex matrices. Copyright © 2017 Elsevier B.V. All rights reserved.

[Determination of six plant growth regulator residues in strawberry by liquid chromatography-quadrupole time of flight mass spectrometry].

PubMed

Liu, Jingjing; Gong, Ping; Zhang, Xiaomei; Wang, Jianhua; Wang, Jingtang

2012-10-01

A novel method was established for the determination of six plant growth regulators (PGRs), 2,4-dichlorophenoxy acetic (2,4-D), 4-chlorophenoxy-acetic acid (CAP), 4-(3-indolyl)-butyric acid (BAA), forchlorfenuron (CPPU), abscisic acid (ABA) and trans-zeatin (ZT) in strawberry using liquid chromatography-quadrupole-time of flight mass spectrometry (LC-Q TOF MS). The Quick, Easy, Cheap, Effective, Rugged and Safe method (QuEChERS) has been validated for the extraction. In this QuEChERS method, the sample was extracted by acetonitrile and cleaned up with C18 adsorbent. The extract was measured directly by LC-Q TOF MS with electrospray ionization in negative mode. The compounds were separated on an Eclipse XDB-C8 column (150 mm x 4.6 mm, 5 microm) with acetonitrile-5 mmol/L ammonium acetate-0. 1% formic acid as mobile phase under gradient elution. The confirmatory analysis was carried out by determining the accurate masses of all compounds and fragment ions upon Target MS/MS. The limits of detection (LODs) were between 1 microg/kg and 5 microg/kg. The linear range was 0.005-1.0 mg/L for each analyte. The recoveries ranged from 87% to 107% with the relative standard deviations (RSDs) less than 10% (n = 6). The method was proved to be simple and accurate.

Determination of formetanate hydrochloride in fruit samples using liquid chromatography-mass selective detection or -tandem mass spectrometry.

PubMed

Podhorniak, Lynda V; Kamel, Alaa; Rains, Diane M

2010-05-26

A rapid multiresidue method that captures residues of the insecticide formetanate hydrochloride (FHCl) in selected fruits is described. The method was used to provide residue data for dietary exposure determinations of FHCl. Using an acetonitrile extraction with a dispersive cleanup based on AOAC International method 2007.01, also known as QuEChERS, which was further modified and streamlined, thousands of samples were successfully analyzed for FHCl residues. FHCl levels were determined both by liquid chromatography-single-stage mass spectrometry (LC-MS) and ultraperformance liquid chromatography (UPLC)-tandem mass spectrometry (LC-MS/MS). The target limit of detection (LOD) and the limit of quantitation (LOQ) achieved for FHCl were 3.33 and 10 ng/g, respectively, with LC-MS and 0.1 and 0.3 ng/g, respectively, with LC-MS/MS. Recoveries at these previously unpublished levels ranged from 95 to 109%. A set of 20-40 samples can be prepared in one working day by two chemists.

Simultaneous Determination of Isopyrazam and Azoxystrobin in Cucumbers by Liquid Chromatography-Tandem Mass Spectrometry.

PubMed

Hu, Dan; Xu, Xu; Cai, Tian; Wang, Wei-Ying; Wu, Chun-Jie; Ye, Li-Ming

2017-12-01

A rapid and sensitive analytical method based on high-performance liquid chromatography-tandem mass spectrometry was developed and validated for the determination of isopyrazam (IZM) and azoxystrobin (AZT) in cucumbers. A modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) method was used as the pretreatment procedure. The samples were extracted with acetonitrile and cleaned up with octadecylsilyl silica (C18) and graphite carbon black. The proposed method resulted in satisfactory recovery of IZM and AZT (91.48 to 114.62%), and relative standard deviations were less than 13.1% at fortification concentrations of 1, 20, and 500 μg kg -1 (n = 3). The limits of quantification for IZM and AZT were 0.498 and 0.499 μg kg -1 , respectively, which are far below the maximum residue level (0.5 mg kg -1 ) established for this type of sample. Matrix effects were also evaluated. This study established a sensitive and fast method for the detection of IZM and AZT in cucumber samples.

Simple and fast analysis of tetrabromobisphenol A, hexabromocyclododecane isomers, and polybrominated diphenyl ethers in serum using solid-phase extraction or QuEChERS extraction followed by tandem mass spectrometry coupled to HPLC and GC.

PubMed

Li, Jian; Chen, Tian; Wang, Yuwei; Shi, Zhixiong; Zhou, Xianqing; Sun, Zhiwei; Wang, Dejun; Wu, Yongning

2017-02-01

Two simplified sample preparation procedures for simultaneous extraction and clean-up of tetrabromobisphenol A, α-, β-, and γ-hexabromocyclododecane and polybrominated diphenyl ethers in human serum were developed and validated. The first procedure was based on solid-phase extraction. Sample extraction, purification, and lipid removal were carried out directly on an Oasis HLB cartridge. The second procedure was a quick, easy, cheap, effective, rugged, and safe-based approach using octadecyl-modified silica particles as a sorbent. After sample extraction and cleanup, tetrabromobisphenol A/hexabromocyclododecane was separated from polybrominated diphenyl ethers by using a Si-based cartridge. Tetrabromobisphenol A and hexabromocyclododecane were then detected by high-performance liquid chromatography coupled to tandem mass spectrometry, while polybrominated diphenyl ethers were detected by gas chromatography coupled to tandem mass spectrometry. The results of the spike recovery test using fetal bovine serum showed that the average recoveries of the analytes ranged from 87.3 to 115.3% with relative standard deviations equal to or lower than 13.4 %. Limits of detection of the analytes were in the range of 0.4-19 pg/mL except for decabromodiphenyl ether. The developed method was successfully applied to routine analysis of human serum samples from occupational workers and the general population. Extremely high serum polybrominated diphenyl ethers levels up to 3.32 × 10 4 ng/g lipid weight were found in occupational workers. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rapid determination of 9 aromatic amines in mainstream cigarette smoke by modified dispersive liquid liquid microextraction and ultraperformance convergence chromatography tandem mass spectrometry.

PubMed

Deng, Huimin; Yang, Fei; Li, Zhonghao; Bian, Zhaoyang; Fan, Ziyan; Wang, Ying; Liu, Shanshan; Tang, Gangling

2017-07-21

Aromatic amines in mainstream cigarette smoke have long been monitored due to their carcinogenic toxicity. In this work, a reliable and rapid method was developed for the simultaneous determination of 9 aromatic amines in mainstream cigarette smoke by modified dispersive liquid liquid microextraction (DLLME) and ultraperformance convergence chromatography tandem mass spectrometry (UPC 2 -MS/MS). Briefly, the particulate phase of the cigarette smoke was captured by a Cambridge filter pad, and diluted hydrogen chloride aqueous solution is employed to extract the aromatic amines under mechanical shaking. After alkalization with sodium hydroxide solution, small amount of toluene was introduced to further extract and enrich aromatic amines by modified DLLME under vortexing. After centrifugation, toluene phase was purified by a universal QuEChERS cleanup kit and was finally analyzed by UPC 2 -MS/MS. Attributing to the superior performance of UPC 2 -MS/MS, this novel approach allowed the separation and determination of 9 aromatic amines within 5.0min with satisfactory resolution and sensitivity. The proposed method was finally validated using Kentucky reference cigarette 3R4F, and emission levels of targeted aromatic amines determined were comparable to previously reported methods At three different spiked levels, the recoveries of most analytes were ranged from 74.01% to 120.50% with relative standard deviation (RSD) less than 12%, except that the recovery of p-toluidine at low spiked level and 3-aminobiphenyl at medium spiked level was 62.77% and 69.37% respectively. Thus, this work provides a novel alternative method for the simultaneous analysis of 9 aromatic amines in mainstream cigarette smoke. Copyright © 2017 Elsevier B.V. All rights reserved.

Development, validation and matrix effect of a QuEChERS method for the analysis of organochlorine pesticides in fish tissue.

PubMed

Stremel, Tatiana R De O; Domingues, Cinthia E; Zittel, Rosimara; Silva, Cleber P; Weinert, Patricia L; Monteiro, Franciele C; Campos, Sandro X

2018-04-03

This study aims to develop and validate a method to determine OCPs in fish tissues, minimizing the consumption of sample and reagents, by using a modified QuEChERS along with ultrasound, d-SPE and gas chromatography with an electron capture detector (GC-ECD), refraining the pooling. Different factorial designs were employed to optimize the sample preparation phase. The validation method presented a recovery of around 77.3% and 110.8%, with RSD lower than 13% and the detection limits were between 0.24 and 2.88 μgkg -1 , revealing good sensitiveness and accuracy. The method was satisfactorily applied to the analysis of tissues from different species of fish and OCPs residues were detected. The proposed method was shown effective to determine OCPs low concentrations in fish tissues, using small sample mass (0.5 g), making the sample analyses viable without the need for grouping (pool).

Evaluation of an analytical methodology using QuEChERS and GC-SQ/MS for the investigation of the level of pesticide residues in Brazilian melons.

PubMed

da Silva Sousa, Jonas; de Castro, Rubens Carius; de Albuquerque Andrade, Gilliane; Lima, Cleidiane Gomes; Lima, Lucélia Kátia; Milhome, Maria Aparecida Liberato; do Nascimento, Ronaldo Ferreira

2013-12-01

A multiresidue method based on the sample preparation by modified QuEChERS and detection by gas chromatography coupled to single quadruple mass spectrometers (GC-SQ/MS) was used for the analysis of 35 multiclass pesticides in melons (Cucumis melo inodorus) produced in Ceara-Brazil. The rates of recovery for pesticides studied were satisfactory (except for the etridiazole), ranging from 85% to 117% with a relative standard deviation (RSD) of less than 15%, at concentrations between 0.05 and 0.20 mg kg(-1). The limit of quantification (LOQ) for most compounds was below the MRLs established in Brazil. The combined relative uncertainty (Uc) and expanded uncertainty (Ue) was determined using repeatability, recovery and calibration curves data for each pesticide. Analysis of commercial melons samples revealed the presence of pesticides bifenthrin and imazalil at levels below the MRLs established by ANVISA, EU and USEPA. Copyright © 2013 Elsevier Ltd. All rights reserved.

Multi-residue determination of 47 organic compounds in water, soil, sediment and fish-Turia River as case study.

PubMed

Carmona, Eric; Andreu, Vicente; Picó, Yolanda

2017-11-30

A sensitive and reliable method based on solid-liquid extraction (SLE) using McIlvaine-Na 2 EDTA buffer (pH=4.5)-methanol and solid-phase extraction (SPE) clean up prior to ultra-high-performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS) was applied to determine 47 organic contaminants in fish, soil and sediments. The SPE procedure to clean-up the extracts was also used as extraction method to determine these compounds in water. Recoveries ranged from 38 to 104% for all matrices with RSDs<30%. Limits of Quantification for the target compounds were in the range of 10-50ng/g for soil, 2-40ng/g for sediment, 5-30ng/g for fish and 0.3-26ng/L for water. Furthermore, the proposed method was compared to QuEChERS (widely used for environmental matrices) that involves extraction with buffered acetonitrile (pH 5.5) and dispersive SPE clean-up. The results obtained (recoveries>50% for 36 compounds in front of 9, matrix effect<20% for 31 compounds against 21, and LOQs <25ngg -1 for 38 compounds against 22) indicates that the proposed method is more efficient than QuEChERS, The method was applied to monitoring these compounds along the Turia River. In river waters, Paracetamol (175ngL -1 ), ibuprofen (153ngL -1 ) and bisphenol A (41ngL -1 ) were the compounds most frequently detected while in sediments were vildagliptin (7ngg -1 ) and metoprolol (31ngg -1 ) and in fish, bisphenol A (33ngg -1 ) or sulfamethoxazole (13ngg -1 ). Copyright © 2017 Elsevier B.V. All rights reserved.

Multi-residue analysis of emerging pollutants in benthic invertebrates by modified micro-quick-easy-cheap-efficient-rugged-safe extraction and nanoliquid chromatography-nanospray-tandem mass spectrometry analysis.

PubMed

Berlioz-Barbier, Alexandra; Buleté, Audrey; Faburé, Juliette; Garric, Jeanne; Cren-Olivé, Cécile; Vulliet, Emmanuelle

2014-11-07

Aquatic ecosystems are continuously contaminated by agricultural and industrial sources. Although the consequences of this pollution are gradually becoming visible, their potential impacts on aquatic ecosystems are poorly known, particularly regarding the risk of bioaccumulation in different trophic levels. To establish a causality relationship between bioaccumulation and disease, experiments on biotic matrices must be performed. In this context, a multi-residue method for the analysis of 35 emerging pollutants in three benthic invertebrates (Potamopyrgus antipodarum, Gammarus fossarum, and Chironomus riparius) has been developed. Because the variation in response of each individual must be taken into account in ecotoxicological studies, the entire analytical chain was miniaturised, thereby reducing the required sample size to a minimum of one individual and scaling the method accordingly. A new extraction strategy based on a modified, optimised and miniaturised "QuEChERS" approach is reported. The procedure involves salting out liquid-liquid extraction of approximately 10-20mg of matrix followed by nano-liquid chromatography-nano electospray ionisation coupled with tandem mass spectrometry. The validated analytical procedure exhibited recoveries between 40 and 98% for all the target compounds and enabled the determination of pollutants on an individual scale in the ng g(-1) concentration. The method was subsequently applied to determine the levels of target analytes in several encaged organisms which were exposed upstream and downstream of an effluent discharge. The results highlighted a bioaccumulation of certain targeted emerging pollutants in three freshwater invertebrates, as well as inter-species differences. 18 out of 35 compounds were detected and eight were quantified. The highest concentrations were measured for ibuprofen in G. fossarum, reaching up to 105 ng g(-1). Copyright © 2014 Elsevier B.V. All rights reserved.

Chitosan from shrimp shells: A renewable sorbent applied to the clean-up step of the QuEChERS method in order to determine multi-residues of veterinary drugs in different types of milk.

PubMed

Arias, Jean Lucas de Oliveira; Schneider, Antunielle; Batista-Andrade, Jahir Antonio; Vieira, Augusto Alves; Caldas, Sergiane Souza; Primel, Ednei Gilberto

2018-02-01

Clean extracts are essential in LC-MS/MS, since the matrix effect can interfere in the analysis. Alternative materials which can be used as sorbents, such as chitosan in the clean-up step, are cheap and green options. In this study, chitosan from shrimp shell waste was evaluated as a sorbent in the QuEChERS method in order to determine multi-residues of veterinary drugs in different types of milk, i. e., fatty matrices. After optimization, the method showed correlation coefficients above 0.99, LOQs ranged between 1 and 50μgkg -1 and recoveries ranged between 62 and 125%, with RSD<20% for all veterinary drugs in all types of milk under study. The clean-up step which employed chitosan proved to be effective, since it reduced both the matrix effect (from values between -40 and -10% to values from -10 to +10%) and the extract turbidity (up to 95%). When the proposed method was applied to different milk samples, residues of albendazole (49μgkg -1 ), sulfamethazine (

Simple and sensitive monitoring of β2-agonist residues in meat by liquid chromatography-tandem mass spectrometry using a QuEChERS with preconcentration as the sample treatment.

PubMed

Xiong, Lin; Gao, Ya-Qin; Li, Wei-Hong; Yang, Xiao-Lin; Shimo, Shimo Peter

2015-07-01

A liquid chromatography with tandem mass spectrometric detection (LC-MS/MS) method was established for the simultaneous determination of the levels of 10 β2-agonists in meat. The samples were extracted using an aqueous acidic solution and cleaned up using a Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) technique utilising a DVB-NVP-SO3Na sorbent synthesised in-house. First, the β2-agonist residues were extracted in an aqueous acidic solution, followed by matrix solid-phase dispersion for clean-up. The linearities of the method were R(2)=0.9925-0.9998, with RSDs of 2.7-15.3% and 73.7-103.5% recoveries. Very low limits of detection (LOD) and quantitation (LOQ) of 0.2-0.9 μg/kg and 0.8-3.2 μg/kg, respectively, were achieved for spiked meat. The values obtained were lower than the maximum residue limits (MRLs) established by the EU and China. These results clearly demonstrate the feasibility of the proposed approach. The evaluated method provided reliable screening, quantification and identification of 10 β2-agonists in meat. Copyright © 2015 Elsevier Ltd. All rights reserved.

New approaches for extraction and determination of betaine from Beta vulgaris samples by hydrophilic interaction liquid chromatography-tandem mass spectrometry.

PubMed

Rivoira, Luca; Studzińska, Sylwia; Szultka-Młyńska, Malgorzata; Bruzzoniti, Maria Concetta; Buszewski, Bogusław

2017-08-01

Betaine is one of most studied biologically active compounds, due its role in the main biological processes. Although it may be found in several plants and roots, such as the Beta vulgaris family, present in typical diets, just a few analytical methods have been developed for its extraction from roots. A new, quick and effective procedure for the isolation and determination of betaine from two different varieties of B. vulgaris (red and gold) is presented. For betaine extraction, an accelerated solvent extraction (ASE) was coupled with solid-phase extraction. For betaine determination, a separation method based on hydrophilic interaction chromatography coupled with tandem mass spectrometry was optimized for a sensible detection of betaine by means of experimental design. Recoveries were about 93%, with RSD <5%, for both the matrices, without evidence of interfering species. The total content of betaine in extracts of various parts of plants (juice, peel, root) have been determined, obtaining concentrations in the range 3000-4000 mg/L for the juice and in the range 2-5 mg/g for the pulp and for the peel. The B. vulgaris gold species exhibited a higher concentration of betaine, compared to the red variety. Additionally, a micro extraction by packed sorbent technique and a modified quick, easy, cheap, rugged and safe (QuEChERS) procedure, were also tested and compared. Despite the lower recoveries of the latter, with respect to the ASE/SPE procedure (75-89%, RSD <1.5%), the ease of the method, which can be applied without the SPE purification procedure, can represent a positive improvement. Graphical abstract Determination of betaine from Beta vulgaris samples.

Multiresidue method for the determination of pesticides in Oolong tea using QuEChERS by gas chromatography-triple quadrupole tandem mass spectrometry.

PubMed

Wu, Chia-Chang

2017-08-15

We propose a simple, rapid analytical method for determination of 89 pesticides in Oolong tea by GC/MS/MS. Samples were extracted via QuEChERS. The limits of detection and quantification range of the 89 pesticides were 1-25μgL -1 and 10-50μgL -1 , respectively. Good separation was attained in less than 36min. A wide linear range of 1-250μgL -1 was observed with r 2 values from 0.9955 to 0.9998. Pesticide-free tea powder spiked at 50 and 100μgL -1 . Recovery ranges of the 86 (50μgL -1 ) and 83 (100μgL -1 ) pesticides were from 60% to 120%. Relative standard deviations were less than 20%. The laboratory proficiency test (FAPAS, 2014) shows satisfactory (|z|<2) z-score values. The proposed monitoring technique rapidly and efficiently screens, multiple pesticides in Oolong tea. Copyright © 2017 Elsevier Ltd. All rights reserved.

Multiclass mycotoxin analysis in edible oils using a simple solvent extraction method and liquid chromatography with tandem mass spectrometry.

PubMed

Eom, Taeyong; Cho, Hyun-Deok; Kim, Junghyun; Park, Mihee; An, Jinyoung; Kim, Moosung; Kim, Sheen-Hee; Han, Sang Beom

2017-11-01

A simple and rapid method for the simultaneous determination of 11 mycotoxins - aflatoxins B 1 , B 2 , G 1 and G 2 ; fumonisins B 1 , B 2 and B 3 ; ochratoxin A; zearalenone; deoxynivalenol; and T-2 toxin - in edible oils was established using liquid chromatography tandem mass spectrometry (LC-MS/MS). In this study, QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe), QuEChERS with dispersive liquid-liquid microextraction, and solvent extraction were examined for sample preparation. Among these methods, solvent extraction with a mixture of formic acid/acetonitrile (5/95, v/v) successfully extracted all target mycotoxins. Subsequently, a defatting process using n-hexane was employed to remove the fats present in the edible oil samples. Mass spectrometry was carried out using electrospray ionisation in polarity switching mode with multiple reaction monitoring. The developed LC-MS/MS method was validated by assessing the specificity, linearity, recovery, limit of quantification (LOQ), accuracy and precision with reference to Commission Regulation (EC) 401/2006. Mycotoxin recoveries of 51.6-82.8% were achieved in addition to LOQs ranging from 0.025 ng/g to 1 ng/g. The edible oils proved to be relatively uncomplicated matrices and the developed method was applied to 9 edible oil samples, including soybean oil, corn oil and rice bran oil, to evaluate potential mycotoxin contamination. The levels of detection were significantly lower than the international regulatory standards. Therefore, we expect that our developed method, based on simple, two-step sample preparation process, will be suitable for the large-scale screening of mycotoxin contamination in edible oils.

New sorbent in the dispersive solid phase extraction step of quick, easy, cheap, effective, rugged, and safe for the extraction of organic contaminants in drinking water treatment sludge.

PubMed

Cerqueira, Maristela B R; Caldas, Sergiane S; Primel, Ednei G

2014-04-04

Recent studies have shown a decrease in the concentration of pesticides, pharmaceuticals and personal care products (PCPs) in water after treatment. A possible explanation for this phenomenon is that these compounds may adhere to the sludge; however, investigation of these compounds in drinking water treatment sludge has been scarce. The sludge generated by drinking water treatment plants during flocculation and decantation steps should get some special attention not only because it has been classified as non-inert waste but also because it is a very complex matrix, consisting essentially of inorganic (sand, argil and silt) and organic (humic substances) compounds. In the first step of this study, three QuEChERS methods were used, and then compared, for the extraction of pesticides (atrazine, simazine, clomazone and tebuconazole), pharmaceuticals (amitriptyline, caffeine, diclofenac and ibuprofen) and PCPs (methylparaben, propylparaben, triclocarban and bisphenol A) from drinking water treatment sludge. Afterwards, the study of different sorbents in the dispersive solid phase extraction (d-SPE) step was evaluated. Finally, a new QuEChERS method employing chitin, obtained from shrimp shell waste, was performed in the d-SPE step. After having been optimized, the method showed limits of quantification (LOQ) between 1 and 50 μg kg(-1) and the analytical curves showed r values higher than 0.98, when liquid chromatography tandem mass spectrometry was employed. Recoveries ranged between 50 and 120% with RSD≤15%. The matrix effect was evaluated and compensated with matrix-matched calibration. The method was applied to drinking water treatment sludge samples and methylparaben and tebuconazole were found in concentration

Development and validation of a QuEChERS based liquid chromatography tandem mass spectrometry method for the determination of multiple mycotoxins in spices.

PubMed

Yogendrarajah, Pratheeba; Van Poucke, Christof; De Meulenaer, Bruno; De Saeger, Sarah

2013-07-05

A reliable and rapid method for the determination of multiple mycotoxins was developed using a QuEChERS (quick, easy, cheap, effective, rugged and safe) based extraction procedure in highly pigmented and complex spice matrices, namely red chilli (Capsicum annum ssp.), black and white pepper (Piper nigrum ssp.). High-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) was used for the quantification and confirmation of 17 chemically diversified mycotoxins. Different extraction procedures were studied and optimized in order to obtain better recoveries. Mycotoxins were extracted from the hydrated spices using acidified acetonitrile (1% formic acid), followed by partitioning with NaCl and anhydrous MgSO4; excluding the use of dispersive-solid phase extraction. Significant matrix effect was compensated using the matrix matched calibration curves. Electrospray ionization at positive mode was applied to simultaneously detect all the mycotoxins in a single run time of 20min. Multiple reaction monitoring mode, choosing at least two abundant fragment ions per analyte was applied. Coefficients of determination obtained were in the range of 0.9844-0.9997. Recoveries (ranging from 75% to 117%) were in accordance with the performance criteria required by the European Commission. Intra-day reproducibility ranged from 4% to 22% for most of the mycotoxins. The limit of quantification ranged from 2.3 to 146μgkg(-1). The validated method was finally applied to screen mycotoxins in ten of each spice matrix. Aflatoxins, ochratoxin, fumonisins, sterigmatocystin and citrinin were among the detected analytes. Positive findings were further confirmed using relative ion intensities. The potentiality of the method to be used for confirmatory purposes according to Commission Decision 2002/657/EC was assessed. Copyright © 2013 Elsevier B.V. All rights reserved.

Development and validation of an ultra performance liquid chromatography Q-Exactive Orbitrap mass spectrometry for the determination of fipronil and its metabolites in tea and chrysanthemum.

PubMed

Chen, Hongping; Gao, Guanwei; Liu, Pingxiang; Pan, Meiling; Chai, Yunfeng; Liu, Xin; Lu, Chengyin

2018-04-25

A fast, sensitive and reliable method for the determination of fipronil and its metabolites in tea and chrysanthemum was developed using a modified QuEChERS technique and an ultra performance liquid chromatography Q-Exactive Orbitrap mass spectrometry. The mixture of adsorbents containing primary secondary amine (PSA), octadecylsilane (C 18 ) and carbon nanotubes (CNTs), was used as QuEChERS adsorbents. The use of mass resolution at 70000 full width at half maximum (FWHM) and narrow mass windows at 5 ppm achieved high selectivity and repeatability. Satisfactory linearity with correlative coefficient (R 2 ) higher than 0.996 was achieved for all compounds. Recoveries at three levels (2, 10 and 50 μg kg -1 ) ranged from 86% to 112%, while the intra- and inter-day accuracies were less than 15%. Limits of quantification for fipronil and its metabolites were 2 μg kg -1 , which fulfils the requirement of maximum residue limits formulated by European Union and Japan. Copyright © 2017 Elsevier Ltd. All rights reserved.

Determination of ribavirin in chicken muscle by quick, easy, cheap, effective, rugged and safe method and liquid chromatography-tandem mass spectrometry.

PubMed

Wu, Yin-Liang; Chen, Ruo-Xia; Zhu, Lie; Lv, Yan; Zhu, Yong; Zhao, Jian

2016-02-15

A new analytical method for the determination of ribavirin in chicken muscle using a QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method and liquid chromatography-tandem mass spectrometry (LC-MS-MS) was developed and validated. Samples were extracted with acidified methanol (methanol:acetic acid, 99:1, v/v). The extract was further purified by QuEChERS method using primary-secondary amine (PSA) and C18. Finally, the extract was dried by nitrogen under 45°C and reconstituted in water. The separation was performed on a Hypercarb analytical column under a gradient elution. The mobile phase was composed of water buffered with ammonium acetate (2.0mM) and acetonitrile. The proposed method was validated according to the European Commission Decision 2002/657/EC. The values of the decision limit (CCα) and the detection capability (CCβ) were 1.1 and 1.5μg/kg, respectively. The mean recoveries of ribavirin ranged from 94.2% to 99.2%. The repeatability (expressed as coefficient of variation, CVr) of the method ranged from 4.5% to 4.9% and the reproducibility (CVR) of the method ranged from 4.8% to 5.4%. The method is demonstrated to be suitable for the determination of ribavirin in chicken muscle in conformity with the current EU performance requirements through validation. The total time required for the analysis of one sample, including sample preparation, was about 45min. Copyright © 2016 Elsevier B.V. All rights reserved.

Matrix-effect free multi-residue analysis of veterinary drugs in food samples of animal origin by nanoflow liquid chromatography high resolution mass spectrometry.

PubMed

Alcántara-Durán, Jaime; Moreno-González, David; Gilbert-López, Bienvenida; Molina-Díaz, Antonio; García-Reyes, Juan F

2018-04-15

In this work, a sensitive method based on nanoflow liquid chromatography high-resolution mass spectrometry has been developed for the multiresidue determination of veterinary drugs residues in honey, veal muscle, egg and milk. Salting-out supported liquid extraction was employed as sample treatment for milk, veal muscle and egg, while a modified QuEChERS procedure was used in honey. The enhancement of sensitivity provided by the nanoflow LC system also allowed the implementation of high dilution factors as high as 100:1. For all matrices tested, matrix effects were negligible starting from a dilution factor of 100, enabling, thus, the use of external standard calibration instead of matrix-matched calibration of each sample, and the subsequent increase of laboratory throughput. At spiked levels as low as 0.1 or 1 µg kg -1 before the 1:100 dilution, the obtained signals were still significantly higher than the instrumental limit of quantitation (S/N 10). Copyright © 2017 Elsevier Ltd. All rights reserved.

Development of a multiresidue method for the determination of endocrine disrupters in fish fillet using gas chromatography-triple quadrupole tandem mass spectrometry.

PubMed

Munaretto, Juliana S; Ferronato, Giovana; Ribeiro, Lucila C; Martins, Manoel L; Adaime, Martha B; Zanella, Renato

2013-11-15

Endocrine Disrupter Compounds (EDCs) are responsible for alterations in the endocrine system functions. Aquatic organisms are able to accumulate EDCs residues, being the major source of contamination for top predators and human consumers. This study aimed to develop and validate a method for the determination of 40 EDCs in fish fillet using modified QuEChERS and Gas Chromatography coupled with Mass Spectrometry in tandem (GC-MS/MS). A factorial design was used to optimize the extraction procedure. Method validation presented recoveries from 70.1% to 120.0% with RSD<20% and method limit of detection ranged from 0.3 to 7.5 µg kg(-1), showing good accuracy and precision. This method was successfully applied to the analysis of fish fillet from different species and residues of bisphenol A, chlorpyrifos and bifenthrin were detected. The proposed method proved to be effective for the determination of EDCs in fish fillet at very low concentration levels. © 2013 Elsevier B.V. All rights reserved.

QuEChERS GC-MS validation and monitoring of pesticide residues in different foods in the tomato classification group.

PubMed

Ramírez Restrepo, Andrés; Gallo Ortiz, Andrés Fernando; Hoyos Ossa, Duvan Esteban; Peñuela Mesa, Gustavo Antonio

2014-09-01

The objective of this study was to validate (SANCO/12495/2011 and NTC-ISO/IEC 17025) multi-residue multi-class methods using QuEChERS sample preparation and GC-MS for the analysis of regulated pesticides in tomatoes (Solanum lycopersicum), tamarillos (Solanum betaceum) and goldenberries (Physalis peruviana). These Latin American products are representative and widely produced in Antioquia (Colombia). Sample preparation followed the UNE-EN 15662 method (150 mg MgSO4, 25mg primary secondary amines and 25mg of octadecylsiloxane for cleanup; graphitized carbon black was added for tomatoes). Extracts were injected using a programmed temperature-vaporizing injector. The residues were validated over a range from 0.02 mg/kg to 0.20 mg/kg, with 24 analytes validated in tomatoes, 33 in tamarillos and 28 in goldenberries. An initial risk assessment was enabled by monitoring 24 samples in the municipalities of El Peñol, Marinilla and San Vicente Ferrer. Risks were found for tomatoes, but no significant risks were found for tamarillos or goldenberries. Copyright © 2014 Elsevier Ltd. All rights reserved.

Evaluation of two fast and easy methods for pesticide residue analysis in fatty food matrixes.

PubMed

Lehotay, Steven J; Mastovská, Katerina; Yun, Seon Jong

2005-01-01

Two rapid methods of sample preparation and analysis of fatty foods (e.g., milk, eggs, and avocado) were evaluated and compared for 32 pesticide residues representing a wide range of physicochemical properties. One method, dubbed the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method for pesticide residue analysis, entailed extraction of 15 g sample with 15 mL acetonitrile (MeCN) containing 1% acetic acid followed by addition of 6 g anhydrous magnesium sulfate and 1.5 g sodium acetate. After centrifugation, 1 mL of the buffered MeCN extract underwent a cleanup step (in a technique known as dispersive solid-phase extraction) using 50 mg each of C18 and primary secondary amine sorbents plus 150 mg MgSO4. The second method incorporated a form of matrix solid-phase dispersion (MSPD), in which 0.5 g sample plus 2 g C18 and 2 g anhydrous sodium sulfate was mixed in a mortar and pestle and added above a 2 g Florisil column on a vacuum manifold. Then, 5 x 2 mL MeCN was used to elute the pesticide analytes from the sample into a collection tube, and the extract was concentrated to 0.5 mL by evaporation. Extracts in both methods were analyzed concurrently by gas chromatography/mass spectrometry and liquid chromatography/tandem mass spectrometry. The recoveries of semi-polar and polar pesticides were typically 100% in both methods (except that basic pesticides, such as thiabendazole and imazalil, were not recovered in the MSPD method), but recovery of nonpolar pesticides decreased as fat content of the sample increased. This trend was more pronounced in the QuEChERS method, in which case the most lipophilic analyte tested, hexachlorobenzene, gave 27 +/- 1% recovery (n=6) in avocado (15% fat) with a<10 ng/g limit of quantitation.

Simultaneous Analysis of 3-MCPD and 1,3-DCP in Asian Style Sauces Using QuEChERS Extraction and Gas Chromatography-Triple Quadrupole Mass Spectrometry.

PubMed

Genualdi, Susan; Nyman, Patricia; DeJager, Lowri

2017-02-01

Acid hydrolyzed vegetable protein (aHVP) is used for flavoring a wide variety of foods and also in the production of nonfermented soy sauce. During the production of aHVP, chloropropanols including 3-monochloropropane-1,2-diol (3-MCPD) and 1,3 dichloropropane-2-ol (1,3-DCP) can be formed through the reaction of the hydrochloric acid catalyst and residual fat and the reaction of 3-MCPD with acetic acid, respectively. 3-MCPD is a carcinogen, and 1,3-DCP has been classified as a genotoxic carcinogen. The European Union (EU) has set a maximum concentration of 0.02 mg/kg of 3-MCPD in aHVP, and the Food and Drug Administration (FDA) set a guidance limit of 1 mg/kg of 3-MCPD in aHVP. 1,3-DCP is not an approved food additive, and the Joint FAO/WHO Expert Committee on Food Additives (JEFCA) has set a limit at 0.005 mg/kg, which is close to the estimated method detection limit. Currently there are few analytical methods for the simultaneous determination of 3-MCPD and 1,3-DCP without derivatization due to differences in their physical chemical properties and reactivity. A new method was developed using QuEChERS (quick, easy, cheap, effective, rugged, and safe) with direct analysis of the extract without derivatization using gas chromatography-triple quadrupole mass spectrometry (GC-QQQ). Additionally, a market sampling of 60 soy sauce samples was performed in 2015 to determine if concentrations have changed since the FDA limit was set in 2008. The sampling results were compared between the new QuEChERS method and a method using phenylboronic acid (PBA) as a derivatizing agent for 3-MCPD analysis. The concentrations of 3-MCPD detected in soy sauce samples collected in 2015 (

Simultaneous Analysis of 3-MCPD and 1,3-DCP in Asian Style Sauces Using QuEChERS Extraction and Gas Chromatography–Triple Quadrupole Mass Spectrometry

PubMed Central

Genualdi, Susan; Nyman, Patricia; DeJager, Lowri

2017-01-01

Acid hydrolyzed vegetable protein (aHVP) is used for flavoring a wide variety of foods and also in the production of nonfermented soy sauce. During the production of aHVP, chloropropanols including 3-monochloropropane-1,2-diol (3-MCPD) and 1,3 dichloropropane-2-ol (1,3-DCP) can be formed through the reaction of the hydrochloric acid catalyst and residual fat and the reaction of 3-MCPD with acetic acid, respectively. 3-MCPD is a carcinogen, and 1,3-DCP has been classified as a genotoxic carcinogen. The European Union (EU) has set a maximum concentration of 0.02 mg/kg of 3-MCPD in aHVP, and the Food and Drug Administration (FDA) set a guidance limit of 1 mg/kg of 3-MCPD in aHVP. 1,3-DCP is not an approved food additive, and the Joint FAO/WHO Expert Committee on Food Additives (JEFCA) has set a limit at 0.005 mg/kg, which is close to the estimated method detection limit. Currently there are few analytical methods for the simultaneous determination of 3-MCPD and 1,3-DCP without derivatization due to differences in their physical chemical properties and reactivity. A new method was developed using QuEChERS (quick, easy, cheap, effective, rugged, and safe) with direct analysis of the extract without derivatization using gas chromatography–triple quadrupole mass spectrometry (GC-QQQ). Additionally, a market sampling of 60 soy sauce samples was performed in 2015 to determine if concentrations have changed since the FDA limit was set in 2008. The sampling results were compared between the new QuEChERS method and a method using phenylboronic acid (PBA) as a derivatizing agent for 3-MCPD analysis. The concentrations of 3-MCPD detected in soy sauce samples collected in 2015 (

The fate of spirotetramat and dissipation metabolites in Apiaceae and Brassicaceae leaf-root and soil system under greenhouse conditions estimated by modified QuEChERS/LC-MS/MS.

PubMed

Łozowicka, Bożena; Mojsak, Patrycja; Kaczyński, Piotr; Konecki, Rafał; Borusiewicz, Andrzej

2017-12-15

The aim of this study was to investigate the dissipation of spirotetramat and its four metabolites (B-enol, B-keto, B-mono and B-glu) in different parts of vegetables belong to the minor crops (Appiacea and Brassicaceae) and soil from cultivation. The challenge of this study was to apply an optimized clean up step in QuEChERS to obtain one universal sorbent for different complex matrices like leaves with high levels of pigments, roots containing acids, sugars, polyphenolls and pigments and soil with organic ingredients. Eight commercial (Florisil, neutral alumina, GCB, PSA, C18, diatomaceous earth, VERDE and ChloroFiltr) and one organic (Chitosan) sorbents were tested. A modified clean up step in QuEChERS methodology was used for analysis. The dissipation of spirotetramat and its metabolites was described according to a first-order (FO) kinetics equation with R 2 between 0.9055 and 0.9838. The results showed that the time after 50% (DT 50 ) of the substance degraded was different for soil, roots and leaves, and amounted to 0.2day, 2.8-2.9days and 2.1-2.4days, respectively. The terminal residues of spiroteramat (expressed as the sum of spirotetramat, B-enol, B-glu, B-keto and B-mono) were much lower than the MRLs. Copyright © 2017 Elsevier B.V. All rights reserved.

Status and effect of pesticide residues in soils under different land uses of Andaman Islands, India.

PubMed

Murugan, A V; Swarnam, T P; Gnanasambandan, S

2013-10-01

Pesticides are shown to have a great effect on soil organisms, but the effect varies with pesticide group and concentration, and is modified by soil organic carbon content and soil texture. In the humid tropical islands of Andaman, India, no systematic study was carried out on pesticide residues in soils of different land uses. The present study used the modified QuEChERS method for multiresidue extraction from soils and detection with a gas chromatograph. DDT and its various metabolites, α-endosulfan, β-endosulfan, endosulfan sulfate, aldrin, and fenvalerate, were detected from the study area. Among the different pesticide groups detected, endosulfan and DDT accounted for 41.7 % each followed by aldrin (16.7 %) and synthetic pyrethroid (8.3 %). A significantly higher concentration of pesticide residues was detected in rice-vegetable grown in the valley followed by rice-fallow and vegetable-fallow in the coastal plains. Soil microbial biomass carbon is negatively correlated with the total pesticide residues in soils, and it varied from 181.2 to 350.6 mg kg(-1). Pesticide residues have adversely affected the soil microbial populations, more significantly the bacterial population. The Azotobacter population has decreased to the extent of 51.8 % while actinomycetes were the least affected though accounted for 32 % when compared to the soils with no residue.

Simultaneous determination of flubendiamide its metabolite desiodo flubendiamide residues in cabbage, tomato and pigeon pea by HPLC.

PubMed

Paramasivam, M; Banerjee, Hemanta

2011-10-01

A sensitive and simple method for simultaneous analysis of flubendiamide and its metabolite desiodo flubendiamide in cabbage, tomato and pigeon pea has been developed. The residues were extracted with QuEChERS method followed by dispersive solid-phase extraction with primary secondary amine sorbent to remove co extractives, prior to analysis by HPLC coupled with UV-Vis detector. The recoveries of flubendiamide and desiodo flubendiamide were ranged from 85.1 to 98.5% and 85.9 to 97.1% respectively with relative standard deviations (RSD) less than 5% and sensitivity of 0.01 μg g(-1). The method offers a less expensive and safer alternative to the existing residue analysis methods for vegetables. © Springer Science+Business Media, LLC 2011

Analysis of pharmaceutical adulterants in plant food supplements by UHPLC-MS/MS.

PubMed

Paíga, Paula; Rodrigues, Manuela J E; Correia, Manuela; Amaral, Joana S; Oliveira, M Beatriz P P; Delerue-Matos, Cristina

2017-03-01

A method based on the Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) extraction and ultra-high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS) was successfully developed and validated for the analysis of 26 pharmaceutical compounds belonging to different therapeutic classes (anorexics, stimulants, anxiolytics, antidepressants and laxatives), which are all prone to be illegally added into weight-loss plant food supplements (PFS) for their pharmacological activity. Internal standard calibration with six isotopically labelled compounds rendered good linearity in the range of 5 to 1000μg/l, depending on the compound, and good sensitivity with limits of quantification in the range of 0.02-9.80μg/l. Recoveries were assessed for all the 16 samples analysed and were found between 70% and 120% for over 90% of the analytes. The average recovery value was 90.8%, for the different studied matrices (liquids, liquid ampoules, tablets and capsules), with RSD values lower than 10% for all forms. The changes introduced to the QuEChERS procedure maintained the good performance characteristics of the extraction method while preserving the chromatographic system for the introduction of unwanted matrix compounds. Synephrine was the only compound detected and quantified in one sample, but at a very low concentration (768μg/l) and its presence may be due to the plant extracts used in the formulation, as synephrine is known to be a natural constituent of Citrus aurantium amara. Despite none of the 16 evaluated samples were found to be adulterated by the illegal addition of the drugs included in this work, the developed methodology can be very useful for monitoring the adulteration of weight-loss PFS. Copyright © 2016 Elsevier B.V. All rights reserved.

Residue analysis of four diacylhydrazine insecticides in fruits and vegetables by Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) method using ultra-performance liquid chromatography coupled to tandem mass spectrometry.

PubMed

Liu, Xingang; Xu, Jun; Dong, Fengshou; Li, Yuanbo; Song, Wenchen; Zheng, Yongquan

2011-08-01

The new analytical method using Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) procedure for simultaneous determination of diacylhydrazine insecticide residues in fruits and vegetables was developed using ultra-performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS). The four insecticides (tebufenozide, methoxfenozide, chromafenozide, and halofenozide) were extracted from six fruit and vegetable matrices using acetonitrile and subsequently cleaned up using primary secondary amine (PSA) or octadecylsilane (C18) as sorbent prior to UPLC-MS/MS analysis. The determination of the target compounds was achieved in less than 3.0 min using an electrospray ionization source in positive mode (ESI+) for tebufenozide, methoxfenozide, and halofenozide and in negative mode (ESI-) for chromafenozide. The limits of detection were below 0.6 μg kg(-1), while the limit of quantification did not exceed 2 μg kg(-1) in different matrices. The QuEChERS procedure by using two sorbents (PSA and C18) and the matrix-matched standards gave satisfactory recoveries and relative standard deviation (RSD) values in different matrices at four spiked levels (0.01, 0.05, 0.1, and 1 mg kg(-1)). The overall average recoveries for this method in apple, grape, cucumber, tomato, cabbage, and spinach at four levels ranged from 74.2% to 112.5% with RSDs in the range of 1.4-13.8% (n = 5) for all analytes. This study provides a theoretical basis for China to draw up maximum residue limits and analytical method for diacylhydrazine insecticide in vegetables and fruits.

Multiresidue pesticide analysis of tuber and root commodities by QuEchERS extraction and ultra-performance liquid chromatography coupled to tandem mass spectrometry.

PubMed

Garrido Frenich, Antonia; Martín Fernández, María del Mar; Díaz Moreno, Laura; Martínez Vidal, Jose Lúis; López-Gutiérrez, Noelia

2012-01-01

A simple, rapid, and reliable multiresidue method to determine 84 pesticides in potato and carrot samples by ultra-performance liquid chromatography coupled to MS/MS has been developed and fully validated for routine analysis according to ISO/IEC 17025:2005. The method makes use of a buffered Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) sample preparation procedure based on a single extraction with acidified acetonitrile, followed by partitioning with salts. Chromatographic conditions were optimized in order to achieve a rapid separation in the multiple reaction monitoring mode. Performance characteristics of the method, including an estimation of measurement uncertainty using validation data, are reported for both matrixes. Calibration curves were linear from 0.010 to 0.150 mg/kg for most compounds. The LOD and LOQ were 0.006 and 0.010 mg/kg, respectively, except for fluorocloridone, fluquinconazol, and hexitiazox, which were 0.030 and 0.050 mg/kg, respectively. Recoveries obtained were in the range 70-116%, with intraday precision values < or = 20% RSD and interday precision values < or = 25% RSD at two different concentration levels. The overall uncertainty of the method was estimated at two concentrations as being lower than 34% in all cases. The method has been applied to the analysis of 70 vegetable samples, and imidacloprid and linuron were the pesticides most frequently found in potato and carrot commodities, respectively.

Magnitude of cyantraniliprole residues in tomato following open field application: pre-harvest interval determination and risk assessment.

PubMed

Malhat, Farag; Kasiotis, Konstantinos M; Shalaby, Shehata

2018-02-05

Cyantraniliprole is an anthranilic diamide insecticide, belonging to the ryanoid class, with a broad range of applications against several pests. In the presented work, a reliable analytical technique employing high-performance liquid chromatography coupled with photodiode array detector (HPLC-DAD) for analyzing cyantraniliprole residues in tomato was developed. The method was then applied to field-incurred tomato samples collected after applications under open field conditions. The latter aimed to ensure the safe application of cyantraniliprole to tomato and contribute the derived residue data to the risk assessment under field conditions. Sample preparation involved a single step extraction with acetonitrile and sodium chloride for partitioning. The extract was purified utilizing florisil as cleanup reagent. The developed method was further evaluated by comparing the analytical results with those obtained using the QuEChERS technique. The novel method outbalanced QuEChERS regarding matrix interferences in the analysis, while it met all guideline criteria. Hence, it showed excellent linearity over the assayed concentration and yielded satisfactory recovery rate in the range of 88.9 to 96.5%. The half-life of degradation of cyantraniliprole was determined at 2.6 days. Based on the Codex MRL, the pre-harvest interval (PHI) for cyantraniliprole on tomato was 3 days, after treatment at the recommended dose. To our knowledge, the present work provides the first record on PHI determination of cyantraniliprole in tomato under open field conditions in Egypt and the broad Mediterranean region.

Development of a method for the analysis of hormones and pharmaceuticals in earthworms by quick, easy, cheap, effective, rugged and safe (QuEChERS) extraction followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS).

PubMed

Bergé, Alexandre; Vulliet, Emmanuelle

2015-10-01

The earthworm represents a kind of creature in contact with the soil surface and usually exposed to a variety of organic pollutants from human activities. Therefore, it can be considered as an organism of choice for identifying pollution or better understanding the input of contaminants in food chains in particular through the contributions of sludge. Moreover, the use of organisms such as soil invertebrates is to be developed for ecotoxicological risk assessment of pollutants. In this context, a simple, rapid and effective multi-residue method was developed for the determination of 31 compounds including 11 steroids, 14 veterinary antibiotics and 6 human contaminants (paracetamol, sulfamethoxazole, fluvoxamine, carbamazepine, ibuprofen, bisphenol A) in earthworm. The sample preparation procedure was based on a salting-out extraction with acetonitrile (QuEChERS approach) that was optimised with regard to the acetonitrile/water ratio used in the extraction step, the choice of the clean-up and the quantity of the matrix. The optimised extraction method exhibited recoveries that comprised between 44 and 98 % for all the tested compounds. The limits of detection of all compounds were below 14 ng g(-1) and the limits of quantification (LOQ) comprised between 1.6 and 40 ng g(-1) (wet weight). The method was therefore applied to determine the levels of pharmaceuticals and hormones in six earthworm samples collected in various soils. Concentrations up to 195 ng g(-1) for bisphenol A were determined, between a few nanograms per gram and 43.1 ng g(-1) (estriol) for hormones and between a few nanograms per gram and 73.5 ng g(-1) (florfenicol) for pharmaceuticals. Experiments were also conducted in laboratory conditions to evaluate the accumulation of the target substances by earthworm.

A statistical approach to determine fluxapyroxad and its three metabolites in soils, sediment and sludge based on a combination of chemometric tools and a modified quick, easy, cheap, effective, rugged and safe method.

PubMed

Li, Shasha; Liu, Xingang; Zhu, Yulong; Dong, Fengshou; Xu, Jun; Li, Minmin; Zheng, Yongquan

2014-09-05

An effective method for the quantification of fluxapyroxad and its three metabolites in soils, sediment and sludge was developed using ultrahigh performance chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS). Both the extraction and clean-up steps of the QuEChERS procedure were optimised using a chemometric tool, which was expected to facilitate the rapid analysis with minimal procedures. Several operating parameters (MeCN/acetic acid ratio in the extraction solution (i.e., acetic acid percentage), water volume, extraction time, PSA amount, C18 amount, and GCB amount) were investigated using a Plackett-Burman (P-B) screening design. Afterward, the significant factors (acetic acid percentage, water volume, and PSA amount) obtained were optimised using central composite design (CCD) combined with the desirability function (DF) to determine the optimum experimental conditions. The optimised procedure provides high-level linearity for all studied compounds with correlation coefficients ranging between 0.9972 and 0.9999. The detection limits were in the range of 0.1 to 1.0μg/kg and the limits of quantitation (LOQs) were between 0.5 and 3.4μg/kg with relative standard deviations (RSD) between 2.3% and 9.6% (n=6). Therefore, the developed protocol can serve as a simple and sensitive tool for monitoring fluxapyroxad and its three metabolites in soil, sediment and sludge samples. Copyright © 2014 Elsevier B.V. All rights reserved.

Organochlorine pesticide residues in strawberries from integrated pest management and organic farming.

PubMed

Fernandes, Virginia C; Domingues, Valentina F; Mateus, Nuno; Delerue-Matos, Cristina

2011-07-27

A rapid, specific, and sensitive method based on the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) method and a cleanup using dispersive solid-phase extraction with MgSO(4), PSA, and C18 sorbents has been developed for the routine analysis of 14 pesticides in strawberries. The analyses were performed by three different analytical methodologies: gas chromatography (GC) with electron capture detection (ECD), mass spectrometry (MS), and tandem mass spectrometry (MS/MS). The recoveries for all the pesticides studied were from 46 to 128%, with relative standard deviation of <15% in the concentration range of 0.005-0.250 mg/kg. The limit of detection (LOD) for all compounds met maximum residue limits (MRL) accepted in Portugal for organochlorine pesticides (OCP). A survey study of strawberries produced in Portugal in the years 2009-2010 obtained from organic farming (OF) and integrated pest management (IPM) was developed. Lindane and β-endosulfan were detected above the MRL in OF and IPM. Other OCP (aldrin, o,p'-DDT and their metabolites, and methoxychlor) were found below the MRL. The OCP residues detected decreased from 2009 to 2010. The QuEChERS method was successfully applied to the analysis of strawberry samples.

Trace analysis of three fungicides in animal origin foods with a modified QuEChERS method and liquid chromatography-tandem mass spectrometry.

PubMed

Mu, Zhaobin; Feng, Xiaoxiao; Zhang, Yun; Zhang, Hongyan

2016-02-01

A multi-residue method based on modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) sample preparation, followed by liquid chromatography tandem mass spectrometry (LC-MS/MS), was developed and validated for the determination of three selected fungicides (propiconazole, pyraclostrobin, and isopyrazam) in seven animal origin foods. The overall recoveries at the three spiking levels of 0.005, 0.05, and 0.5 mg kg(-1) spanned between 72.3 and 101.4% with relative standard deviation (RSD) values between 0.7 and 14.9%. The method shows good linearity in the concentrations between 0.001 and 1 mg L(-1) with the coefficient of determination (R (2)) value >0.99 for each target analyte. The limit of detections (LODs) for target analytes were between 0.04 and 1.26 μg kg(-1), and the limit of quantifications (LOQs) were between 0.13 and 4.20 μg kg(-1). The matrix effect for each individual compound was evaluated through the study of ratios of the areas obtained in solvent and matrix standards. The optimized method provided a negligible matrix effect for propiconazole within 20%, whereas for pyraclostrobin and isopyrazam, the matrix effect was relatively significant with a maximum value of 49.8%. The developed method has been successfully applied to the analysis of 210 animal origin samples obtained from 16 provinces of China. The results suggested that the developed method was satisfactory for trace analysis of three fungicides in animal origin foods.

Analysis of non-steroidal anti-inflammatory drugs in milk using QuEChERS and liquid chromatography coupled to mass spectrometry: triple quadrupole versus Q-Orbitrap mass analyzers.

PubMed

Rúbies, Antoni; Guo, Lili; Centrich, Francesc; Granados, Mercè

2016-08-01

We developed a Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) method for the high throughput determination of 10 non-steroidal anti-inflammatory drugs (NSAIDs) in milk samples using high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) with a triple quadrupole (QqQ) instrument and an electrospray ionization (ESI) source. The new extraction procedure is highly efficient, and we obtained absolute recoveries in the range 78.1-97.1 % for the extraction and clean-up steps. Chromatographic separation is performed in the gradient mode with a biphenyl column and acidic mobile phases consisting of water and acetonitrile containing formic acid. The chromatographic run time was about 12 min, and NSAID peaks showed a good symmetry factor. For MS/MS detection, we used multiple reaction monitoring (MRM) mode, using ESI in both positive and negative modes. Our method has been validated in compliance with the European Commission Decision 657/2002/EC, and we obtained very satisfactory results in inter-laboratory testing. Furthermore, we explored the use of a hybrid high resolution mass spectrometer, combining a quadrupole and an Orbitrap mass analyzer, for high resolution (HR) MS/MS detection of NSAIDs. We achieved lower NSAID quantification limits with Q-Orbitrap high resolution mass spectrometry (HRMS/MS) detection than those achieved with the QqQ instrument; however, its main feature is its very high selectivity, which makes HRMS/MS particularly suitable for confirmatory analysis.

Determination of 255 pesticides in edible vegetable oils using QuEChERS method and gas chromatography tandem mass spectrometry.

PubMed

He, Zeying; Wang, Yuehua; Wang, Lu; Peng, Yi; Wang, Wenwen; Liu, Xiaowei

2017-02-01

In this study, a simple and high-throughput method for determination of 255 pesticides in vegetable oils was developed based on QuEChERS sample preparation method combined with gas chromatography-triple quadrupole mass spectrometry. Different clean-up approaches were tested: A, 150 mg PSA + 150 mg C18; B, 250 mg PSA + 250 mg C18; C, 250 mg PSA + 250 mg C18 + 15 mg GCB; D, 250 mg PSA + 250 mg C18 + 50 mg GCB; and E, EMR-Lipid TM . Best clean-up capacity was observed for EMR clean-up. The extraction procedures and parameters, including extraction time, solvent/sample ratio, and buffer system, were also thoroughly investigated and optimized. The limits of quantification (LOQ) ranged between 5 and 50 μg kg -1 , and for the majority of the pesticides the LOQs were 5 μg kg -1 , which were below the regulatory MRLs. Most recoveries at seven spiking levels were in the range of 70-120 % with RSDs <20 % indicating satisfactory accuracy. The coefficient of determination (r 2 ) was >0.99 within the calibration linearity range of 2-500 μg L -1 for the majority of the pesticides. This method was proved to be simple, sensitive, and effective, which can be applied for large-scale pesticide screening and quantification in vegetable oils.

QuEChERS, a sample preparation technique that is “catching on”: an up-to-date interview with its inventors

USDA-ARS?s Scientific Manuscript database

The technique of QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) is only 7 years old, yet it is revolutionizing the manner in which multiresidue, multiclass pesticide analysis (and perhaps beyond) is performed. Columnist Ron Majors sits down with inventors Steve Lehotay and Michelangelo An...

Determination of six parabens residues in fresh-cut vegetables using QuEChERS with multi-walled carbon nanotubes and high performance liquid chromatography-tandem mass spectrometry

USDA-ARS?s Scientific Manuscript database

In this study, an optimized QuEChERS sample preparation method was developed to analyze residues of six parabens: methyl-, ethyl-, n-propyl-, isopropyl-, n-butyl-, and isobutyl-paraben in five fresh-cut vegetables (potato, broccoli, carrot, celery and cabbage) with high performance liquid chromatogr...

Feasibility and application of an HPLC/UVD to determine dinotefuran and its shorter wavelength metabolites residues in melon with tandem mass confirmation.

PubMed

Rahman, Md Musfiqur; Park, Jong-Hyouk; Abd El-Aty, A M; Choi, Jeong-Heui; Yang, Angel; Park, Ki Hun; Nashir Uddin Al Mahmud, Md; Im, Geon-Jae; Shim, Jae-Han

2013-01-15

A new analytical method was developed for dinotefuran and its metabolites, MNG, UF, and DN, in melon using high-performance liquid chromatography (HPLC) coupled with an ultraviolet detector (UVD). Due to shorter wavelength, lower sensitivity to UV detection, and high water miscibility of some metabolites, QuEChERs acetate-buffered version was modified for extraction and purification. Mobile phases with different ion pairing or ionisation agents were tested in different reverse phase columns, and ammonium bicarbonate buffer was found as the best choice to increase the sensitivity of target analytes to the UV detector. After failure of dispersive SPE clean-up with primary secondary amine, different solid phase extraction cartridges (SPE) were used to check the protecting capability of analytes against matrix interference. Finally, samples were extracted with a simple and rapid method using acetonitrile and salts, and purified through C(18)SPE. The method was validated at two spiking levels (three replicates for each) in the matrix. Good recoveries were observed for all of the analytes and ranged between 70.6% and 93.5%, with relative standard deviations of less than 10%. Calibration curves were linear over the calibration ranges for all the analytes with r(2)≥ 0.998. Limits of detection ranged from 0.02 to 0.05 mg kg(-1), whereas limits of quantitation ranged from 0.06 to 0.16 mg kg(-1) for dinotefuran and its metabolites. The method was successfully applied to real samples, where dinotefuran and UF residues were found in the field-incurred melon samples. Residues were confirmed via LC-tandem mass spectrometry (LC-MS/MS) in positive-ion electrospray ionisation (ESI(+)) mode. Copyright © 2012 Elsevier Ltd. All rights reserved.

UHPLC-MS/MS determination of ochratoxin A and fumonisins in coffee using QuEChERS extraction combined with mixed-mode SPE purification.

PubMed

Nielsen, Kristian Fog; Ngemela, Archard Ferdinand; Jensen, Lene Bai; de Medeiros, Lívia Soman; Rasmussen, Peter Have

2015-01-28

A method was developed for simultaneous determination of the mycotoxins: ochratoxin A (OTA) and fumonisins B2 (FB2), B4 (FB4), and B6 (FB6) in green, roasted, and instant coffee. Extraction was performed by QuEChERS (quick, easy, cheap, effective, rugged, and safe) under acidic conditions followed by mixed-mode reversed phase-anion exchange solid phase extraction. OTA and FB2 were detected at levels down to 0.5 and 2 μg/kg by UHPLC-MS/MS and quantitated via isotope dilution using U-(13)C-labeled FB2 and OTA as internal standards. Mixing 20% isopropanol in the acetonitrile of the acidic UHPLC gradient system increased the signal intensity by 50% and decreased the ion-suppression with 50-75% in roasted coffee samples. About half of the roasted coffee samples (n = 57, from 9 countries) contained detectable levels of OTA, however, with only 5 samples above the EU regulatory limit of 5 μg/kg and the highest with 21 μg/kg. None of the 25 instant coffee samples contained OTA above the EU regulatory level of 10 μg/kg. Nonetheless, the toxin could be detected in 56% of the analyzed instant coffee samples. Fumonisins were not detected in any of the roasted or instant coffee samples (n = 82). However, in the green coffee samples (n = 18) almost half of the samples were positive with a maximum value of 164 μg/kg (sum of FB2, FB4, and FB6). This discrepancy between green coffee and processed coffees indicated that the fumonisins decompose during the roasting process, which was confirmed in roasting experiments. Here fumonisins could not be detected after roasting of the green, 164 μg/kg coffee, sample. Under the same conditions, OTA was reduced from 2.4 to 0.5 μg/kg.

Use of ammonium formate in QuEChERS for high-throughput analysis of pesticides in food by fast, low-pressure gas chromatography and liquid chromatography tandem mass spectrometry

USDA-ARS?s Scientific Manuscript database

The “quick, easy, cheap, effective, rugged, and safe” (QuEChERS) approach to sample preparation is widely applied in pesticide residue analysis, but the use of magnesium sulfate for salting out in the method is not ideal for mass spectrometry. In this study we developed and evaluated three new diffe...

Simultaneous analysis of herbicides pendimethalin, oxyfluorfen, imazethapyr and quizalofop-p-ethyl by LC-MS/MS and safety evaluation of their harvest time residues in peanut (Arachis hypogaea L.).

PubMed

Saha, Ajoy; Shabeer T P, Ahammed; Banerjee, Kaushik; Hingmire, Sandip; Bhaduri, Debarati; Jain, N K; Utture, Sagar

2015-07-01

This paper reports a simple and rapid method for simultaneous determination of the residues of selected herbicides viz. pendimethalin, oxyfluorfen, imazethapyr and quizalofop-p-ethyl in peanut by liquid chromatography-tandem mass spectrometry (LC-MS/MS). A modified approach of the QuEChERS methodology was used to extract the herbicides from the peanut kernel without any clean-up. The method showed excellent linearity (r(2) > 0.99) with no significant matrix effect. Accuracy of the method in terms of average recoveries of all the four herbicides ranged between 69.4 -94.4 % at spiking levels of 0.05, 0.10 and 0.25 mg kg(-1) with intra-day and inter-day precision RSD (%) between 2.6-16.6 and 8.0-11.3, respectively. Limit of quantification (LOQs) was 5.0 μg kg(-1) for pendimethalin, imazethapyr and quizalofop-p-ethyl and 10.0 μg kg(-1) for oxyfluorfen. The expanded uncertainties were <11 % for determination of these herbicides in peanut. The proposed method was successfully applied for analysis of these herbicide residues in peanut samples harvested from the experimental field and the residues were below the detection level.

Analysis of sulfonamides, tilmicosin and avermectins residues in typical animal matrices with multi-plug filtration cleanup by liquid chromatography-tandem mass spectrometry detection.

PubMed

Qin, Yuhong; Jatamunua, Freedom; Zhang, Jingru; Li, Yanjie; Han, Yongtao; Zou, Nan; Shan, Jihao; Jiang, Yanbin; Pan, Canping

2017-05-15

The frequent use of various veterinary drugs could lead to residue bioaccumulation in animal tissues, which could cause dietary risks to human health. In order to quickly analyze the residues, a liquid chromatography tandem mass spectrometry (LC-MS/MS) method was developed for detecting Sulfonamides, Tilmicosin and Avermectins (AVMs) residues in animal samples. For sample preparation, modified QuEChERS (quick, easy, cheap, effective, rugged and safe) and ultrasound-assisted extraction (UAE) methods were used. For sample cleanup, n-Hexane delipidation and multi-plug filtration cleanup (m-PFC) method based on primary-secondary amine (PSA) and octadecyl-silica (C18) were used, followed by LC-MS/MS analysis. It was validated on 7 animal matrices (bovine, caprine, swine meat and their kidneys, milk) at two fortified concentration levels of 5 and 100μg/kg. The recoveries ranged from 82 to 107% for all analytes with relative standard deviations (RSDs) less than 15%. Matrix-matched calibrations were performed with coefficients of determination above 0.998 for all analytes within concentration levels of 5-500μg/kg. The developed method was successfully used to analysis veterinary drugs of real animal samples from local markets. Copyright © 2017 Elsevier B.V. All rights reserved.

Dietary risk assessment of pesticides from vegetables and drinking water in gardening areas in Burkina Faso.

PubMed

Lehmann, Edouard; Turrero, Nuria; Kolia, Marius; Konaté, Yacouba; de Alencastro, Luiz Felippe

2017-12-01

Vegetables and water samples have been collected around the lake of Loumbila in Burkina Faso. Pesticides residues in food commodities were analyzed using a modified QuEChERS extraction method prior analysis on GC-MS and UPLC-MS/MS of 31 pesticides. Maximum Residue Limits (MRLs) were exceeded in 36% of the samples for seven pesticides: acetamiprid, carbofuran, chlorpyrifos, lambda-cyhalothrin, dieldrin, imidacloprid and profenofos. Exceedance of MRLs suggests a risk for the consumers and limits the opportunities of exportation. In order to define estimated daily intake, dietary surveys were conducted on 126 gardeners using a 24hours recall method. Single pesticide and cumulative exposure risks were assessed for children and adults. Risk was identified for: chlorpyrifos and lambda-cyhalothrin in acute and chronic exposure scenarios. Hazardous chronic exposure to the endocrine disruptor and probable carcinogen dieldrin was also detected. In the studied population, cumulative dietary exposure presented a risk (acute and chronic) for children and adults in respectively >17% and 4% of the cases when considering the worst case scenarios. Processing factor largely influenced the risk of occurrence suggesting that simple washing of vegetables with water considerably reduced the risk of hazardous exposure. Copyright © 2017 Elsevier B.V. All rights reserved.

Determination of tocopherols and sitosterols in seeds and nuts by QuEChERS-liquid chromatography.

PubMed

Delgado-Zamarreño, M Milagros; Fernández-Prieto, Cristina; Bustamante-Rangel, Myriam; Pérez-Martín, Lara

2016-02-01

In the present work a simple, reliable and affordable sample treatment method for the simultaneous analysis of tocopherols and free phytosterols in nuts was developed. Analyte extraction was carried out using the QuEChERS methodology and analyte separation and detection were accomplished using HPLC-DAD. The use of this methodology for the extraction of natural occurring substances provides advantages such as speed, simplicity and ease of use. The parameters evaluated for the validation of the method developed included the linearity of the calibration plots, the detection and quantification limits, repeatability, reproducibility and recovery. The proposed method was successfully applied to the analysis of tocopherols and free phytosterols in samples of almonds, cashew nuts, hazelnuts, peanuts, tiger nuts, sun flower seeds and pistachios. Copyright © 2015 Elsevier Ltd. All rights reserved.

Fast and easy extraction combined with high resolution-mass spectrometry for residue analysis of two anticonvulsants and their transformation products in marine mussels.

PubMed

Martínez Bueno, M J; Boillot, C; Fenet, H; Chiron, S; Casellas, C; Gómez, E

2013-08-30

Environmental field studies have shown that carbamazepine (Cbz) is one of the most frequently detected human pharmaceuticals in different aquatic compartments. However, little data is available on the detection of this substance and its transformation products in aquatic organisms. This study was thus mainly carried out to optimize and validate a simple and sensitive analytical methodology for the detection, characterization and quantification of Cbz and oxcarbazepine (Ox), two anticonvulsants, and six of their main transformation products in marine mussels (Mytilus galloprovincialis). A modified QuEChERS extraction method followed by analysis with liquid chromatography coupled to high resolution mass spectrometry (HRMS) was used. The analyses were performed using two-stage fragmentation to reveal the different fragmentation pathways that are highly useful for the identification of isomeric compounds, a common problem when several transformation products are analyzed. The developed analytical method allowed determination of the target analytes in the lower ng/g concentration levels. The mean recovery ranged from 67 to 110%. The relative standard deviation was under 11% in the intra-day and 18% in the inter-day analyses, respectively. Finally, the method was applied to marine mussel samples collected from Mediterranean Sea cultures in southeastern France. Residues of the psychiatric drug Cbz were occasionally found at levels up to 3.5ng/g dw. Lastly, in this study, other non-target compounds, such as caffeine, metoprolol, cotinine and ketoprofen, were identified in the real samples analyzed. Copyright © 2013 Elsevier B.V. All rights reserved.

Body burden of pesticides and wastewater-derived pollutants on freshwater invertebrates: Method development and application in the Danube River.

PubMed

Inostroza, Pedro A; Wicht, Anna-Jorina; Huber, Thomas; Nagy, Claudia; Brack, Werner; Krauss, Martin

2016-07-01

While environmental risk assessment is typically based on toxicant concentrations in water and/or sediment, awareness is increasing that internal concentrations or body burdens are the key to understand adverse effects in organisms. In order to link environmental micropollutants as causes of observed effects, there is an increasing demand for methods to analyse these chemicals in organisms. Here, a multi-target screening method based on pulverised liquid extraction (PuLE) and a modified QuEChERS approach with an additional hexane phase was developed. It is capable to extract and quantify organic micropollutants of diverse chemical classes in freshwater invertebrates. The method was tested on gammarids from the Danube River (within the Joint Danube Survey 3) and target compounds were analysed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Furthermore, a non-target screening using high resolution-tandem mass spectrometry (LC-HRMS/MS) was conducted. A total of 17 pollutants were detected and/or quantified in gammarids at low concentrations. Pesticide concentrations ranged from 0.1 to 6.52 ng g(-1) (wet weight), those of wastewater-derived pollutants from 0.1 to 2.83 ng g(-1) (wet weight). The presence of wastewater-derived pollutants was prominent at all spots sampled. Using non-target screening, we could successfully identify several chlorinated compounds. These results demonstrate for the first time the presence of pesticides and wastewater-derived pollutants in invertebrates of the Danube River. Copyright © 2016 Elsevier Ltd. All rights reserved.

Dispersive Solid Phase Extraction for the Analysis of Veterinary Drugs Applied to Food Samples: A Review

PubMed Central

Islas, Gabriela; Hernandez, Prisciliano

2017-01-01

To achieve analytical success, it is necessary to develop thorough clean-up procedures to extract analytes from the matrix. Dispersive solid phase extraction (DSPE) has been used as a pretreatment technique for the analysis of several compounds. This technique is based on the dispersion of a solid sorbent in liquid samples in the extraction isolation and clean-up of different analytes from complex matrices. DSPE has found a wide range of applications in several fields, and it is considered to be a selective, robust, and versatile technique. The applications of dispersive techniques in the analysis of veterinary drugs in different matrices involve magnetic sorbents, molecularly imprinted polymers, carbon-based nanomaterials, and the Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) method. Techniques based on DSPE permit minimization of additional steps such as precipitation, centrifugation, and filtration, which decreases the manipulation of the sample. In this review, we describe the main procedures used for synthesis, characterization, and application of this pretreatment technique and how it has been applied to food analysis. PMID:29181027

[Rapid screening and confirmation of 205 pesticide residues in rice by QuEChERS and liquid chromatography-mass spectrometry].

PubMed

Chen, Xi; Cheng, Lei; Qu, Shichao; Huang, Daliang; Liu, Jiacheng; Cui, Han; Jia, Yanbo; Ji, Mingshan

2015-10-01

A method for rapid screening and confirmation of 205 pesticide residues in rice was developed by combining QuEChERS and high performance liquid chromatography-triple quadrupole-linear ion trap mass spectrometry (LC-Q-TRAP/MS). The rice samples were extracted with acetonitrile, and then cleaned up with primary secondary amine (PSA), anhydrous magnesium sulfate (MgSO4) and C18 adsorbent. Finally, the samples were detected by LC-Q-TRAP/MS in multiple reaction monitoring with information-dependent acquisition of enhanced product ion (MRM-IDA-EPI) mode followed with database searching. A total of 205 pesticide residues were confirmed by retention times, ion pairs and the database searching using EPI library, and quantified by external standard method. All the pesticides showed good linearities with linear correlation coefficients all above 0.995. The limits of quantification (LOQs) for the 205 pesticides were 0.5-10.0 μg/kg. The average recoveries of the 205 pesticides ranged from 62.4% to 127.1% with the relative standard deviations (RSDs) of 1.0% - 20.0% at spiked levels of 10 μg/kg and 50 μg/kg, and only 20 min were needed for the analysis of an actual rice sample. In brief, the method is fast, accurate and highly sensitive, and is suitable for the screening and confirmation of pesticide residues in rice.

Pesticide residues in fruit samples: comparison of different QuEChERS methods using liquid chromatography-tandem mass spectrometry.

PubMed

Christia, C; Bizani, E; Christophoridis, C; Fytianos, K

2015-09-01

Acetate- and citrate-buffered quick, easy, cheap, effective, rugged, safe (QuEChERS) pretreatment methods were evaluated for the determination of various pesticides in peaches, grapes, apples, bananas, pears, and strawberries from various regions of Greece, using LC-MS/MS. The purposes of this study were (i) to evaluate which type of QuEChERS method was the most appropriate and effective for each matrix; (ii) to apply the selected QuEChERS method for each matrix, in order to detect and quantify pesticide residues in various fruit samples using UPLC-MS/MS; (iii) to examine the concentration distribution of pesticide classes among fruit originating from various areas; and (iv) to assess pesticide concentration distribution between peel and flesh of fruit in order to evaluate the penetration of pesticide residues in the fruit flesh. Acetate-buffered QuEChERS was found to be the most suitable technique for most of the fruit matrices. According to the recovery values at two different concentration levels, peaches should preferably be treated by the citrate-buffered type, whereas grapes, bananas, apples, pears, and strawberries are best treated by the acetate-buffered version, although the differences in efficiency were small. The addition of graphitized carbon black significantly decreases the recovery of specific pesticides in all matrices except for strawberries. The majority of values do not exceed the official maximum residue levels set by the European Commission. Organophosphates proved to be the most commonly detected category along with triazines-triazoles-conazoles group and by carbamates. Apples and pears seem to be the most contaminated fruit matrices among those tested. Distribution of pesticide classes shows variations between different regions, suggesting different pesticide application practices. In the case of peaches and pears, there is an equal distribution of detected pesticides between peel and flesh, indicating penetration of contaminants into the fruit flesh.

Screening of 23 β-lactams in foodstuffs by LC-MS/MS using an alkaline QuEChERS-like extraction.

PubMed

Bessaire, Thomas; Mujahid, Claudia; Beck, Andrea; Tarres, Adrienne; Savoy, Marie-Claude; Woo, Pei-Mun; Mottier, Pascal; Desmarchelier, Aurélien

2018-04-01

A fast and robust high performance LC-MS/MS screening method was developed for the analysis of β-lactam antibiotics in foods of animal origin: eggs, raw milk, processed dairy ingredients, infant formula, and meat- and fish-based products including baby foods. QuEChERS extraction with some adaptations enabled 23 drugs to be simultaneously monitored. Screening target concentrations were set at levels adequate to ensure compliance with current European, Chinese, US and Canadian regulations. The method was fully validated according to the European Community Reference Laboratories Residues Guidelines using 93 food samples of different composition. False-negative and false-positive rates were below 5% for all analytes. The method is adequate for use in high-routine laboratories. A 1-year study was additionally conducted to assess the stability of the 23 analytes in the working standard solution.

Metabolic and Dynamic Profiling for Risk Assessment of Fluopyram, a Typical Phenylamide Fungicide Widely Applied in Vegetable Ecosystem

PubMed Central

Wei, Peng; Liu, Yanan; Li, Wenzhuo; Qian, Yuan; Nie, Yanxia; Kim, Dongyeop; Wang, Mengcen

2016-01-01

Fluopyram, a typical phenylamide fungicide, was widely applied to protect fruit vegetables from fungal pathogens-responsible yield loss. Highly linked to the ecological and dietary risks, its residual and metabolic profiles in the fruit vegetable ecosystem still remained obscure. Here, an approach using modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) extraction combined with GC-MS/MS analysis was developed to investigate fluopyram fate in the typical fruit vegetables including tomato, cucumber, pepper under the greenhouse environment. Fluopyram dissipated in accordance with the first-order rate dynamics equation with the maximum half-life of 5.7 d. Cleveage of fluopyram into 2-trifluoromethyl benzamide and subsequent formation of 3-chloro-5-(trifluoromethyl) pyridine-2-acetic acid and 3-chloro-5-(trifluoromethyl) picolinic acid was elucidated to be its ubiquitous metabolic pathway. Moreover, the incurrence of fluopyram at the pre-harvest interval (PHI) of 7–21 d was between 0.0108 and 0.1603 mg/kg, and the Hazard Quotients (HQs) were calculated to be less than 1, indicating temporary safety on consumption of the fruit vegetables incurred with fluopyram, irrespective of the uncertain toxicity of the metabolites. Taken together, our findings reveal the residual essential of fluopyram in the typical agricultural ecosystem, and would advance the further insight into ecological risk posed by this fungicide associated with its metabolites. PMID:27654708

Detection of β-Lactams and Chloramphenicol Residues in Raw Milk-Development and Application of an HPLC-DAD Method in Comparison with Microbial Inhibition Assays.

PubMed

Karageorgou, Eftychia; Christoforidou, Sofia; Ioannidou, Maria; Psomas, Evdoxios; Samouris, Georgios

2018-06-01

The present study was carried out to assess the detection sensitivity of four microbial inhibition assays (MIAs) in comparison with the results obtained by the High Performance Liquid Chromatography with Diode-Array Detection (HPLC-DAD) method for antibiotics of the β-lactam group and chloramphenicol in fortified raw milk samples. MIAs presented fairly good results when detecting β-lactams, whereas none were able to detect chloramphenicol at or above the permissible limits. HPLC analysis revealed high recoveries of examined compounds, whereas all detection limits observed were lower than their respective maximum residue limits (MRL) values. The extraction and clean-up procedure of antibiotics was performed by a modified matrix solid phase dispersion procedure using a mixture of Plexa by Agilent and QuEChERS as a sorbent. The HPLC method developed was validated, determining the accuracy, precision, linearity, decision limit, and detection capability. Both methods were used to monitor raw milk samples of several cows and sheep, obtained from producers in different regions of Greece, for the presence of examined antibiotic residues. Results obtained showed that MIAs could be used effectively and routinely to detect antibiotic residues in several milk types. However, in some cases, spoilage of milk samples revealed that the kits' sensitivity could be strongly affected, whereas this fact does not affect the effectiveness of HPLC-DAD analysis.

Metabolic and Dynamic Profiling for Risk Assessment of Fluopyram, a Typical Phenylamide Fungicide Widely Applied in Vegetable Ecosystem

NASA Astrophysics Data System (ADS)

Wei, Peng; Liu, Yanan; Li, Wenzhuo; Qian, Yuan; Nie, Yanxia; Kim, Dongyeop; Wang, Mengcen

2016-09-01

Fluopyram, a typical phenylamide fungicide, was widely applied to protect fruit vegetables from fungal pathogens-responsible yield loss. Highly linked to the ecological and dietary risks, its residual and metabolic profiles in the fruit vegetable ecosystem still remained obscure. Here, an approach using modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) extraction combined with GC-MS/MS analysis was developed to investigate fluopyram fate in the typical fruit vegetables including tomato, cucumber, pepper under the greenhouse environment. Fluopyram dissipated in accordance with the first-order rate dynamics equation with the maximum half-life of 5.7 d. Cleveage of fluopyram into 2-trifluoromethyl benzamide and subsequent formation of 3-chloro-5-(trifluoromethyl) pyridine-2-acetic acid and 3-chloro-5-(trifluoromethyl) picolinic acid was elucidated to be its ubiquitous metabolic pathway. Moreover, the incurrence of fluopyram at the pre-harvest interval (PHI) of 7-21 d was between 0.0108 and 0.1603 mg/kg, and the Hazard Quotients (HQs) were calculated to be less than 1, indicating temporary safety on consumption of the fruit vegetables incurred with fluopyram, irrespective of the uncertain toxicity of the metabolites. Taken together, our findings reveal the residual essential of fluopyram in the typical agricultural ecosystem, and would advance the further insight into ecological risk posed by this fungicide associated with its metabolites.

Rapid and Simultaneous Analysis of 360 Pesticides in Brown Rice, Spinach, Orange, and Potato Using Microbore GC-MS/MS.

PubMed

Lee, Jonghwa; Kim, Leesun; Shin, Yongho; Lee, Junghak; Lee, Jiho; Kim, Eunhye; Moon, Joon-Kwan; Kim, Jeong-Han

2017-04-26

A multiresidue method for the simultaneous and rapid analysis of 360 pesticides in representative agricultural produce (brown rice, orange, spinach, and potato) was developed using a modified QuEChERS procedure combined with gas chromatography-tandem mass spectrometry (GC-MS/MS). Selected reaction monitoring transition parameters (e.g., collision energy, precursor and product ions) in MS/MS were optimized to achieve the best selectivity and sensitivity for a wide range of GC-amenable pesticides. A short (20 m) microbore (0.18 mm i.d.) column resulted in better signal-to-noise ratio with reduced analysis time than a conventional narrowbore column (30 m × 0.25 mm i.d.). The priming injection dramatically increased peak areas by masking effect on a new GC liner. The limit of quantitation was <0.01 mg/kg, and the correlation coefficients (r 2 ) of matrix-matched standards were >0.99 within the range of 0.0025-0.1 mg/kg. Acetonitrile with 0.1% formic acid without additional buffer salts was used for pesticide extraction, whereas only primary-secondary amine (PSA) was used for dispersive solid phase extraction (dSPE) cleanup, to achieve good recoveries for most of the target analytes. The recoveries ranged from 70 to 120% with relative standard deviations of ≤20% at 0.01 and 0.05 mg/kg spiking levels (n = 6) in all samples, indicating acceptable accuracy and precision of the method. Seventeen real samples from local markets were analyzed by using the optimized method, and 14 pesticides in 11 incurred samples were found at below the maximum residue limits.

Multiresidue method for the determination of 77 pesticides in wine using QuEChERS sample preparation and gas chromatography with mass spectrometry.

PubMed

Jiang, Y; Li, X; Xu, J; Pan, C; Zhang, J; Niu, W

2009-06-01

A method based on a QuEChERS (quick, easy, cheap, effective, rugged, safe) sample preparation method and gas chromatography with mass spectrometric detection by selected ion monitoring (GC/MS-SIM) was developed for simultaneous determination of 77 pesticide residues in wine. An extraction of 10 ml of sample with acetonitrile followed by liquid-liquid partition formed by the addition of 4 g MgSO(4) and 3 g NaCl was applied in the sample preparation. The clean-up was carried out by applying dispersive solid-phase with 150 mg MgSO(4) as well as 50 mg primary secondary amine (PSA). One quantitation ion and at least two identification ions were selected in the analytical method for each pesticide compound by GC/MS. The recovery data were obtained by spiking blank samples at two concentration levels (0.05 and 0.2 mg l(-1)). The recoveries of all pesticides were in the range 70-110%, with intra-day precision of less than 15%, and the inter-day precision of less than 22% and 15% for 0.05 and 0.2 mg l(-1) fortification levels, respectively. Linearity was between 0.02 and 2 mg l(-1) with determination coefficients (R(2)) greater than 0.98 for all compounds. The limits of quantification (LOQs) for the 77 pesticides ranged from 0.003 to 0.05 mg l(-1). This method was applied for routine analysis in market products.

[Determination of six anticoccidials in chicken using QuEChERS combined with ultra high liquid chromatography-high resolution mass spectrometry].

PubMed

Muharem, Muhteber; Yan, Hua; Xu, Shan; Feng, Nan; Hao, Jie; Zhu, Chenqi; Guo, Shuang; Zhang, Zhaohui; Han, Nanyin

2015-11-01

An ultra high liquid chromatography-Q Exactive orbitrap mass spectrometry multi-residue method has been developed for the determination of six anticoccidials residues (dinitlmide, nicarbazin, diclazuril, toltrazuril, monensin and salinomycin) in chicken tissue. Sample preparation was based on QuEChERS method, using 1% (v/v) trichloroacetic acid/acetonitrile aqueous solution (3:7, v/v) as the extraction solvent and salting-out with sodium chloride followed by clean-up with 50 mg/mL primary secondary amine (PSA) +50 mg/mL neutral alumina (Alumina-N) dispersive solid phase extraction (DSPE). The separation of the compounds in liquid chromatography was carried out using a Waters Acquity UPLC BEH C8 column (100 mm x 2.1 mm, 1.7 μm) with mobile phases consisting of methanol-5 mmol/L ammonium acetate aqueous solution in gradient elution. The Q Exactive orbitrap mass spectrometric detection was carried out with positive and negative electrospray ionization simultaneously. The results showed the linear ranges of the six target compounds were as follows: dinitolmide, 1.0-30.0 μg/L; nicarbazin, 0.2-6.0 μg/L; diclazuril and toltrazuril, 2.0-60.0 [μg/L; monensin and salinomycin, 4.0-120.0 μg/L. The external standard method was used for quantification. The spiked recoveries at three levels for the six anticoccidials ranged from 67.7% to 126.8%. The relative standard deviations (RSDs) were ≤ 10.4%. The limits of quantification (LOQs) were as follows: dinitolmide, 2.50 μg/kg; nicarbazin, 0.50 μg/kg; diclazuril and toltrazuril, 5.00 μg/kg; monensin and salinomycin, 20.00 μg/kg. The developed method is easy of operation and of high sensitivity. It can meet the requirements of daily inspection.

Analytical strategies for organic food packaging contaminants.

PubMed

Sanchis, Yovana; Yusà, Vicent; Coscollà, Clara

2017-03-24

In this review, we present current approaches in the analysis of food-packaging contaminants. Gas and liquid chromatography coupled to mass spectrometry detection have been widely used in the analysis of some relevant families of these compounds such as primary aromatic amines, bisphenol A, bisphenol A diglycidyl ether and related compounds, UV-ink photoinitiators, perfluorinated compounds, phthalates and non-intentionally added substances. Main applications for sample treatment and different types of food-contact material migration studies have been also discussed. Pressurized Liquid Extraction, Solid-Phase Microextraction, Focused Ultrasound Solid-Liquid Extraction and Quechers have been mainly used in the extraction of food contact material (FCM) contaminants, due to the trend of minimising solvent consumption, automatization of sample preparation and integration of extraction and clean-up steps. Recent advances in analytical methodologies have allowed unequivocal identification and confirmation of these contaminants using Liquid Chromatography coupled to High Resolution Mass Spectrometry (LC-HRMS) through mass accuracy and isotopic pattern applying. LC-HRMS has been used in the target analysis of primary aromatic amines in different plastic materials, but few studies have been carried out applying this technique in post-target and non-target analysis of FCM contaminants. Copyright © 2017 Elsevier B.V. All rights reserved.

Increasing productivity for the analysis of trace contaminants in food by gas chromatography-mass spectrometry using automated liner exchange, backflushing and heart-cutting.

PubMed

David, Frank; Tienpont, Bart; Devos, Christophe; Lerch, Oliver; Sandra, Pat

2013-10-25

Laboratories focusing on residue analysis in food are continuously seeking to increase sample throughput by minimizing sample preparation. Generic sample extraction methods such as QuEChERS lack selectivity and consequently extracts are not free from non-volatile material that contaminates the analytical system. Co-extracted matrix constituents interfere with target analytes, even if highly sensitive and selective GC-MS/MS is used. A number of GC approaches are described that can be used to increase laboratory productivity. These techniques include automated inlet liner exchange and column backflushing for preservation of the performance of the analytical system and heart-cutting two-dimensional GC for increasing sensitivity and selectivity. The application of these tools is illustrated by the analysis of pesticides in vegetables and fruits, PCBs in milk powder and coplanar PCBs in fish. It is demonstrated that considerable increase in productivity can be achieved by decreasing instrument down-time, while analytical performance is equal or better compared to conventional trace contaminant analysis. Copyright © 2013 Elsevier B.V. All rights reserved.

Application of dispersive solid phase extraction for trace analysis of toxic chemicals in foods.

PubMed

Neely, Sarah; Martin, Jordan; da Cruz, Natalia Ferreira; Piester, Gavin; Robinson, Morgan; Okoniewski, Richard; Tran, Buu N

2018-05-29

The objectives of this study were to develop and validate a method for the identification of toxic organic chemicals, including groups of controlled substances, alkaloids and pesticides that are highly toxic and considered threats to public health. This project aims to ensure our laboratory's readiness to respond to emergencies involving our food supply in cooperation with the Food Emergency Response Network (FERN) program. The food matrices were homogenized in a blender or food processor prior to extraction with an acetonitrile-water mixture using a QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) procedure. The extracts were then analyzed by either gas chromatography-mass spectrometry (GC-MS) or liquid chromatography-electrospray tandem mass spectrometry (LC-ESI/MS/MS). Method validation was performed on a variety of food matrices including lettuce, grapes, milk, chicken, pork and beef. MDLs for the toxic compounds ranged from 0.01 to 0.66 mg/kg (ppm). The findings in this study will provide a valuable resource for the determination of toxic chemicals in food matrices for emergency response situations. Copyright © 2018. Published by Elsevier B.V.

Validation Study on a Rapid Method for Simultaneous Determination of Pesticide Residues in Vegetables and Fruits by LC-MS/MS.

PubMed

Sato, Tamaki; Miyamoto, Iori; Uemura, Masako; Nakatani, Tadashi; Kakutani, Naoya; Yamano, Tetsuo

2016-01-01

A validation study was carried out on a rapid method for the simultaneous determination of pesticide residues in vegetables and fruits by LC-MS/MS. Preparation of the test solution was performed by a solid-phase extraction technique with QuEChERS (STQ method). Pesticide residues were extracted with acetonitrile using a homogenizer, followed by salting-out and dehydration at the same time. The acetonitrile layer was purified with C18 and PSA mini-columns. The method was assessed for 130 pesticide residues in 14 kinds of vegetables and fruits at the concentration level of 0.01 μg/g according to the method validation guideline of the Ministry of Health, Labour and Welfare of Japan. As a result 75 to 120 pesticide residues were determined satisfactorily in the tested samples. Thus, this method could be useful for a rapid and simultaneous determination of multi-class pesticide residues in various vegetables and fruits.

Air-assisted liquid-liquid microextraction integrated with QuEChERS for determining endocrine-disrupting compounds in fish by high-performance liquid chromatography-tandem mass spectrometry.

PubMed

Luo, Zhoufei; Lu, Jing; Li, Haipu; Tu, Yi; Wan, Yuehao; Yang, Zhaoguang

2018-09-15

A new, sensitive, and rapid method based on the Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) approach and air-assisted liquid-liquid microextraction (AALLME) technology was developed for the determination of 20 endocrine-disrupting compounds (EDCs) in fish by high-performance liquid chromatography-tandem mass spectrometry. The method first integrates AALLME into QuEChERS to achieve clean-up and enrichment of the EDCs in one step. A self-made glass tube was enfolded with plasticine to withstand the high centrifugal force. The established method was developed by optimization of the parameters. High linearities (R 2  > 0.9924) and recoveries (78.2-118.6%) at three spiked levels (5, 10, and 20 ng g -1 ), and low relative standard deviation values (1.1-14.5%) and limits of detection (0.03-0.80 ng g -1 ) were obtained. The method comparison shows that the proposed method is superior as it involves less organic solvent usage, simple operation and high efficiency. This method was successfully applied to different fishes for analyzing EDCs. Copyright © 2018 Elsevier Ltd. All rights reserved.

Automated multi-plug filtration cleanup for liquid chromatographic-tandem mass spectrometric pesticide multi-residue analysis in representative crop commodities.

PubMed

Qin, Yuhong; Zhang, Jingru; Zhang, Yuan; Li, Fangbing; Han, Yongtao; Zou, Nan; Xu, Haowei; Qian, Meiyuan; Pan, Canping

2016-09-02

An automated multi-plug filtration cleanup (m-PFC) method on modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) extracts was developed. The automatic device was aimed to reduce labor-consuming manual operation workload in the cleanup steps. It could control the volume and the speed of pulling and pushing cycles accurately. In this work, m-PFC was based on multi-walled carbon nanotubes (MWCNTs) mixed with other sorbents and anhydrous magnesium sulfate (MgSO4) in a packed tip for analysis of pesticide multi-residues in crop commodities followed by liquid chromatography with tandem mass spectrometric (LC-MS/MS) detection. It was validated by analyzing 25 pesticides in six representative matrices spiked at two concentration levels of 10 and 100μg/kg. Salts, sorbents, m-PFC procedure, automated pulling and pushing volume, automated pulling speed, and pushing speed for each matrix were optimized. After optimization, two general automated m-PFC methods were introduced to relatively simple (apple, citrus fruit, peanut) and relatively complex (spinach, leek, green tea) matrices. Spike recoveries were within 83 and 108% and 1-14% RSD for most analytes in the tested matrices. Matrix-matched calibrations were performed with the coefficients of determination >0.997 between concentration levels of 10 and 1000μg/kg. The developed method was successfully applied to the determination of pesticide residues in market samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Development of a method for the simultaneous determination of multi-class pesticides in earthworms by liquid chromatography coupled to tandem electrospray mass spectrometry.

PubMed

Daniele, Gaëlle; Lafay, Florent; Pelosi, Céline; Fritsch, Clémentine; Vulliet, Emmanuelle

2018-06-04

Agricultural intensification, and in particular the use of pesticides, leads over the years to a loss of biodiversity and a decline of ecosystem services in cultivated zones and agricultural landscapes. Among the animal communities involved in the functioning of agro-ecosystems, earthworms are ubiquitous and recognized as indicators of land uses and cultural practices. However, little data is available on the levels of pesticides in such organisms in natura, which would allow estimating their actual exposure and the potentially resulting impacts. Thus, the objective of this study was to develop a sensitive analytical methodology to detect and quantify 27 currently used pesticides in earthworms (Allolobophora chlorotica). A modified QuEChERS extraction was implemented on individual earthworms. This step was followed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). The whole analytical method was validated on spiked earthworm blank samples, with regard to linearity (from 1 to 100 method limit of quantification, r 2  > 0.95), intra-day precision (relative standard deviation (RSD) < 15%), inter-day precision (RSD < 20%), recoveries (mainly in the range 70-110%), and limits of detection and of quantification (inferior to 5 ng/g for most of the pesticides). The developed method was successfully applied to determine the concentrations of pesticides in nine individuals collected in natura. Up to five of the selected pesticides have been detected in one individual. Graphical abstract.

Gas chromatography with mass spectrometry for the quantification of ethylene glycol ethers in different household cleaning products.

PubMed

Pastor-Belda, Marta; Campillo, Natalia; Hernández-Córdoba, Manuel; Viñas, Pilar

2016-06-01

A rapid and simple procedure is reported for the determination of six ethylene glycol ethers in cleaning products and detergents using gas chromatography with mass spectrometry. The analytes were extracted from 2.0 g samples in acetonitrile (3 mL) and the extract was submitted to a clean-up step by QuEChERS method, using a mixture containing 0.3 g magnesium sulfate, 0.15 g primary/secondary amine, and 0.05 g C18 . The clean acetonitrile extract (1 μL) was injected into the chromatographic system. No matrix effect was observed, so the quantification of the samples was carried out against external standards. Detection limits were in the range 3.0-27 ng/g for the six ethylene glycol ethers. The recoveries obtained, using the optimized procedure, were in the 89.4-118% range, with relative standard deviations lower than 14%. Twenty-three different household cleaning products, including glass cleaner, degreaser, floor, softeners, and clothes and dishwashing detergents, were analyzed. Large interindividual variations were observed between samples and compounds. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fast analysis of 4-tertoctylphenol, pentachlorophenol and 4-nonylphenol in river sediments by QuEChERS extraction procedure combined with GC-QqQ-MS/MS.

PubMed

Czech, T; Bonilla, N Barco; Gambus, F; González, R Romero; Marín-Sáez, J; Vidal, J L Martínez; Frenich, A Garrido

2016-07-01

A quick, easy, cheap, effective, rugged and safe (QuEChERS)-based extraction method has been optimized for the determination of pentachlorophenol, 4-tertoctylphenol and 4-nonylphenol in river sediments. The extraction method was followed by gas chromatography-triple quadrupole tandem mass spectrometry (GC-QqQ-MS/MS) analysis, which ensures the reliable identification of the target compounds. The proposed method has been validated allowing the successful determination of the selected compounds, with recoveries ranging from 72 to 96%, when three concentration levels were evaluated (10, 50 and 100μgkg(-1)) and inter-day and intra-day precision, expressed as relative standard deviation (RSD), were lower than 20%. The method showed limits of detection (LODs) and limits of quantification (LOQs) ranging from 0.1 to 2.0μgkg(-1) and from 0.5 to 5.0μgkg(-1), respectively. Finally, 25 real samples from Poland have been analyzed, and only 4-tertoctylphenol was detected at concentrations up to 8.9μgkg(-1) of soil dry weight. Copyright © 2016 Elsevier B.V. All rights reserved.

Multi-pesticides residue analysis of grains using modified magnetic nanoparticle adsorbent for facile and efficient cleanup.

PubMed

Liu, Zhenzhen; Qi, Peipei; Wang, Xiangyun; Wang, Zhiwei; Xu, Xiahong; Chen, Wenxue; Wu, Liyu; Zhang, Hu; Wang, Qiang; Wang, Xinquan

2017-09-01

A facile, rapid sample pretreatment method was developed based on magnetic nanoparticles for multi-pesticides residue analysis of grains. Magnetite (Fe 3 O 4 ) nanoparticles modified with 3-(N,N-diethylamino)propyltrimethoxysilane (Fe 3 O 4 -PSA) and commercial C18 were selected as the cleanup adsorbents to remove the target interferences of the matrix, such as fatty acids and non-polar compounds. Rice was used as the representative grain sample for method optimization. The amount of Fe 3 O 4 -PSA and C18 were systematically investigated for selecting the suitable purification conditions, and the simultaneous determination of 50 pesticides and 8 related metabolites in rice was established by liquid chromatography-tandem mass spectrometry. Under the optimal conditions, the method validation was performed including linearity, sensitivity, matrix effect, recovery and precision, which all satisfy the requirement for pesticides residue analysis. Compared to the conventional QuEChERS method with non-magnetic material as cleanup adsorbent, the present method can save 30% of the pretreatment time, giving the high throughput analysis possible. Copyright © 2017 Elsevier Ltd. All rights reserved.

Alternative sorbents for the dispersive solid-phase extraction step in quick, easy, cheap, effective, rugged and safe method for extraction of pesticides from rice paddy soils with determination by liquid chromatography tandem mass spectrometry.

PubMed

Arias, Jean Lucas de Oliveira; Rombaldi, Caroline; Caldas, Sergiane Souza; Primel, Ednei Gilberto

2014-09-19

The clean-up step is essential to reduce interferences, improve quantification and help to maintain the integrity of the chromatographic system when working with complex matrices. In this study, alternative materials were evaluated as sorbents in the dispersive solid-phase extraction (D-SPE) for the determination and extraction of seventeen pesticides from rice paddy soil samples by the quick, easy, cheap, effective, rugged and safe (QuEChERS) method coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS). Chitin, chitosan, diatomaceous earth and PSA were compared in terms of extraction efficiency and matrix effect. The best results were achieved when chitosan was used. Quantification limits ranged from 0.1 to 100μgkg(-1). Calibration curves showed correlation coefficient values higher than 0.98. Results of accuracy and precision in the spiked soil samples between 60% and 120%, with a relative standard deviation lower than 20%, were reached for 15 out of 17 pesticides. The matrix effect was evaluated and only one compound was influenced by the matrix components, showing medium effect. Results showed that alternative materials are more effective and less expensive than traditional sorbents which have been usually employed, i.e., they may be used in the D-SPE step during the extraction of pesticides from rice paddy soils. Copyright © 2014 Elsevier B.V. All rights reserved.

Determination of coumarin in seasonal bakery products using QuEChERS and GC-MS.

PubMed

Vetter, F; Müller, C; Stöckelhuber, M; Bracher, F

2017-06-01

Cinnamon is a traditional herbal drug, but more importantly, it is used as a flavor compound in the production of foodstuff. Due to the content of significant concentrations of coumarin in Cassia cinnamon, effective control of the coumarin content in seasonal bakery products like ginger bread and cinnamon biscuits is urgently needed. Here we present a novel, fast and fully validated protocol for the determination of coumarin in marketed bakery products using the QuEChERS sample preparation technique in combination with GC-MS analysis. Ten grams of homogenized sample was mixed with 20 mL acetonitrile/water (1:1) and 5 g magnesium sulfate/sodium chloride mixture (4:1). The organic phase was cleaned by dSPE with 25 mg magnesium sulfate/PSA (5:1). The LOD was 0.15 μg/mL and the LOQ 0.50 μg/mL. We detected a mean coumarin content of 19.5 μg/kg in 9 out of 14 seasonal food products (ranging from 1.45 to 39.4 mg/kg). No coumarin was detected in five cinnamon containing products. With this investigation we demonstrate that the QuEChERS sample preparation, previously applied mainly to the analysis of pesticides in vegetables, is also suitable for other complex matrices.

Accurate determination of selected pesticides in soya beans by liquid chromatography coupled to isotope dilution mass spectrometry.

PubMed

Huertas Pérez, J F; Sejerøe-Olsen, B; Fernández Alba, A R; Schimmel, H; Dabrio, M

2015-05-01

A sensitive, accurate and simple liquid chromatography coupled with mass spectrometry method for the determination of 10 selected pesticides in soya beans has been developed and validated. The method is intended for use during the characterization of selected pesticides in a reference material. In this process, high accuracy and appropriate uncertainty levels associated to the analytical measurements are of utmost importance. The analytical procedure is based on sample extraction by the use of a modified QuEChERS (quick, easy, cheap, effective, rugged, safe) extraction and subsequent clean-up of the extract with C18, PSA and Florisil. Analytes were separated on a C18 column using gradient elution with water-methanol/2.5 mM ammonium acetate mobile phase, and finally identified and quantified by triple quadrupole mass spectrometry in the multiple reaction monitoring mode (MRM). Reliable and accurate quantification of the analytes was achieved by means of stable isotope-labelled analogues employed as internal standards (IS) and calibration with pure substance solutions containing both, the isotopically labelled and native compounds. Exceptions were made for thiodicarb and malaoxon where the isotopically labelled congeners were not commercially available at the time of analysis. For the quantification of those compounds methomyl-(13)C2(15)N and malathion-D10 were used respectively. The method was validated according to the general principles covered by DG SANCO guidelines. However, validation criteria were set more stringently. Mean recoveries were in the range of 86-103% with RSDs lower than 8.1%. Repeatability and intermediate precision were in the range of 3.9-7.6% and 1.9-8.7% respectively. LODs were theoretically estimated and experimentally confirmed to be in the range 0.001-0.005 mg kg(-1) in the matrix, while LOQs established as the lowest spiking mass fractionation level were in the range 0.01-0.05 mg kg(-1). The method reliably identifies and quantifies the selected pesticides in soya beans at appropriate uncertainty levels, making it suitable for the characterization of candidate reference materials. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

UNE-EN ISO/IEC 17025:2005-accredited method for the determination of pesticide residues in fruit and vegetable samples by LC-MS/MS.

PubMed

Camino-Sánchez, F J; Zafra-Gómez, A; Oliver-Rodríguez, B; Ballesteros, O; Navalón, A; Crovetto, G; Vílchez, J L

2010-11-01

A rapid, simple and sensitive multi-residue method was developed and validated for the simultaneous quantification and confirmation of 69 pesticides in fruit and vegetables using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The samples were extracted following the quick, easy, cheap, effective, rugged and safe method known as QuEChERS. Mass spectrometric conditions were individually optimised for each analyte in order to achieve maximum sensitivity in multiple reaction monitoring (MRM) mode. Using the developed chromatographic conditions, 69 pesticides can be separated in less than 17 min. Two selected reaction monitoring (SRM) assays were used for each pesticide to obtain simultaneous quantification and identification in one run. With this method in SRM mode, more than 150 pesticides can be analysed and quantified, but their confirmation is not possible in all cases according to the European regulations on pesticide residues. Nine common representative matrices (zucchini, melon, cucumber, watermelon, tomato, garlic, eggplant, lettuce and pepper) were selected to investigate the effect of different matrices on recovery and precision. Mean recoveries ranged from 70% to 120%, with relative standard deviations (RSDs) lower than 20% for all the pesticides. The proposed method was applied to the analysis of more than 2000 vegetable samples from the extensive greenhouse cultivation in the province of Almeria, Spain, during one year. The methodology combines the advantages of both QuEChERS and LC-MS/MS producing a very rapid, sensitive, accurate and reliable procedure that can be applied in routine analytical laboratories. The method was validated and accredited according to UNE-EN-ISO/IEC 17025:2005 international standard (accreditation number 278/LE1027).

Improved Analytical Method for Determination of Cholesterol-Oxidation Products in Meat and Animal Fat by QuEChERS Coupled with Gas Chromatography-Mass Spectrometry.

PubMed

Chiu, Che-Wei; Kao, Tsai-Hua; Chen, Bing-Huei

2018-04-04

Cholesterol is widely present in animal fats and meat products and can undergo oxidation to form cholesterol-oxidation products (COPs) during heating. The objective of this study was to develop a QuEChERS method for the determination of COPs in edible animal fats and meat products via gas chromatography-mass spectrometry in which the required solvent volume and extraction time were reduced. By employing a DB-5MS capillary column (30 m × 0.25 mm i.d., 0.25 μm film thickness) and a temperature-programming method, seven COPs, cholesterol, and the internal standard 5α-cholestane could be separated within 19 min. The limits of detection and limits of quantitation based on the COP standards ranged from 0.16 to 180 ng/mL and from 0.32 to 400 ng/mL, respectively, and the recoveries ranged from 89.1 to 107.6% for boiled pork and from 80.5 to 105.6% for lard. The intraday variabilities for boiled pork and lard ranged from 2.27 to 6.87% and from 1.52 to 9.78%, respectively, whereas the interday variabilities ranged from 1.81 to 7.89% and from 3.57 to 9.26%, respectively. Among the various meat samples, fish showed the highest level of COPs (31.84 μg/g). For the edible fats, the COP contents in tallow (22.79-60.15 μg/g) were much higher than those in lard (0.152-2.55 μg/g) and butter (0.526-1.36 μg/g). Collectively, this method can be applied to determine COPs in cholesterol-containing foodstuffs.

Ractopamine analysis in pig kidney, liver and lungs: A validation of the method scope extension using QuEChERS as a sample preparation step.

PubMed

Feddern, Vivian; Aroeira, Carolina Naves; Molognoni, Luciano; Gressler, Vanessa; Daguer, Heitor; Dalla Costa, Osmar Antonio; Castillo, Carmen Josefina Contreras; de Lima, Gustavo Julio Mello Monteiro

2018-05-23

Ractopamine has been allowed by some countries as a repartitioning additive in pig diet, since it promotes protein synthesis and fat lipolysis. Most regulatory agencies only propose the ractopamine assessment in meat, kidney, liver and fat. Aiming at contributing to the scarcity data regarding this analyte in pig lungs, we extended the scope of a LC-MS method to evaluate pig offals. Homogenized tissue samples were extracted by a QuEChERS procedure; following by clean up steps and further tandem mass spectrometry determination. Method performance was evaluated through specificity, recovery, linearity, reproducibility, repeatability, decision limit (CC α ), and detection capability (CC β ), in accordance to the Commission Decision 2002/657/EC. Regression coefficients (R 2 ) between 0.994 and 0.999 were achieved for kidney, liver and lungs. Recoveries ranged from 92.0 to 127%. CC α and CC β values ranged from 3.65 to 4.86 μg kg -1 , and from 6.27 to 7.21 μg kg -1 , respectively. These values were under the maximum residue limits suggested by Codex Alimentarius, which are 90 and 40 μg kg -1 for kidney and liver, respectively. When applied to real samples up to 22.5, 92 and 1003 μg kg -1 of ractopamine residues were detected in pig liver, kidney and lungs, respectively. The results allowed concluding that the proposed analytical method is capable to detect ractopamine residues in all evaluated matrices. Therefore, it can be successfully applied and used as a routine method in laboratories of residue analysis. Copyright © 2018. Published by Elsevier B.V.

Determination of steroid hormones and their metabolite in several types of meat samples by ultra high performance liquid chromatography-Orbitrap high resolution mass spectrometry.

PubMed

López-García, Marina; Romero-González, Roberto; Garrido Frenich, Antonia

2018-03-09

A new analytical method based on ultra-high performance liquid chromatography (UHPLC) coupled to Orbitrap high resolution mass spectrometry (Orbitrap-HRMS) has been developed for the determination of steroid hormones (hydrocortisone, cortisone, progesterone, prednisone, prednisolone, testosterone, melengesterol acetate, hydrocortisone-21-acetate, cortisone-21-acetate, testosterone propionate, 17α-methyltestosterone, 6α-methylprednisolone and medroxyprogesterone) and their metabolite (17α-hydroxyprogesterone) in three meat samples (chicken, pork and beef). Two different extraction approaches were tested (QuEChERS "quick, easy, cheap, effective, rugged and safe" and "dilute and shoot"), observing that the QuEChERS method provided the best results in terms of recovery. A clean-up step was applied comparing several sorbents, obtaining the best results when florisil and aluminum oxide were used. The optimized method was validated, obtaining suitable results for all validation parameters in the three meat matrices evaluated. Recovery values ranged from 70% to 103% (except for prednisone in beef samples), meanwhile repeatability and reproducibility were obtained at values lower than 18% and 21%, respectively. The limit of quantification (LOQ) was established for most of the compounds at 1.0 μg/kg, except for testosterone in chicken and hydrocortisone-21-acetate and cortisone-21-acetate in pork at 2.0 μg/kg. Decision limit (CCα) and detection capability (CCβ) values ranged from 1.0-2.7 μg/kg and 1.9-5.5 μg/kg, respectively, in the three matrices. Finally, thirty one meat samples were analyzed and two hormones, progesterone and hydrocortisone, were detected in a beef and pork sample at 1.7 and 2.8 μg/kg respectively. Copyright © 2018 Elsevier B.V. All rights reserved.

Validation of QuEChERS analytical technique for organochlorines and synthetic pyrethroids in fruits and vegetables using GC-ECD.

PubMed

Dubey, J K; Patyal, S K; Sharma, Ajay

2018-03-19

In the present day scenario of increasing awareness and concern about the pesticides, it is very important to ensure the quality of data being generated in pesticide residue analysis. To impart confidence in the products, terms like quality assurance and quality control are used as an integral part of quality management. In order to ensure better quality of results in pesticide residue analysis, validation of analytical methods to be used is extremely important. Keeping in view the importance of validation of method, the validation of QuEChERS (quick, easy, cheap, effective, rugged, and safe) a multiresidue method for extraction of 13 organochlorines and seven synthetic pyrethroids in fruits and vegetables followed by GC ECD for quantification was done so as to use this method for analysis of samples received in the laboratory. The method has been validated as per the Guidelines issued by SANCO (French words Sante for Health and Consommateurs for Consumers) in accordance with their document SANCO/XXXX/2013. Various parameters analyzed, viz., linearity, specificity, repeatability, reproducibility, and ruggedness were found to have acceptable values with a per cent RSD of less than 10%. Limit of quantification (LOQ) for the organochlorines was established to be 0.01 and 0.05 mg kg -1 for the synthetic pyrethroids. The uncertainty of the measurement (MU) for all these compounds ranged between 1 and 10%. The matrix-match calibration was used to compensate the matrix effect on the quantification of the compounds. The overall recovery of the method ranged between 80 and 120%. These results demonstrate the applicability and acceptability of this method in routine estimation of pesticide residues of these 20 pesticides in the fruits and vegetables by the laboratory.

Volatile methylsiloxanes in personal care products - Using QuEChERS as a "green" analytical approach.

PubMed

Capela, Daniela; Homem, Vera; Alves, Arminda; Santos, Lúcia

2016-08-01

Organosiloxanes, namely volatile methylsiloxanes (VMSs) are one of the most relevant classes of ingredients incorporated in personal care products (PCPs), such as creams and lotions, bath soaps and hair care products. Their use has caused concern among the scientific community due to their potential toxic behaviour to human health and environment. This manuscript reports the first application of QuEChERS ("Quick, Easy, Cheap, Effective, Rugged and Safe") extraction followed by gas chromatography - mass spectrometry analysis to determine VMSs in cosmetics and personal care products. Eight VMSs, four linear (L2-L5) and four cyclic (D3-D6) were investigated in 36 samples. The validated method was able to remove the interfering matrix components, conducting to high recovery percentages (74-104%) and low relative standard deviations (<18%). A linear behaviour was observed in the range of 0.005-2.50mgL(-1) (correlation coefficient, R(2)>0.996) and limits of detection ranged from 0.17ngg(-1) (L2) to 3.75ngg(-1) (L5). Matrix effects were also investigated for all analysed compounds and matrices and showed not to be significant. Global uncertainty of the proposed methodology was also estimated using a bottom-up approach being between 5% and 35% (on average). Finally, the method was satisfactorily applied to the analysis of 36 personal care products. As expected, results showed the existence of VMSs in all analysed samples in concentrations up to 754µgg(-1). D4 and D5 were more frequently detected while body moisturizers, facial creams and shampoos showed the highest levels of VMSs. Copyright © 2016 Elsevier B.V. All rights reserved.

Determination of acrylamide in dried fruits and edible seeds using QuEChERS extraction and LC separation with MS detection.

PubMed

De Paola, Eleonora Laura; Montevecchi, Giuseppe; Masino, Francesca; Garbini, Davide; Barbanera, Martino; Antonelli, Andrea

2017-02-15

Acrylamide is a carcinogenic and neurotoxic process contaminant that is generated from food components during heat treatment, while it is absent in raw foodstuffs. Its level in food arouses great concern. A method for acrylamide extraction and determination in dried fruits (dried prunes and raisins) and edible seeds (almonds, hazelnuts, peanuts, pine nuts, pistachios, and walnuts) using a QuEChERS-LC-ESI-MS-Triple Quadrupole approach was set up. Linearity, sensitivity, accuracy, and precision of the method were satisfactory. Dried prunes and peanuts were the only samples appreciably contaminated, 14.7-124.3 and 10.0-42.9μg/kg, respectively, as a consequence of the drying process. In fact, prunes are dried at 70-80°C for a quite long time (24-36h), while peanuts undergo a roasting process at 160-180°C for 25-30min. The relative standard deviations, accuracy, LOD, and LOQ show that the method provides a reliable approach to acrylamide determination in different matrices. Copyright © 2016 Elsevier Ltd. All rights reserved.

Simultaneous determination of 117 pesticides and 30 mycotoxins in raw coffee, without clean-up, by LC-ESI-MS/MS analysis.

PubMed

Reichert, Bárbara; de Kok, André; Pizzutti, Ionara Regina; Scholten, Jos; Cardoso, Carmem Dickow; Spanjer, Martien

2018-04-03

This paper describes the optimization and validation of an acetonitrile based method for simultaneous extraction of multiple pesticides and mycotoxins from raw coffee beans followed by LC-ESI-MS/MS determination. Before extraction, the raw coffee samples were milled and then slurried with water. The slurried samples were spiked with two separate standard solutions, one containing 131 pesticides and a second with 35 mycotoxins, which were divided into 3 groups of different relative concentration levels. Optimization of the QuEChERS approach included performance tests with acetonitrile acidified with acetic acid or formic acid, with or without buffer and with or without clean-up of the extracts before LC-ESI-MS/MS analysis. For the clean-up step, seven d-SPE sorbents and their various mixtures were evaluated. After method optimization a complete validation study was carried out to ensure adequate performance of the extraction and chromatographic methods. The samples were spiked at 3 concentrations levels with both mycotoxins and pesticides (with 6 replicates at each level, n = 6) and then submitted to the extraction procedure. Before LC-ESI-MS/MS analysis, the acetonitrile extracts were diluted 2-fold with methanol, in order to improve the chromatographic performance of the early-eluting polar analytes. Calibration standard solutions were prepared in organic solvent and in blank coffee extract at 7 concentration levels and analyzed 6 times each. The method was assessed for accuracy (recovery %), precision (RSD%), selectivity, linearity (r 2 ), limit of quantification (LOQ) and matrix effects (%). Copyright © 2017 Elsevier B.V. All rights reserved.

Determination of endrin and δ-keto endrin in five food products of animal origin using GC-μECD: A modified QuEChERS approach to traditional detection.

PubMed

Rahman, Md Musfiqur; Lee, Han Sol; Abd El-Aty, A M; Kabir, Md Humayun; Chung, Hyung Suk; Park, Jong-Hyouk; Kim, Mi-Ra; Kim, Ji-Hyun; Shin, Ho-Chul; Shin, Sung Shik; Shim, Jae-Han

2018-10-15

A simple quick, easy, cheap, effective, rugged, and safe (QuEChERS)-based method was developed for the analysis of endrin and its metabolite, δ-keto endrin, in five animal-derived food products (chicken, pork, beef, egg, and milk) using a gas chromatography-micro electron capture detector (GC-μECD). Samples were extracted with acidified acetonitrile, salted out with magnesium sulfate and sodium acetate, and finally purified with a dual layer solid-phase extraction cartridge (SPE) that contains both Supelclean ENVI-Carb (upper layer) and primary secondary amine (lower layer) SPE sorbents. A seven-point external calibration curve was constructed both for the solvent and matrix for both compounds. Good linearity was achieved for both analytes, with coefficients of determination (R 2 ) ≥ 0.9960. The limits of detection (LODs) were 0.003 mg/kg, whereas the limits of quantification (LOQ) were 0.01 mg/kg, which were 10 times lower than the extraneous maximum residue limit (EMRL) designated by CODEX Alimentarius for the specified matrices. The method was validated via recovery performances in triplicates, with three fortification levels equivalent to LOQ, 2 × LOQ, and 10 × LOQ. The method provided excellent recoveries, ranging between 75.63 and 117.92%, with relative standard deviations (RSD) ≤ 8.52% for both analytes in various matrices. The developed method was successfully applied to monitor market samples collected from 20 different places throughout the Republic of Korea, and none of the tested analytes were found in the analyzed samples. Conclusively, we could propose that the current method can be used for routine analysis of endrin and δ-keto endrin in any type of fatty food matrix. Copyright © 2018 Elsevier Ltd. All rights reserved.

Evaluation of the QuEChERS Method and Gas Chromatography–Mass Spectrometry for the Analysis Pesticide Residues in Water and Sediment

PubMed Central

de Macedo, A. N.; Vicente, G. H. L.; Nogueira, A. R. A.

2010-01-01

A method for the determination of pesticide residues in water and sediment was developed using the QuEChERS method followed by gas chromatography – mass spectrometry. The method was validated in terms of accuracy, specificity, linearity, detection and quantification limits. The recovery percentages obtained for the pesticides in water at different concentrations ranged from 63 to 116%, with relative standard deviations below 12%. The corresponding results from the sediment ranged from 48 to 115% with relative standard deviations below 16%. The limits of detection for the pesticides in water and sediment were below 0.003 mg L−1 and 0.02 mg kg−1, respectively. PMID:21165598

Disappearance of six pesticides in fresh and processed zucchini, bioavailability and health risk assessment.

PubMed

Oliva, J; Cermeño, S; Cámara, M A; Martínez, G; Barba, A

2017-08-15

A field study was carried out on the dissipation of three insecticides and three fungicides during the freezing of zucchini. A simultaneous residue analysis method is validated using QuEChERS extraction with acetonitrile and CG-MS and LC-MS analysis. The residues detected after field application never exceeded the established maximum residue limits. The processing factors calculated (fresh product/frozen product) are lower than 1, indicating a clear influence of the stages of the freezing process, especially the washing and blanching. The in vitro study of bioavailability establishes a low percentage of stomach absorption capacity. The level of residues detected in fresh zucchini and the Estimated Daily Intake calculated for Spain suggest that there is no risk of acute toxicity due to dietary exposure. Copyright © 2017 Elsevier Ltd. All rights reserved.

Pesticide Residues in Honey from the Major Honey Producing Forest Belts in Ghana.

PubMed

Darko, Godfred; Addai Tabi, Jonah; Adjaloo, Michael Kodwo; Borquaye, Lawrence Sheringham

2017-01-01

Concentrations of pesticides residues in honey sampled from the major honey producing forest belts in Ghana were determined. Samples were purposively collected and extracted using the QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) method and analysed for synthetic pyrethroids, organochlorine, and organophosphate pesticide residues. Aldrin, γ -HCH, β -HCH, ∑endosulfan, cyfluthrin, cypermethrin, deltamethrin, permethrin methoxychlor, ∑DDT, chlorpyrifos, fenvalerate, malathion, dimethoate, and diazinon were all detected at the concentration of 0.01 mg/kg, while cyfluthrin and permethrin were detected at mean concentrations of 0.02 and 0.04 mg/kg, respectively. All the pesticide residues detected were very low and below their respective maximum residue limits set by the European Union. Hence, pesticide residues in honey samples analyzed do not pose any health risk to consumers.

[Determination of six novel amide fungicides in vegetables and fruits by liquid chromatography-tandem mass spectrometry].

PubMed

Chen, Xiaolong; Li, Zhengxiang; Cao, Zhaoyun; Cao, Xiaolin; Chen, Mingxue

2013-10-01

A method was developed for the simultaneous determination of mepanipyrim, silthiofam, boscalid, fluopicolide, mandipropamid, cyflufenamid in vegetables and fruits by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The analytes were extracted from the samples by acetonitrile and purified by Florisil SPE. The six novel amide fungicides were separated on a Poroshell 120 EC-C18 column with the mobile phases of water and acetonitrile, and finally detected by MS/MS with positive electrospray ionization (ESI+) in multiple reaction monitoring (MRM) mode, quantified by external standard method. Under the optimal analytical conditions, the correlation coefficients (r) of the six novel amide fungicides were not lower than 0. 999 0 in the concentration range from 0.5 to 100 microg/L. The limits of detection (S/N > or = 3) of the method were 0.15 microg/kg for boscalid, silthiofam, mandipropamid, cyflufenamid, 0.10 microg/kg for mepanipyrim and 0.17 microg/kg for fluopicolide. The recovery tests were performed for the 7 types of vegetables and the 3 types of fruits at the spiked levels of 0.5, 5 and 50 microg/kg, and the recoveries of the six analytes ranged from 65% to 124% with the relative standard deviations (RSDs, n = 5) of 1%-18%. The matrix effects in vegetables and fruits of the six amide fungicides were significantly reduced by the purification of Florisil SPE compared with the modified QuEChERS. The method is easy, fast, sensitive and accurate, and can meet the requirements of the determination of the six amide fungicide residues in vegetables and fruits.

Simultaneous determination of three pesticide adjuvant residues in plant-derived agro-products using liquid chromatography-tandem mass spectrometry.

PubMed

Li, Hui; Jiang, Zejun; Cao, Xiaolin; Su, Hang; Shao, Hua; Jin, Fen; Abd El-Aty, A M; Wang, Jing

2017-12-15

Herein, an accurate and reliable isotope-labelled internal standard method was developed and validated for simultaneous determination of three polar pesticide adjuvants, namely 2-pyrrolidone, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone in plant-derived agro-products. Matrices, including apple, cabbage, tomato, cucumber, rice, and wheat were extracted with a modified quick, easy, cheap, effective, rugged, and safe "QuEChERS" method and purified with a new clean-up sorbent (Z-Sep). A hydrophilic interaction liquid chromatography column (HILIC), exhibiting a lipophilic-hydrophilic character, was used to separate the three analytes over 10min using liquid chromatography-tandem mass spectrometry (LC-MS/MS). Matrix effects in various matrices were evaluated and an isotope-labelled internal standard method was employed to compensate for ion enhancement/suppression effects. At three fortification levels (2.0, 5.0, and 20.0μg/kg), the mean recoveries ranged from 78.5 to 112.1% with relative standard deviations (RSDs)<11.0% for all tested analytes. The limits of detection (LODs) and quantification (LOQs) were 0.04-0.45 and 0.12-1.58μg/kg in various matrices, respectively. The developed experimental protocol was successfully applied to monitor different samples purchased from local markets in Beijing, China. In conclusion, the developed method exhibited both high sensitivity and satisfactory accuracy and is suitable for the simultaneous determination of the three tested pesticide adjuvant residues in agro-products of plant origin. Copyright © 2017 Elsevier B.V. All rights reserved.

Contributing effect of various washing procedures and additives on the decline pattern of diethofencarb in crown daisy, a model of leafy vegetables.

PubMed

Kim, Sung-Woo; Abd El-Aty, A M; Choi, Jeong-Heui; Lee, Young-Jun; Lieu, Truong T B; Chung, Hyung Suk; Rahman, Md Musfiqur; Choi, Ok-Ja; Shin, Ho-Chul; Rhee, Gyu-Seek; Chang, Moon-Ik; Kim, Hee Jung; Shim, Jae-Han

2016-06-15

The effects of various washing procedures, including stagnant, running, and stagnant and running tap water, and the use of washing solutions and additives, namely NaCl (1% and 2%), vinegar (2%, 5%, and 10%), detergent (0.5% and 1%), and charcoal (1% and 2%), on the reduction rate of diethofencarb were estimated in field-incurred crown daisy, a model of leafy vegetables, grown under greenhouses located in 3 different areas (Gwangju, Naju, and Muan). The original Quick, Easy, Cheap, Effective, Rugged, and Safe "QuEChERS" method was modified for extraction and liquid chromatography-tandem mass spectrometry (LC/MS/MS) was used for analysis. The recovery of diethofencarb in unwashed and washed samples was satisfactory and ranged between 84.28% and 115.32% with relative standard deviations (RSDs) of <6%. The residual levels decreased following washing with stagnant, running, and stagnant+running tap water (i.e., decline in levels increased from 65.08% to 85.02%, 69.99 to 86.79, and 74.75 to 88.96, respectively). The percentage of decline increased and ranged from 77.46% to 91.19% following washing with various solutions. Application of 1% detergent was found to be the most effective washing method for reducing the residues in crown daisy. Additionally, washing with stagnant and running tap water or even stagnant water for 5 min might reduce the residue levels substantially, making the prepared food safe for human consumption. Copyright © 2016 Elsevier Ltd. All rights reserved.

Residue behaviors and risk assessment of flonicamid and its metabolites in the cabbage field ecosystem.

PubMed

Wang, Shanshan; Jin, Fen; Cao, Xiaolin; Shao, Yong; Wang, Jian; She, Yongxin; Qi, Yan; Zhang, Chao; Li, Hui; Jin, Maojun; Wang, Jing; Shao, Hua; Zheng, Lufei

2018-06-13

Flonicamid, a novel selective systemic pesticide, can effectively control a broad range of insect pests. However, the dissipation behaviors and the terminal residues of flonicamid and its metabolites in some crops and soils remain unclear. Herein, an easy, sensitive and reliable method using a modified QuEChERS extraction coupled with LC-MS/MS for the simultaneous analysis of flonicamid and its metabolites in cabbage and soil was developed. Based on this method, the dissipation behaviors of flonicamid and its metabolites as well as their persistence in cabbage and soil during harvest were investigated. Flonicamid degraded rapidly, and the half-lives of flonicamid only and total residues (the sum of flonicamid and its metabolites) were 1.49-4.59 and 1.97-4.99 days in cabbage, and 2.12-7.97 and 2.04-7.62 days in soil, respectively. When 50% flonicamid WG was sprayed once or twice at the recommended dose and 1.5-fold the recommended dose, the highest residues of total flonicamid in cabbage and soil from different pre-harvest intervals (3, 7 and 14 days) were 0.070 and 0.054 mg kg -1 , respectively. The risk quotient (RQ) of flonicamid based on the consumption data from China was below 16.84%, indicating that the use of flonicamid is non-hazardous to humans. These results could not only guide the safe and responsible use of flonicamid in agriculture but also help the Chinese government establish the maximum residue level (MRL) for flonicamid in cabbage. Copyright © 2018 Elsevier Inc. All rights reserved.

Reply to comments on "Volatile methylsiloxanes in personal care products - Using QuEChERS as a "green" analytical approach" published in Talanta 174 (2017) 156-157.

PubMed

Capela, Daniela; Homem, Vera; Alves, Arminda; Santos, Lúcia

2018-03-01

Recently, Pierre Germain from CES - Silicon Europe published a comment on the paper "Volatile methylsiloxanes in personal care products - Using QuEChERS as a "green" analytical approach", raising concerns that the artefacts employed in the analysis of cyclic volatile methylsiloxanes (cVMS) were not adequately controlled, while using this example as an opportunity to emphasize the difficulties associated with siloxanes analyses in complex matrices such as personal care products (PCPs). We are now addressing these concerns and conveying some clarifications regarding the experiments performed to validate the analytical method adequately. Those details were not included in the original publication because the objective was the quantification of VMS in several PCPs. Copyright © 2017 Elsevier B.V. All rights reserved.

Recent Modifications and Validation of QuEChERS-dSPE Coupled to LC-MS and GC-MS Instruments for Determination of Pesticide/Agrochemical Residues in Fruits and Vegetables: Review.

PubMed

Lawal, Abubakar; Wong, Richard Chee Seng; Tan, Guan Huat; Abdulra'uf, Lukman Bola; Alsharif, Ali Mohamed Ali

2018-04-21

Fruits and vegetables constitute a major type of food consumed daily apart from whole grains. Unfortunately, the residual deposits of pesticides in these products are becoming a major health concern for human consumption. Consequently, the outcome of the long-term accumulation of pesticide residues has posed many health issues to both humans and animals in the environment. However, the residues have previously been determined using conventionally known techniques, which include liquid-liquid extraction, solid-phase extraction (SPE) and the recently used liquid-phase microextraction techniques. Despite the positive technological effects of these methods, their limitations include; time-consuming, operational difficulty, use of toxic organic solvents, low selective property and expensive extraction setups, with shorter lifespan of instrumental performances. Thus, the potential and maximum use of these methods for pesticides residue determination has resulted in the urgent need for better techniques that will overcome the highlighted drawbacks. Alternatively, attention has been drawn recently towards the use of quick, easy, cheap, effective, rugged and safe technique (QuEChERS) coupled with dispersive solid-phase extraction (dSPE) to overcome the setback challenges experienced by the previous technologies. Conclusively, the reviewed QuEChERS-dSPE techniques and the recent cleanup modifications justifiably prove to be reliable for routine determination and monitoring the concentration levels of pesticide residues using advanced instruments such as high-performance liquid chromatography, liquid chromatography-mass spectrometry and gas chromatography-mass spectrometry.

Acetonitrile extraction and dual-layer solid phase extraction clean-up for pesticide residue analysis in propolis.

PubMed

Oellig, Claudia

2016-05-06

Propolis is a very complex mixture of substances that is produced by honey bees and is known to be a rather challenging matrix for residue analysis. Besides resins, flavonoids and phenols, high amount of wax is co-extracted resulting in immense matrix effects. Therefore a suitable clean-up is crucial and indispensable. In this study, a reliable solid phase extraction (SPE) clean-up was developed for pesticide residue analysis in propolis. The clean-up success was quickly and easily monitored by high-performance thin-layer chromatography with different detection possibilities. The final method consists of the extraction of propolis with acetonitrile according to the QuEChERS method followed by an effective extract purification on dual-layer SPE cartridges with spherical hydrophobic polystyrene-divinylbenzene resin/primary secondary amine as sorbent and a mixture of toluene/acetone (95:5, v/v) for elution. Besides fat-soluble components like waxes, flavonoids, and terpenoids, more polar compounds like organic acids, fatty acids, sugars and anthocyanins were also removed to large extent. Method performance was assessed by recovery experiments at spiking levels of 0.5 and 1mg/kg (n=5) for fourteen pesticides that are relevant for propolis. Mean recoveries determined by HPLC-MS against solvent standards were between 40 and 101%, while calculation against matrix-matched standards provided recoveries of 79-104%. Precision of recovery, assessed by relative standard deviations, were below 9%. Thus, the developed dual-layer SPE clean-up enables the reliable pesticide residue analysis in propolis and provides a suitable alternative to time-consuming clean-up procedures proposed in literature. Copyright © 2016 Elsevier B.V. All rights reserved.

Selective solid-phase extraction using a molecularly imprinted polymer for the analysis of patulin in apple-based foods.

PubMed

Lucci, Paolo; Moret, Sabrina; Bettin, Sara; Conte, Lanfranco

2017-01-01

The aim of this work was to evaluate the use of a molecularly imprinted polymer as a selective solid-phase extraction sorbent for the clean-up and pre-concentration of patulin from apple-based food products. Ultra high pressure liquid chromatography coupled to ultraviolet absorbance detection was used for the analysis of patulin. The molecularly imprinted polymer was applied, for the first time, to the determination of patulin in apple juice, puree and jam samples spiked within the maximum levels specified by the European Commission No. 1881/2006. High recoveries (>77%) were obtained. The method was validated and found to be linear in the range 2-100 μg/kg with correlation coefficients greater than 0.965 and repeatability relative standard deviation below 11% in all cases. Compared with dispersive solid-phase extraction (QuEChERS method) and octadecyl sorbent, the molecularly imprinted polymer showed higher recoveries and selectivity for patulin. The application of Affinisep molecularly imprinted polymer as a selective sorbent material for detection of patulin fulfilled the method performance criteria required by the Commission Regulation No. 401/2006, demonstrating the suitability of the technique for the control of patulin at low ppb levels in different apple-based foods such as juice, puree and jam samples. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Linking Environmental Exposure with Public Health: Dichlorodiphenyltrichloroethane Extracted from Soils and Water of Recently Exposed Communities of Selected Locations in Zambia

PubMed Central

Sipilanyambe Munyinda, Nosiku; Michelo, Charles; Sichilongo, Kwenga

2015-01-01

Background. In 2000, a Zambian private mining company reintroduced the use of dichlorodiphenyltrichloroethane (DDT) to control malaria in two districts. From 2000 to 2010, DDT had been applied in homes without any studies conducted to ascertain its fate in the environment. We aimed to quantify the presence of DDT and its metabolites in the soil and water around communities where it was recently used. Methods. We collected superficial soil and water samples from drinking sources of three study areas. DDT was extracted by QuEChERS method and solid phase extraction for soils and water, respectively. Analysis was by gas chromatography-mass spectrometry. A revalidated method with limits of detection ranging from 0.034 to 0.04 ppb was used. Results. Median levels of total DDT were found at 100.4 (IQR 90.9–110) and 725.4 ng/L (IQR 540–774.5) for soils and water, respectively. No DDT above detection limits was detected in the reference area. These results are clinically significant given the persistent characteristics of DDT. Conclusion. DDT presence in these media suggests possible limitations in the environmental safeguards during IRS. Such occurrence could have potential effects on humans, especially children; hence, there is a need to further examine possible associations between this exposure and humans. PMID:26579199

Residual determination and risk assessment of buprofezin in plum (Prunus domestica) grown in open-field conditions following the application of three different formulations.

PubMed

Kabir, Md Humayun; Abd El-Aty, A M; Kim, Sung-Woo; Lee, Han Sol; Rahman, Md Musfiqur; Lee, Young-Jun; Chung, Hyung Suk; Lieu, Truong; Choi, Jeong-Heui; Shin, Ho-Chul; Im, Geon-Jae; Hong, Su Myeong; Shim, Jae-Han

2016-11-01

This study was conducted to characterize the residual level and perform a risk assessment on buprofezin formulated as an emulsifiable concentrate, wettable powder, and suspension concentrate over various treatment schedules in plum (Prunus domestica). The samples were extracted with an AOAC quick, easy, cheap, effective, rugged, and safe, 'QuEChERS', method after major modifications. As intrinsic interferences were observed in blank plum samples following dispersive-solid phase extraction (consisting of primary secondary amine and C 18 sorbents), amino cartridges were used for solid-phase extraction. Analysis was carried out using liquid chromatography with diode array detection and confirmed by liquid chromatography-tandem mass spectrometry. The method showed excellent linearity with determination coefficient (R 2  = 1) and satisfactory recoveries (at two spiking levels, 0.5 and 2.5 mg/kg) between 90.98 and 94.74% with relative standard deviation (RSD) ≤8%. The limit of quantification (0.05 mg/kg) was considerably lower than the maximum residue limit (2 mg/kg) set by the Codex Alimentarius. Absolute residue levels for emulsifiable concentrates were highest, perhaps owing to the dilution rate and adjuvant. Notably, all formulation residues were lower than the maximum residue limit, and safety data proved that the fruits are safe for consumers. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Dissipation, residues and risk assessment of spirotetramat and its four metabolites in citrus and soil under field conditions by LC-MS/MS.

PubMed

Zhang, Qingtao; Chen, Yuling; Wang, Shouyi; Yu, Yurong; Lu, Ping; Hu, Deyu; Yang, Zaihui

2018-04-01

A modified Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) method for the simultaneous determination of spirotetramat and its four metabolite residues in citrus, peel, pulp and soil was developed and validated by liquid chromatography with tandem mass spectrometry (LC-MS/MS). The samples were extracted with acetonitrile (1%, glacial acetic acid, v/v) and purified using primary secondary amine and octadecylsilane. The limit of detection was 0.01-0.13 mg/kg, whereas that of quantification was 0.02-0.40 mg/kg for spirotetramat and its metabolites. The average recoveries of spirotetramat, spirotetramat-enol, spirotetramat-mono-hydroxy, spirotetramat-enol-glucoside and spirotetramat-ketohydroxy in all matrices were 73.33-107.91%, 75.93-114.85%, 76.44-100.78%, 71.46-103.19% and 73.08-105.27%, respectively, with relative standard deviations < 12.32%. The dissipation dynamics of spirotetramat in citrus and soil followed first-order kinetics, with half-lives of 2.3-8.5 days in the three sampling locations. The terminal residues of spirotetramat in four matrices at the three locations were measured below the 1.0 mg/kg maximum residue limit set by China, and residues were found to be concentrated on the peel. The risk assessment of citrus was evaluated using risk quotients. The risk quotient values were found to be significantly <1, suggesting that the risk to human health was negligible when using the recommended doses of spirotetramat in citrus. These results could provide guidance for the safe and proper application of spirotetramat in citrus in China. Copyright © 2017 John Wiley & Sons, Ltd.

Maximum residue level validation of triclabendazole marker residues in bovine liver, muscle and milk matrices by ultra high pressure liquid chromatography tandem mass spectrometry.

PubMed

Whelan, Michelle; O'Mahony, John; Moloney, Mary; Cooper, Kevin M; Furey, Ambrose; Kennedy, D Glenn; Danaher, Martin

2013-02-01

Triclabendazole is the only anthelmintic drug, which is active against immature, mature and adult stages of fluke. The objective of this work was to develop an analytical method to quantify and confirm the presence of triclabendazole residues around the MRL. In this work, a new analytical method was developed, which extended dynamic range to 1-100 and 5-1000 μg kg(-1) for milk and tissue, respectively. This was achieved using a mobile phase containing trifluoroacetic acid (pK(a) of 0.3), which resulted in the formation of the protonated pseudomolecular ions, [M+H](+), of triclabendazole metabolites. Insufficient ionisation of common mobile phase additives due to low pK(a) values (<2) was identified as the cause of poor linearity. The new mobile phase conditions allowed the analysis of triclabendazole residues in liver, muscle and milk encompassing their EU maximum residue levels (MRL) (250, 225 and 10 μg kg(-1) respectively). Triclabendazole residues were extracted using a modified QuEChERS method and analysed by positive electrospray ionisation mass spectrometry with all analytes eluted by 2.23 min. The method was validated at the MRL according to Commission Decision (CD) 2002/657/EC criteria. The decision limit (CCα) of the method was in the range of 250.8-287.2, 2554.9-290.8 and 10.9-12.1 μg kg(-1) for liver, muscle and milk, respectively. The performance of the method was successfully verified for triclabendazole in muscle by participating in a proficiency study, the method was also applied to incurred liver, muscle and milk samples. Copyright © 2012 Elsevier B.V. All rights reserved.

Factors influencing the extraction of pharmaceuticals from sewage sludge and soil: an experimental design approach.

PubMed

Ferhi, Sabrina; Bourdat-Deschamps, Marjolaine; Daudin, Jean-Jacques; Houot, Sabine; Nélieu, Sylvie

2016-09-01

Pharmaceuticals can enter the environment when organic waste products are recycled on agricultural soils. The extraction of pharmaceuticals is a challenging step in their analysis. The very different extraction conditions proposed in the literature make the choice of the right method for multi-residue analysis difficult. This study aimed at evaluating, with experimental design methodology, the influence of the nature, pH and composition of the extraction medium on the extraction recovery of 14 pharmaceuticals, including 8 antibiotics, from soil and sewage sludge. Preliminary experimental designs showed that acetonitrile and citrate-phosphate buffer were the best extractants. Then, a response surface design demonstrated that many cross-product and squared terms had significant effects, explaining the shapes of the response surfaces. It also allowed optimising the pharmaceutical recoveries in soil and sludge. The optimal conditions were interpreted considering the ionisation states of the compounds, their solubility in the extraction medium and their interactions with the solid matrix. To perform the analysis, a compromise was made for each matrix. After a QuEChERS purification, the samples were analysed by online SPE-UHPLC-MS-MS. Both methods were simple and economical. They were validated with the accuracy profile methodology for soil and sludge and characterised for another type of soil, digested sludge and composted sludge. Trueness globally ranged between 80 and 120 % recovery, and inter- and intra-day precisions were globally below 20 % relative standard deviation. Various pharmaceuticals were present in environmental samples, with concentration levels ranging from a few micrograms per kilogramme up to thousands of micrograms per kilogramme. Graphical abstract Influence of the extraction medium on the extraction recovery of 14 pharmaceuticals. Influence of the ionisation state, the solubility and the interactions of pharmaceuticals with solid matrix. Analysis of different soils and organic waste products.

Determination of ten pyrethroids in various fruit juices: comparison of dispersive liquid-liquid microextraction sample preparation and QuEChERS method combined with dispersive liquid-liquid microextraction.

PubMed

Zhang, Yaohai; Zhang, Xuelian; Jiao, Bining

2014-09-15

Dispersive liquid-liquid microextraction (DLLME) sample preparation and the quick, easy, cheap, effective, rugged and safe (QuEChERS) method combined with DLLME were developed and compared for the analysis of ten pyrethroids in various fruit juices using gas chromatography-electron capture detection (GC-ECD). QuEChERS-DLLME method has found its widespread applications to all the fruit juices including those samples with more complex matrices (orange, lemon, kiwi and mango) while DLLME was confined to the fruit juices with simpler matrices (apple, pear, grape and peach). The two methods provided acceptable recoveries and repeatability. In addition, the applicabilities of two methods were demonstrated with the real samples and further confirmed by gas chromatography-mass spectrometry (GC-MS). Copyright © 2014. Published by Elsevier Ltd.

Development and validation of a multiclass method for the quantification of veterinary drug residues in honey and royal jelly by liquid chromatography-tandem mass spectrometry.

PubMed

Jin, Yue; Zhang, Jinzhen; Zhao, Wen; Zhang, Wenwen; Wang, Lin; Zhou, Jinhui; Li, Yi

2017-04-15

The aim of this study was to develop an analytical method for the analysis of a wide range of veterinary drugs in honey and royal jelly. A modified sample preparation procedure based on the quick, easy, cheap, effective, rugged and safe (QuEChERS) method was developed, followed by liquid chromatography tandem mass spectrometry determination. Use of the single sample preparation method for analysis of 42 veterinary drugs becomes more valuable because honey and royal jelly belong to completely different complex matrices. Another main advantage of the proposed method is its ability to identify and quantify 42 veterinary drugs with higher sensitivity than reference methods of China. This work has shown that the reported method was demonstrated to be convenient and reliable for the quick monitoring of veterinary drugs in honey and royal jelly samples. Copyright © 2016 Elsevier Ltd. All rights reserved.

Dissipation Pattern, Processing Factors, and Safety Evaluation for Dimethoate and Its Metabolite (Omethoate) in Tea (Camellia Sinensis).

PubMed

Pan, Rong; Chen, Hong-Ping; Zhang, Ming-Lu; Wang, Qing-Hua; Jiang, Ying; Liu, Xin

2015-01-01

Residue levels of dimethoate and its oxon metabolite (omethoate) during tea planting, manufacturing, and brewing were investigated using a modified QuEChERS sample preparation and gas chromatography. Dissipation of dimethoate and its metabolite in tea plantation followed the first-order kinetic with a half-life of 1.08-1.27 d. Tea manufacturing has positive effects on dimethoate dissipation. Processing factors of dimethoate are in the range of 2.11-2.41 and 1.41-1.70 during green tea and black tea manufacturing, respectively. Omethoate underwent generation as well as dissipation during tea manufacturing. Sum of dimethoate and omethoate led to a large portion of 80.5-84.9% transferring into tea infusion. Results of safety evaluation indicated that omethoate could bring higher human health risk than dimethoate due to its higher hazard quotient by drinking tea. These results would provide information for the establishment of maximum residue limit and instruction for the application of dimethoate formulation on tea crop.

Facile synthesis of amine-functional reduced graphene oxides as modified quick, easy, cheap, effective, rugged and safe adsorbent for multi-pesticide residues analysis of tea.

PubMed

Ma, Guicen; Zhang, Minglu; Zhu, Li; Chen, Hongping; Liu, Xin; Lu, Chengyin

2018-01-05

Amine-functional reduced graphene oxide (amine-rGO) with different carbon chain length amino groups were successfully synthesized. The graphene oxides (GO) reduction as well as amino grafting were achieved simultaneously in one step via a facile solvothermal synthetic strategy. The obtained materials were characterized by X-ray diffraction, Raman spectroscopy, Fourier-transform infrared spectrometry and X-ray photoelectron spectroscopy to confirm the modification of GO with different amino groups. The adsorption performance of catechins and caffeine from tea acetonitrile extracts on different amine functional rGO samples were evaluated. It was found that tributylamine-functional rGO (tri-BuA-rGO) exhibited the highest adsorption ability for catechins and caffeine compared to GO and other amino group functional rGO samples. It was worth to note that the adsorption capacity of catechins on tri-BuA-rGO was 11 times higher than that of GO (203.7mgg -1 vs 18.7mgg -1 ). Electrostatic interaction, π-π interaction and surface hydrophilic-hydrophobic properties of tri-BuA-rGO played important roles in the adsorption of catechins as well as caffeine. The gravimetric analysis confirmed that the tri-BuA-rGO achieved the highest efficient cleanup preformance compared with traditional dispersive solid phase extraction (dSPE) adsorbents like primary-secondary amine (PSA), graphitized carbon black (GCB) or C18. A multi-pesticides analysis method based on tri-BuA-rGO is validated on 33 representative pesticides in tea using gas chromatography coupled to tandem mass spectrometry or high-performance liquid chromatography coupled with tandem mass spectrometry. The analysis method gave a high coefficient of determination (r 2 >0.99) for each pesticide and satisfactory recoveries in a range of 72.1-120.5%. Our study demonstrated that amine functional rGO as a new type of QuEChERS adsorbent is expected to be widely applied for analysis of pesticides at trace levels. Copyright © 2017 Elsevier B.V. All rights reserved.

A multiresidue method for the analysis of 90 pesticides, 16 PAHs, and 22 PCBs in honey using QuEChERS-SPME.

PubMed

Al-Alam, Josephine; Fajloun, Ziad; Chbani, Asma; Millet, Maurice

2017-08-01

An optimized analytical method was developed for the simultaneous analysis of 90 pesticides, 16 polycyclic aromatic hydrocarbons, and 22 polychlorinated biphenyls. The method was based on quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction using acetonitrile followed by a dispersive solid-phase extraction cleanup using primary-secondary amine and octadecyl (C 18 ). The extract obtained was concentrated by evaporation and then reconstituted with acetonitrile to prepare it for chromatographic analysis by liquid chromatography-triple-quadrupole tandem mass spectrometry and gas chromatography-ion-trap tandem mass spectrometry, which was preceded by a preconcentration step using solid-phase microextraction with appropriate fibers. The combination of the two extraction steps ensured efficient extract cleanup. The use of the two analytical instruments allowed the analysis of a large number of pollutants with a high reliability rate. The method developed was validated for linearity, which was studied with use of matrix-matched calibration curves in the concentration range between 10 and 3000 ng g -1 . The correlation coefficient (R 2 ) obtained was higher than 0.98 for most of the target compounds, with a relative standard deviation lower than 20% for repeatability and reproducibility. The limits of detection and quantification were lower than 20 and 60 ng g -1 respectively for the compounds analyzed, and the recoveries were between 60% and 103% for most compounds. Finally, the method was tested for its efficiency on real samples by the analysis of three honey samples in which seven pesticides and nine polycyclic aromatic hydrocarbons were determined. Graphical Abstract ᅟ.

Characterization and quantitation of yohimbine and its analogs in botanicals and dietary supplements using LC/QTOF-MS and LC/QQQ-MS for determination of the presence of bark extract and yohimbine adulteration.

PubMed

Lucas, Derick; Neal-Kababick, James; Zweigenbaum, Jerry

2015-01-01

The compound yohimbine HCl has been restricted in Australia and categorized as a scheduled prescription drug in other parts of the world, including the United States where it is monographed as a drug in the U. S. Pharmacopeia. However, the bark of the yohimbe plant and its extract is considered a botanical that can be used as a dietary supplement in some parts of the world. For these reasons, methods to characterize the indole alkaloids of the bark and quantify yohimbine and its analogs are presented using accurate mass LC/quadrupole time-of-flight (QTOF)-MS and triple quadrupole LC/MS, respectively. Samples were extracted with a QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) method to characterize and quantify the indole alkaloids. With the LC/QTOF-MS in auto MS/MS mode the indole alkaloids were identified, and the isomeric response of each could be used to determine whether the actual bark or extract was in samples of dietary supplements and not adulteration with yohimbine HCl. Analogs were identified and include yohimbic acid, methyl yohimbine, and hydroxyl yohimbine. Many isomers of each were also detected, but identified only by the number of chromatographic peaks. Quantification of yohimbine and ajmalicine spiked extracts showed recoveries of 99 to 103% with RSD of 3.6% or lower and LODs of less than 100 ppt. Calibration of the two standards gave r(2) = 0.9999 in a range from 0.1 to 100 ppb. Dietary supplements quantified for these two compounds showed a range from not detected to 3x the amounts found in the bark.

Evaluation of a recent product to remove lipids and other matrix co-extractives in the analysis of pesticide residues and environmental contaminants in foods.

PubMed

Han, Lijun; Matarrita, Jessie; Sapozhnikova, Yelena; Lehotay, Steven J

2016-06-03

This study demonstrates the application of a novel lipid removal product to the residue analysis of 65 pesticides and 52 environmental contaminants in kale, pork, salmon, and avocado by fast, low pressure gas chromatography - tandem mass spectrometry (LPGC-MS/MS). Sample preparation involves QuEChERS extraction followed by use of EMR-Lipid ("enhanced matrix removal of lipids") and an additional salting out step for cleanup. The optimal amount of EMR-Lipid was determined to be 500mg for 2.5mL extracts for most of the analytes. The co-extractive removal efficiency by the EMR-Lipid cleanup step was 83-98% for fatty samples and 79% for kale, including 76% removal of chlorophyll. Matrix effects were typically less than ±20%, in part because analyte protectants were used in the LPGC-MS/MS analysis. The recoveries of polycyclic aromatic hydrocarbons and diverse pesticides were mostly 70-120%, whereas recoveries of nonpolar polybrominated diphenyl ethers and polychlorinated biphenyls were mostly lower than 70% through the cleanup procedure. With the use of internal standards, method validation results showed that 76-85 of the 117 analytes achieved satisfactory results (recoveries of 70-120% and RSD≤20%) in pork, avocado, and kale, while 53 analytes had satisfactory results in salmon. Detection limits were 5-10ng/g for all but a few analytes. EMR-Lipid is a new sample preparation tool that serves as another useful option for cleanup in multiresidue analysis, particularly of fatty foods. Published by Elsevier B.V.

Liquid chromatography-tandem mass spectrometry method for simultaneous quantification of azoxystrobin and its metabolites, azoxystrobin free acid and 2-hydroxybenzonitrile, in greenhouse-grown lettuce.

PubMed

Gautam, Maheswor; Fomsgaard, Inge S

2017-12-01

Lettuce is an important part of the diet in Europe. The permitted levels of pesticides in lettuce are strictly regulated and there is growing urge among food safety authorities to analyse pesticide metabolites as well. Azoxystrobin is one of pesticides that is frequently detected in lettuce. Although there are several analytical methods for the determination of azoxystrobin in lettuce, a sensitive method for the determination of its metabolites in lettuce is lacking. This study aimed at developing an extraction and LC-MS/MS method for the simultaneous determination of azoxystrobin, and its metabolites azoxystrobin free acid and 2-hydroxybenzonitrile in lettuce. Accelerated solvent extraction, QuEChERS extraction, and shaking extraction were compared using various solvents. The final method consisted of shaking freeze-dried sample in 0.1% formic acid in 80% aqueous acetonitrile. The selected method was validated by spiking each analyte at 125 ng/g and 500 ng/g. The method resulted in acceptable recovery for 2-hydroxybenzonitrile, azoxystrobin free acid, and azoxystrobin, with a RSD of <10%. The matrix-matched calibration curve for each analyte was linear over the range of quantification, with a correlation coefficient ≥0.98. The method was sensitive for the determination of 2-hydroxybenzonitrile, azoxystrobin free acid, and azoxystrobin, with limits of quantification of 0.36, 0.48, and 0.68 ng/g dry weight, respectively. The method was successfully applied to quantify 2-hydroxybenzonitrile, azoxystrobin free acid, and azoxystrobin in greenhouse-grown lettuce.

Optical waveguide lightmode spectroscopy technique-based immunosensor development for aflatoxin B1 determination in spice paprika samples.

PubMed

Majer-Baranyi, Krisztina; Zalán, Zsolt; Mörtl, Mária; Juracsek, Judit; Szendrő, István; Székács, András; Adányi, Nóra

2016-11-15

Optical waveguide lightmode spectroscopy (OWLS) technique has been applied to label-free detection of aflatoxin B1 in a competitive immunoassay format, with the aim to compare the analytical goodness of the developed OWLS immunosenor with HPLC and enzyme-linked immunosorbent assay (ELISA) methods for the detection of aflatoxin in spice paprika matrix. We have also assessed applicability of the QuEChERS method prior to ELISA measurements, and the results were compared to those obtained by traditional solvent extraction followed by immunoaffinity clean-up. The AFB1 content of sixty commercial spice paprika samples from different countries were measured with the developed and optimized OWLS immunosensor. Comparing the results from the indirect immunosensor to that obtained by HPLC or ELISA provided excellent correlation (with regression coefficients above 0.94) indicating that the competitive OWLS immunosensor has a potential for quick determination of aflatoxin B1 in paprika samples. Copyright © 2016 Elsevier Ltd. All rights reserved.

Occurrence of Fusarium mycotoxins and their dietary intake through beer consumption by the European population.

PubMed

Rodríguez-Carrasco, Yelko; Fattore, Margherita; Albrizio, Stefania; Berrada, Houda; Mañes, Jordi

2015-07-01

Since cereals are raw materials for production of beer and beer-based drinks, the occurrence mycotoxins in 154 beer samples was topic of investigation in this study. The analyses were conducted using QuEChERS extraction and gas chromatography-tandem mass spectrometry determination. The analytical method showed recoveries for vast majority of analytes ranged from 70% to 110%, relative standard deviations lower than 15% and limits of detection from 0.05 to 8 μg/L. A significant incidence of HT-2 toxin and deoxynivalenol (DON) were found in 9.1% and 59.7% of total samples, respectively. The exposure of European population to mycotoxins through beer consumption was assessed. No toxicological concern was associated to mycotoxins exposure for average beer consumers. Despite that, for heavy beer drinkers, the contribution of this commodity to the daily intake is not negligible, approaching or even exceeding the safety levels. Copyright © 2015 Elsevier Ltd. All rights reserved.

Flutriafol and pyraclostrobin residues in Brazilian green coffees.

PubMed

de Oliveira, Luiz Alberto Bandeira; Pacheco, Henrique Poltronieri; Scherer, Rodrigo

2016-01-01

The aim of this work was to monitor flutriafol and pyraclostrobin residues in Brazilian green coffees. More than 10,000 samples were analyzed. The pesticides were extracted using the QuEChERS method and analyzed by LC-MS/MS. The validated method is fast, with 5 min runs, and efficient, as precision and accuracy showed RSD no greater than 5% and recoveries within the 88-119% range. LOQ for flutriafol and pyraclostrobin were 0.005 mg/kg. The results of the analyzed samples showed that the percentage of nonconformities regarding flutriafol increased throughout the years, with over 1200 samples (11.8%). On the other hand, just 15 samples (0.15%) presented residues above 10 μg/kg for pyraclostrobin. Considering that flutriafol is a toxic and carcinogenic pesticide, as well as the increase in the number of irregularities throughout the years, it becomes important to implement public actions to assure consumer safety. Copyright © 2015 Elsevier Ltd. All rights reserved.

Occurrence of immunosuppressive drugs and their metabolites in the sewage-impacted Vistula and Utrata Rivers and in tap water from the Warsaw region (Poland).

PubMed

Giebułtowicz, Joanna; Nałęcz-Jawecki, Grzegorz

2016-04-01

Immunosuppresive therapy following organ transplant frequently includes treatment with tacrolimus and mycophenolic acid derivatives. These pharmaceuticals may enter the environment through wastewater treatment plant (WWTP) effluents and may have a potentially harmful effect on aquatic biota. Tacrolimus, mycophenolic acid and their metabolites were measured at specific points of a large Polish river (Vistula), a smaller river (Utrata) and in tap water samples from the Warsaw region. Analysis was performed using liquid chromatography tandem mass spectrometry, after solid phase extraction for water samples, or QuEChERS extraction for sediments. Residues of tacrolimus were below quantitation limits in both water and sediment samples. However, in water samples mycophenolic acid concentrations were measured at up to 180 ng L(-1) downstream of WWTP outfalls. No immunosuppressive drugs were detected in tap water. Concentrations of mycophenolic acid exceeded the predicted no effect concentration (PNEC) value in some Polish surface water, and risk calculations predicted at least twice higher concentrations in some other countries of the European Union. To the best of the authors' knowledge, this is the first report of these immunosuppressive drug concentrations in the environment. Copyright © 2016 Elsevier Ltd. All rights reserved.

Multiresidue analysis of pesticides in straw roughage by liquid chromatography - tandem mass spectrometry

USDA-ARS?s Scientific Manuscript database

A multiresidue analytical method using a modification of the “quick, easy, cheap, effective, rugged, and safe” (QuEChERS) sample preparation approach combined with liquid chromatography–tandem mass spectrometry (LC-MS/MS) analysis was established and validated for the rapid determination of 69 pesti...

Dissipation Pattern, Processing Factors, and Safety Evaluation for Dimethoate and Its Metabolite (Omethoate) in Tea (Camellia Sinensis)

PubMed Central

Pan, Rong; Chen, Hong-Ping; Zhang, Ming-Lu; Wang, Qing-Hua; Jiang, Ying; Liu, Xin

2015-01-01

Residue levels of dimethoate and its oxon metabolite (omethoate) during tea planting, manufacturing, and brewing were investigated using a modified QuEChERS sample preparation and gas chromatography. Dissipation of dimethoate and its metabolite in tea plantation followed the first-order kinetic with a half-life of 1.08–1.27 d. Tea manufacturing has positive effects on dimethoate dissipation. Processing factors of dimethoate are in the range of 2.11–2.41 and 1.41–1.70 during green tea and black tea manufacturing, respectively. Omethoate underwent generation as well as dissipation during tea manufacturing. Sum of dimethoate and omethoate led to a large portion of 80.5–84.9% transferring into tea infusion. Results of safety evaluation indicated that omethoate could bring higher human health risk than dimethoate due to its higher hazard quotient by drinking tea. These results would provide information for the establishment of maximum residue limit and instruction for the application of dimethoate formulation on tea crop. PMID:26406463

Dissipation, transfer and safety evaluation of emamectin benzoate in tea.

PubMed

Zhou, Li; Luo, Fengjian; Zhang, Xinzhong; Jiang, Yaping; Lou, Zhengyun; Chen, Zongmao

2016-07-01

The dissipation and residue of emamectin benzoate in tea leaves and the residue transfer from tea leaves to tea brew were investigated by modified QuEChERS (quick, easy, cheap, effective, rugged and safe) combined with ultra performance liquid chromatography tandem mass (UPLC-MS/MS). The average recoveries ranged 85.3-101.3% with relative standard deviation (RSD) less than 15%. The limits of quantification (LOQ) were 0.005mgkg(-1) in tea leaves and 0.0004mgL(-1) in brew. Emamectin benzoate dissipated rapidly in tea with half-life (t1/2) of 1.0-1.3days. The terminal residues of emamectin benzoate were less than 0.062mgkg(-1). The leaching rate of emamectin benzoate from freshly-made tea to brew was <5%. The risk of emamectin benzoate at the recommended dosage was negligible to humans depending on risk quotient (RQ) value, that was lower than 1 significantly. This study could provide guidance for the safe use of emamectin benzoate and serve as a reference for the establishment of maximum residue limits (MRLs) in China. Copyright © 2016. Published by Elsevier Ltd.

Role of modifiers for analytical-scale supercritical fluid extraction of environmental samples

DOE Office of Scientific and Technical Information (OSTI.GOV)

Langenfeld, J.J.; Hawthorne, S.B.; Miller, D.J.

1994-03-15

Supercritical fluid extraction (SFE) using eight different CO[sub 2] + organic modifier mixtures and one ternary mixture (CO[sub 2] + methanol/toluene) at two different concentrations (1 and 10% v/v) was performed on two certified reference materials including polychlorinated biphenyls (PCBs) from river sediment and polycyclic aromatic hydrocarbons (PAHs) from urban air particulate matter. The modifier identity was more important than modifier concentration for increasing extraction efficiencies. Acidic/basic modifiers including methanol, acetic acid, and aniline greatly enhanced the extraction of PCBs. Low molecular weight PAHs were best extracted with modifiers including aniline, acetic acid, acetonitrile, methanol/toluene, hexane, and diethylamine. In contrast,more » modifiers capable of dipole-induced dipole interactions and [pi]-[pi] interactions such as toluene, diethylamine, and methylene chloride were the best modifiers to use for SFE of high molecular weight PAHs from air particulates. 37 refs., 6 tabs.« less

Influence of pre-treatment process on matrix effect for the determination of musk fragrances in fish and mussel.

PubMed

Vallecillos, Laura; Pocurull, Eva; Borrull, Francesc

2015-03-01

Musk compounds are widely used as fragrances in personal care products. On account of their widespread use and their low biodegradation, they can be found in environmental samples. In our study two extraction methodologies were compared and different clean-up strategies were also studied in order to develop a reliable analytical method, with minimum matrix effect and good detection limits, to determine synthetic musk fragrances- six polycyclic musks, three nitro musks and the degradation product of one polycyclic musk- in fish and mussel samples. The first extraction technique involves a QuEChERS extraction, a consolidate extraction methodology in the field of food analysis of growing interest over recent years, followed by a dispersive solid-phase extraction (dSPE) as clean-up strategy. The second extraction technique consists of a conventional pressurised liquid extraction (PLE) with dichloromethane and an in-cell clean-up to decrease the matrix effect and remove the undesired components(⁎)present in PLE extracts. Large volume injection (LVI) followed by gas chromatography-ion trap-tandem mass spectrometry (GC-IT-MS/MS) was chosen as the separation and detection technique. Validation parameters, such as method detection limits and method quantification limits were found at ng g(-1) levels for both fish and mussel matrices. Good levels of intra-day and inter-day repeatabilities were obtained analysing fish and mussel samples spiked at 50 ng g(-1) (d.w.) (n=5, RSDs<17%). The developed PLE/GC-IT-MS/MS method was successfully applied to determine the target musk fragrances present in fish and mussel samples from the local market in Tarragona and fish samples from the Ebro River. The results showed the presence of galaxolide (2.97-18.04 ng g(-1) (d.w.)) and tonalide (1.17-8.42 ng g(-1) (d.w.)) in all the samples analysed, while the remaining polycyclic musks such as cashmeran, celestolide and phantolide, were only detected in some of the fish samples analysed. None of the samples analysed contained detectable traces of the nitro musks studied. Copyright © 2014 Elsevier B.V. All rights reserved.

[Determination of 6 kinds of plant growth regulator in bean sprout by ultra high performance liquid chromatography-tandem mass spectrometry].

PubMed

Liu, Ping; Fan, Sai; Wu, Guohua; Zhao, Rong; Liu, Wei; Zhao, Xudong

2016-05-01

A method for the simultaneous determination of 6 plant growth regulator (PGR) residues in bean sprout was developed by ultra high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). 6-Benzylaminopurine, isopentennyladenine, 4-chlorophenoxyacetic acid, 4-fluorophenoxyacetic acid, indole-3- acetic acid and indole-3-butyric acid were concerned. Bean sprout samples were extracted by acetonitrile and QuEChERS extraction kit, purified by C18 powers. After centrifugation, the sample liquids was diluted 10 times by ultrapure water. The chromatographic analysis was carried out on an waters acquity UPLC BEH C18 column( 100 mm x 2.1 mm, 1.7 microm). The analyzer confirmed and quantified by mass spectrum of triple quadrupole in the multiple reaction monitoring (MRM) mode and quantified by matrix-matched external standard method. The calibration curves showed good linearity in each range with correlation coefficients greater than 0.998. 3 levels spiked recoveries were carried out using blank bean sprout extraction as substrate, the recoveries ranged from 84.2% to 107.5%, the relative standard deviations (RSDs) ranged from 3.08% to 12.71%. The qualitative limits of detections (S/N = 3) were 0.03-3.0 microg/kg and the quantitative limits(S/N = 10) were 0.1-10.0 microg/kg for the 6 PGRs. The method is simple and easy to operate, with less organic reagent, high sensitivity and good stability. It is suitable for the detection of 6 kinds of plant growth regulators in bean sprouts.

[Determination of three exogenous plant hormone residues in bean sprout by high performance liquid chromatography-quadrupole-time of flight mass spectrometry].

PubMed

Xie, Hanbing; Zhou, Mingying; Zhao, Haifeng; Wang, Yigang; Jiang, Wanfeng; Zhao, Shan

2014-05-01

This study was aimed to the establishment of an analytical method for the determination of three exogenous plant hormone residues in bean sprout by high performance liquid chromatography-quadrupole-time of flight mass spectrometry (HPLC-Q-TOF-MS). The target compounds were gibberellins, 6-benzylaminopurine and parachlorophenoxyacetic acid. The QuEChERS (quick, easy, cheap, effective, rugged, and safe) method was used for sample preparation. The analytes were extracted with a solution containing 1% (v/v, if not specified) acetic, 50% ethanol, 49% acetonitrile, and cleaned-up by dispersive solid-phase extraction with diatomite dispersant, then degreased by hexane. The three target compounds were separated on an Eclipse Plus C18 column (100 mm x 3.0 mm, 1.8 microm) with mobile phases A (water containing 0.1% formic acid) and B (methanol) by gradient elution within 15 min, and detected under negative electrospray ionization (ESI) mode. The quantitative analysis was carried out by extracting the peak area with accurate mass. The confirmatory analysis of the target compounds was performed with the qualitative fragments. The results showed that the limits of quantification (LOQs, S/N = 10) for the three target compounds were from 5.0 microg/kg to 10 microg/kg. The respective mean recoveries were found to be in the range of 79.1%-96.1%, and the RSDs were 5.7%-10.4%. It was applicable to the analysis of the three exogenous plant hormones in bean sprout samples. This method is simple, fast and efficient.

Improved Butanol-Methanol (BUME) Method by Replacing Acetic Acid for Lipid Extraction of Biological Samples.

PubMed

Cruz, Mutya; Wang, Miao; Frisch-Daiello, Jessica; Han, Xianlin

2016-07-01

Extraction of lipids from biological samples is a critical step in lipidomics, especially for shotgun lipidomics where lipid extracts are directly infused into a mass spectrometer. The butanol-methanol (BUME) extraction method was originally developed to extract lipids from plasma samples with 1 % acetic acid. Considering some lipids are sensitive to acidic environments, we modified this protocol by replacing acetic acid with lithium chloride solution and extended the modified extraction to tissue samples. Although no significant reduction of plasmalogen levels in the acidic BUME extracts of rat heart samples was found, the modified method was established to extract various tissue samples, including rat liver, heart, and plasma. Essentially identical profiles of the majority of lipid classes were obtained from the extracts of the modified BUME and traditional Bligh-Dyer methods. However, it was found that neither the original, nor the modified BUME method was suitable for 4-hydroxyalkenal species measurement in biological samples.

Improved Butanol-Methanol (BUME) Method by Replacing Acetic Acid for Lipid Extraction of Biological Samples

PubMed Central

Cruz, Mutya; Wang, Miao; Frisch-Daiello, Jessica; Han, Xianlin

2016-01-01

Extraction of lipids from biological samples is a critical step in lipidomics, especially for shotgun lipidomics where lipid extracts are directly infused into a mass spectrometer. The butanol-methanol (BUME) extraction method was originally developed to extract lipids from plasma samples with 1% acetic acid. Considering some lipids are sensitive to acidic environments, we modified this protocol by replacing acetic acid with lithium chloride solution and extended the modified extraction to tissue samples. Although no significant reduction of plasmalogen levels in the acidic BUME extracts of rat heart samples was found, the modified method was established to extract various tissue samples, including rat liver, heart, and plasma. Essentially identical profiles of the majority of lipid classes were obtained from the extracts of the modified BUME and traditional Bligh-Dyer methods. However, it was found that neither the original, nor the modified BUME method was suitable for 4-hydroxyalkenal species measurement in biological samples. PMID:27245345

A multi-residue method for pesticides analysis in green coffee beans using gas chromatography-negative chemical ionization mass spectrometry in selective ion monitoring mode.

PubMed

Pizzutti, Ionara R; de Kok, Andre; Dickow Cardoso, Carmem; Reichert, Bárbara; de Kroon, Marijke; Wind, Wouter; Weber Righi, Laís; Caiel da Silva, Rosselei

2012-08-17

In this study, a new gas chromatography-mass spectrometry (GC-MS) method, using the very selective negative chemical ionization (NCI) mode, was developed and applied in combination with a modified acetonitrile-based extraction method (QuEChERS) for the analysis of a large number of pesticide residues (51 pesticides, including isomers and degradation products) in green coffee beans. A previously developed integrated sample homogenization and extraction method for both pesticides and mycotoxins analysis was used. An homogeneous slurry of green milled coffee beans and water (ratio 1:4, w/w) was prepared and extracted with acetonitrile/acetic acid (1%), followed by magnesium sulfate addition for phase separation. Aliquots from this extract could be used directly for LC-MS/MS analysis of mycotoxins and LC-amenable pesticides. For GC-MS analysis, a further clean-up was necessary. C18- and PSA-bonded silica were tested as dispersive solid-phase extraction (d-SPE) sorbents, separate and as a mixture, and the best results were obtained using C18-bonded silica. For the optimal sensitivity and selectivity, GC-MS detection in the NCI-selected ion monitoring (SIM) mode had to be used to allow the fast analysis of the difficult coffee bean matrix. The validation was performed by analyzing recovery samples at three different spike concentrations, 10, 20 and 50 μg kg(-1), with 6 replicates (n=6) at each concentration. Linearity (r(2)) of calibration curves, estimated instrument and method limits of detection and limits of quantification (LOD(i), LOD(m), LOQ(i) and LOQ(m), respectively), accuracy (as recovery %), precision (as RSD%) and matrix effects (%) were determined for each individual pesticide. From the 51 analytes (42 parent pesticides, 4 isomers and 5 degradation products) determined by GC-MS (NCI-SIM), approximately 76% showed average recoveries between 70-120% and 75% and RSD ≤ 20% at the lowest spike concentration of 10 μg kg(-1), the target method LOQ. For the spike concentrations of 20 and 50 μg kg(-1), the recoveries and RSDs were even better. The validated LOQ(m) was 10, 20 and 50 μg kg(-1) for respectively 33, 3 and 6 of the analytes studied. For five compounds, the European Union method performance requirements for the validation of a quantitative method (average recoveries between 70-120% and repeatability RSD ≤ 20%) were not achieved and 4 problematic pesticides (captan, captafol, folpet and dicofol) could not be detected as their parent compound, but only via their degradation products. Although the matrix effect (matrix-enhanced detector response) was high for all pesticides studied, the matrix interference was minimal, due to the high selectivity obtained with the GC-NCI-MS detection. Matrix-matched calibration for applying the method in routine analysis is recommended for reliable quantitative results. Copyright © 2012 Elsevier B.V. All rights reserved.

Identification and Quantitation of Furocoumarins in Popularly Consumed Foods in the U.S. Using QuEChERS Extraction Coupled with UPLC-MS/MS Analysis.

PubMed

Melough, Melissa M; Lee, Sang Gil; Cho, Eunyoung; Kim, Kijoon; Provatas, Anthony A; Perkins, Christopher; Park, Min Kyung; Qureshi, Abrar; Chun, Ock K

2017-06-21

Furocoumarins are a class of photoactive compounds found in several plant species and may be responsible for the observed association between consumption of citrus products and the risk of skin cancer. Furocoumarin contents of several foods have been reported previously, but no comprehensive database of furocoumarin content of foods is currently available. Therefore, this study aimed to determine the distribution of furocoumarins in popularly consumed foods in the U.S. Samples of three varieties of each of 29 foods known or suspected to contain furocoumarins were purchased, prepared for analysis using a solid phase extraction method, and analyzed using UPLC-MS/MS for the presence of seven major furocoumarins. Most foods measured contained more than one furocoumarin, and some contained all seven of the furocoumarins examined. Total furocoumarin concentration was greatest in fresh parsley (23215 ng/g), grapefruits (21858 ng/g), lime juice (14580 ng/g), grapefruit juice (95341 ng/g), and limes (9151 ng/g). Bergamottin was found in the greatest proportion of foods sampled (23 of 29), followed by bergapten (19 of 29) and 6'7'-dihydroxybergamottin (16 of 29). These measurements will enable more accurate estimation of dietary furocoumarin exposure and will strengthen future epidemiological work investigating the relationships between furocoumarin intake and health outcomes.

Determination of bromothalonil residues and degradation in apple and soil by QuEChERS and GC-MS/MS.

PubMed

Liu, Huijun; Guo, Baoyuan; Wang, Huili; Li, Jianzhong; Zheng, Lin

2014-04-01

The dissipation and residues of bromothalonil in apple and soil under field condition were analyzed by QuEChERS (quick, easy, cheap, effective, rugged and safe) combined with gas chromatography-mass spectrometer method. The recoveries were ranged from 80.8 % to 106 % with coefficient variation for repeatability ranged from 3.08 % to 7.09 % at fortification levels of 0.02, 0.04 and 0.2 mg/kg in apple and soil. The limit of quantification of the method was 0.31 μg/kg. The dissipation rates of bromothalonil followed the first-order kinetics and the half-lives were from 3.61 to 3.98 days in apple and from 4.65 to 9.29 days in soil. In apple, the terminal residues of bromothalonil were below the China maximum residue limit (0.2 mg/kg) after 7 days of application. This work contributed to provide the basic information for a safe usage of bromothalonil in apple orchard and preventing health problem from consumers in China.

Sorption and degradation of neonicotinoid insecticides in tropical soils.

PubMed

Dankyi, Enock; Gordon, Chris; Carboo, Derick; Apalangya, Vitus A; Fomsgaard, Inge S

2018-05-22

Neonicotinoids are the most widely applied class of insecticides in cocoa farming in Ghana. Despite the intensive application of these insecticides, knowledge of their fate in the Ghanaian and sub-Saharan African environment remains low. This study examined the behavior of neonicotinoids in soils from cocoa plantations in Ghana by estimating their sorption and degradation using established kinetic models and isotherms. Studies of sorption were conducted using the batch equilibrium method on imidacloprid, thiamethoxam, clothianidin, acetamiprid and thiacloprid, while degradation of imidacloprid, thiamethoxam and their respective deuterated counterparts was studied using models proposed by the European forum for coordination of pesticide fate and their use (FOCUS). Analytes were extracted using the quick, easy, cheap, effective, rugged and safe (QuEChERS) procedure and quantified by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Average recoveries were high (≥ 85%) for all analytes. The findings from the study suggest that neonicotinoid insecticides may be persistent in the soils studied based on estimated half-lives > 150 days. The study also revealed generally low-sorption coefficients for neonicotinoids in soils, largely influenced by soil organic carbon.

Validation of a Multiresidue Analysis Method for 379 Pesticides in Human Serum Using Liquid Chromatography-Tandem Mass Spectrometry.

PubMed

Shin, Yongho; Lee, Jonghwa; Lee, Jiho; Lee, Junghak; Kim, Eunhye; Liu, Kwang-Hyeon; Lee, Hye Suk; Kim, Jeong-Han

2018-04-04

A screening method for simultaneous analysis of 379 pesticides in human serum was developed using liquid chromatography-tandem mass spectrometry (LC-MS/MS). Electrospray ionization with positive/negative switching mode of LC-MS/MS was adopted, and scheduled multiple reaction monitoring for each target compound was established. The limit of quantitation was 10 ng/mL for 94.5% of the total pesticides, and the correlation coefficients of calibration were ≥0.990 for 93.9% of the pesticides. For the sample preparation, scaled-down QuEChERS were used. Serum (100 μL) was extracted with acetonitrile (400 μL), partitioned with magnesium sulfate (40 mg) and sodium chloride (10 mg), and the upper layer was used for analysis without further cleanup steps. For the accuracy and precision tests, most of the pesticides showed excellent results in intra- and interday conditions. In the recovery tests at 10, 50, and 250 ng/mL, 85.8-91.8% of all target compounds satisfied the recovery range of 70-120% (relative standard deviation ≤20%).

Long-Term Persistence of Pesticides and TPs in Archived Agricultural Soil Samples and Comparison with Pesticide Application.

PubMed

Chiaia-Hernandez, Aurea C; Keller, Armin; Wächter, Daniel; Steinlin, Christine; Camenzuli, Louise; Hollender, Juliane; Krauss, Martin

2017-09-19

For polar and more degradable pesticides, not many data on long-term persistence in soil under field conditions and real application practices exist. To assess the persistence of pesticides in soil, a multiple-compound screening method (log K ow 1.7-5.5) was developed based on pressurized liquid extraction, QuEChERS and LC-HRMS. The method was applied to study 80 polar pesticides and >90 transformation products (TPs) in archived topsoil samples from the Swiss Soil Monitoring Network (NABO) from 1995 to 2008 with known pesticide application patterns. The results reveal large variations between crop type and field sites. For the majority of the sites 10-15 pesticides were identified with a detection rate of 45% at concentrations between 1 and 330 μg/kg dw in soil. Furthermore, TPs were detected in 47% of the cases where the "parent-compound" was applied. Overall, residues of about 80% of all applied pesticides could be detected with half of these found as TPs with a persistence of more than a decade.

Chemiluminescent Determination of Oxamyl in Drinking Water and Tomato Using Online Postcolumn UV Irradiation in a Chromatographic System.

PubMed

Murillo Pulgarín, José A; García Bermejo, Luisa F; Durán, Armando Carrasquero

2018-03-07

High-performance liquid chromatography (HPLC) was used to separate oxamyl from other pesticides in drinking water and tomato paste. The eluate emerging from the column tail was mixed with an alkaline solution of Co 2+ in EDTA and irradiated with UV light to induce photolysis of the carbamate in order to obtain free radicals and other reactive species that oxidize luminol and produce chemiluminescence (CL) as a result. The intensity of the CL signal was monitored in the form of chromatographic peaks. Under the optimum operating conditions for the HPLC-UV-CL system, the analyte concentration was linearly related to peak area. The limit of detection as determined in accordance with the IUPAC criterion was 0.17 mg L -1 . Oxamyl was successfully extracted with recoveries of 88.7-103.1% from spiked tomato paste by using a simple QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) sample preparation approach. Similar recoveries were obtained from drinking water samples spiked with oxamyl concentrations above the LOD. The proposed method is a simple, fast, accurate choice for quantifying this pesticide.

Validation of a liquid chromatography-electrospray ionization tandem mass spectrometric method to determine six polyether ionophores in raw, UHT, pasteurized and powdered milk.

PubMed

Pereira, Mararlene Ulberg; Spisso, Bernardete Ferraz; Jacob, Silvana do Couto; Monteiro, Mychelle Alves; Ferreira, Rosana Gomes; Carlos, Betânia de Souza; da Nóbrega, Armi Wanderley

2016-04-01

This study aimed to validate a method developed for the determination of six antibiotics from the polyether ionophore class (lasalocid, maduramicin, monensin, narasin, salinomycin and semduramicin) at residue levels in raw, UHT, pasteurized and powdered milk using QuEChERS extraction and high performance liquid chromatography coupled to tandem mass spectrometry (HPLC-MS/MS). The validation was conducted under an in-house laboratory protocol that is primarily based on 2002/657/EC Decision, but takes in account the variability of matrix sources. Overall recoveries between 93% and 113% with relative standard deviations up to 16% were obtained under intermediate precision conditions. CCα calculated values did not exceed 20% the Maximum Residue Limit for monensin and 25% the Maximum Levels for all other substances. The method showed to be simple, fast and suitable for verifying the compliance of raw and processed milk samples regarding the limits recommended by Codex Alimentarius and those adopted in European Community for polyether ionophores. Copyright © 2015 Elsevier Ltd. All rights reserved.

Determination of nonylphenol ethoxylate and octylphenol ethoxylate surfactants in beehive samples by high performance liquid chromatography coupled to mass spectrometry.

PubMed

Chen, Jing; Mullin, Christopher A

2014-09-01

Nonylphenol and octylphenol ethoxylates (NP(EO)n and OP(EO)n) are major toxicants in agrochemicals used around beehives. Here we developed a LC-MS method for analysis of NP(EO)3-13 and OP(EO)3-13 oligomers in bee hive matrices. Less than 2 g of honey, pollen or wax were extracted using the QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) approach. Recoveries for each oligomer in all matrices are between 75% and 111% at three spiked concentrations. The method proved to be rapid, precise and sensitive. Five honey, 10 pollen and 12 wax samples were collected and analysed. NP(EO)n was detected in every sample with concentrations ranging from 26 ppb to 10,239 ppb. Much higher NP(EO)n residues levels were found in wax followed by pollen than in honey. OP(EO)n concentrations on average were more than 10 times lower in pollen and wax. This method demonstrates a probable wide occurrence of alkylphenol ethoxylates in USA beehives. Copyright © 2014 Elsevier Ltd. All rights reserved.

Automated Mini-Column Solid-Phase Extraction Cleanup for High-Throughput Analysis of Chemical Contaminants in Foods by Low-Pressure Gas Chromatography-Tandem Mass Spectrometry.

PubMed

Lehotay, Steven J; Han, Lijun; Sapozhnikova, Yelena

2016-01-01

This study demonstrated the application of an automated high-throughput mini-cartridge solid-phase extraction (mini-SPE) cleanup for the rapid low-pressure gas chromatography-tandem mass spectrometry (LPGC-MS/MS) analysis of pesticides and environmental contaminants in QuEChERS extracts of foods. Cleanup efficiencies and breakthrough volumes using different mini-SPE sorbents were compared using avocado, salmon, pork loin, and kale as representative matrices. Optimum extract load volume was 300 µL for the 45 mg mini-cartridges containing 20/12/12/1 (w/w/w/w) anh. MgSO 4 /PSA (primary secondary amine)/C 18 /CarbonX sorbents used in the final method. In method validation to demonstrate high-throughput capabilities and performance results, 230 spiked extracts of 10 different foods (apple, kiwi, carrot, kale, orange, black olive, wheat grain, dried basil, pork, and salmon) underwent automated mini-SPE cleanup and analysis over the course of 5 days. In all, 325 analyses for 54 pesticides and 43 environmental contaminants (3 analyzed together) were conducted using the 10 min LPGC-MS/MS method without changing the liner or retuning the instrument. Merely, 1 mg equivalent sample injected achieved <5 ng g -1 limits of quantification. With the use of internal standards, method validation results showed that 91 of the 94 analytes including pairs achieved satisfactory results (70-120 % recovery and RSD ≤ 25 %) in the 10 tested food matrices ( n  = 160). Matrix effects were typically less than ±20 %, mainly due to the use of analyte protectants, and minimal human review of software data processing was needed due to summation function integration of analyte peaks. This study demonstrated that the automated mini-SPE + LPGC-MS/MS method yielded accurate results in rugged, high-throughput operations with minimal labor and data review.

Pesticide analysis in coffee leaves using a quick, easy, cheap, effective, rugged and safe approach and liquid chromatography tandem mass spectrometry: Optimization of the clean-up step.

PubMed

Trevisan, Maria Teresa Salles; Owen, Robert Wyn; Calatayud-Vernich, Pau; Breuer, Andrea; Picó, Yolanda

2017-08-25

An analytical method using a quick, easy, cheap, effective, rugged and safe (QuEChERS) procedure for multi-residue determination of 52 pesticides in coffee leaf extractshas been developed and validated according to SANTE/11945/2015 guidelines. Different sorbent combinations for dispersive solid phase extraction (d-SPE) clean-up as well as dispersive liquid-liquid microextraction (DLLME) were tested. The relative standard deviations (RSDs) for the recovery of 87-94% of pesticides added to coffee leaf extracts,was ≤20% for samples spiked at concentrations up to 50ng*g -1 depending on the clean-up procedures. However, samples spiked with a 100ng*g -1 pesticide mixture gave RSDs>20% for most pesticides when d-SPE was carried out adding Supelclean ENVI-Carb 120/400. To explain this fact,the secondary metabolic profile was analyzed in all the extraction and clean-up procedures. Only in the clean-up procedure with the addition of Supel QuE Z-Sep+, does caffeine show a constant adsorption between blank and spiked samples. In other clean-up procedures, the amount of caffeine was higher in those samples spiked with pesticides. This indicates competition between caffeine and pesticides for adsorption to the sorbent. Addition of Supel QuE Z-Sep+ to the procedure revealed only a 32% matrix effect, whereas using PSA+ C18 the matrix effect was close to 97%. The process efficiency is up to 54% with the addition of Supel QuE Z-Sep+ and just up to 7% for the other clean-up procedures. The method was successfully tested in coffee leaves from different types of cultivars. Pesticides were not detected in organic coffee leaf extracts, but thiametoxan was clearly detected in 50% of coffee leaf extracts harvested from coffee trees grown under traditional conditions as determined by UHPLC-TOFMSLC/QqTOF-MS/MS. Copyright © 2017 Elsevier B.V. All rights reserved.

Simultaneous enantioselective determination of phenylpyrazole insecticide flufiprole and its chiral metabolite in paddy field ecosystem by ultra-high performance liquid chromatography/tandem mass spectrometry.

PubMed

Li, Jing; Zhang, Yuting; Cheng, Youpu; Yuan, Shankui; Liu, Lei; Shao, Hui; Li, Hui; Li, Na; Zhao, Pengyue; Guo, Yongze

2016-03-20

A novel and sensitive ultra-high performance liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) method was developed and validated for simultaneous enantioselective determination of flufiprole and its hydrolysis metabolite in paddy field ecosystem. The separation and determination were performed using reversed-phase chromatography on a novel cellulose chiral stationary phase, a Lux Cellulose-4 (150 mm × 2.0 mm) column, under isocratic conditions at 0.25 mL/min flow rate. The effects of other four different polysaccharide-based chiral stationary phases (CSPs) on the separation and simultaneous enantioseparation of the two target compounds were also evaluated. The elution orders of the eluting enantiomers were identified by an optical rotation detector. Modified QuEChERS (acronym for Quick, Easy, Cheap, Effective, Rugged and Safe) method and solid-phase extraction (SPE) were used for the enrichment and cleanup of paddy water, rice straw, brown rice and paddy soil samples, respectively. Parameters including the matrix effect, linearity, precision, accuracy and stability were evaluated. Under the optimal conditions, the mean recoveries for all enantiomers from the above four sample matrix were ranged from 83.6% to 107%, with relative standard deviations (RSD) in the range of 1.0-5.8%. Coefficients of determination R(2)≥0.998 were achieved for each enantiomer in paddy water, rice straw, brown rice and paddy soil matrix calibration curves within the range of 5-500 μg/kg. The limits of quantification (LOQ) for all stereoisomers in the above four matrices were all below 2.0 μg/kg. The methodology was successfully applied for simultaneously enantioselective analysis of flufiprole enantiomers and their chiral metabolite in the real samples, indicating its efficacy in investigating the environmental stereochemistry of flufiprole in paddy field ecosystem. Copyright © 2016 Elsevier B.V. All rights reserved.

Multiresidue pesticide analysis in ginseng and spinach by nontargeted and targeted screening procedures.

PubMed

Hayward, Douglas G; Wong, Jon W; Zhang, Kai; Chang, James; Shi, Feng; Banerjee, Kaushik; Yang, Paul

2011-01-01

Five different mass spectrometers interfaced to GC or LC were evaluated for their application to targeted and nontargeted screening of pesticides in two foods, spinach and ginseng. The five MS systems were capillary GC/MS/MS, GC-high resolution time-of-flight (GC/HR-TOF)-MS, TOF-MS interfaced with a comprehensive multidimensional GC (GCxGC/TOF-MS), an MS/MS ion trap hybrid mass (qTrap) system interfaced with an ultra-performance liquid chromatograph (UPLC-qTrap), and UPLC interfaced to an orbital trap high resolution mass spectrometer (UPLC/Orbitrap HR-MS). Each MS system was tested with spinach and ginseng extracts prepared through a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) procedure. Each matrix was fortified at 10 and 50 ng/g for spinach or 25 and 100 ng/g for ginseng with subsets of 486 pesticides, isomers, and metabolites representing most pesticide classes. HR-TOF-MS was effective in a targeted search for characteristic accurate mass ions and identified 97% of 170 pesticides in ginseng at 25 ng/g. A targeted screen of either ginseng or spinach found 94-95% of pesticides fortified for analysis at 10 ng/g with GC/MS/MS or LC/MS/MS using multiple reaction monitoring (MRM) procedures. Orbitrap-MS successfully found 89% of 177 fortified pesticides in spinach at 25 ng/g using a targeted search of accurate mass pseudomolecular ions in the positive electrospray ionization mode. A comprehensive GCxGC/TOF-MS system provided separation and identification of 342 pesticides and metabolites in a single 32 min acquisition with standards. Only 67 or 81% of the pesticides were identified in ginseng and spinach matrixes at 25 ng/g or 10 ng/g, respectively. MS/MS or qTrap-MS operated in the MRM mode produced the lowest false-negative rates, at 10 ng/g. Improvements to instrumentation, methods, and software are needed for efficient use of nontargeted screens in parallel with triple quadrupole MS.

GC-MS/MS determination and ecological risk assessment of pesticides in aquatic system: A case study in Hooghly River basin in West Bengal, India.

PubMed

Mondal, Rahul; Mukherjee, Ayan; Biswas, Subrata; Kole, Ramen Kumar

2018-04-30

A liquid-liquid extraction (LLE) for water and modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) method for sediment combined with gas chromatography-tandem mass spectrometry (GC-MS/MS) detection in multiple reaction monitoring (MRM) mode was standardized for determination of 31 pesticides. Performance characteristics for the selected pesticides were acceptable according to European Commission's (EC) guidelines for method validation (recovery 70-120%, RSD <20% and R 2 value ≥ 0.99). River, pond and tubewell water and river sediment samples (64 nos.) were collected from Hooghly River basin in West Bengal, India during 2014-2016. About 42% of the samples showed the presence of 19 pesticides with the highest loading of total pesticides (T-pesticides) in river water (3.01 ng mL -1 ) followed by sediment (1.25 ng g -1 ), pond (0.40 ng mL -1 ) and tubewell (0.02 ng mL -1 ) water. The non-agricultural OC (organochlorine) insecticides were detected in all river water and sediment samples mainly due to HCHs (hexachlorocyclohexane) from old source and fresh use of DDTs (dichlorodiphenyltrichloroethane) in local areas. No OC insecticides were detected in pond and tubewell water. Maximum residues of some recommended pesticides in agriculture were obtained in pond water. Most of the river water samples (93.7%) were in excess of EC limit (0.50 ng mL -1 ) of T-pesticides for drinking followed by pond water samples (56.2%). Tubewell water samples were free from T-pesticide threat but exceeded the EC limit (0.10 ng mL -1 ) for single pesticide in case of chlorpyrifos only. Ecological risk on aquatic animals was observed for OCs in river and chlorpyrifos in pond aquatic ecosystem. Copyright © 2018 Elsevier Ltd. All rights reserved.

Date palm pollen allergoid: characterization of its chemical-physical and immunological properties.

PubMed

Mistrello, G; Harfi, H; Roncarolo, D; Kwaasi, A; Zanoni, D; Falagiani, P; Panzani, R

2008-01-01

Date palm (DP) pollen can cause allergic symptoms in people living in different countries. Specific immunotherapy with allergenic extracts by subcutaneous route is effective to cure allergic people. However, the risk of side effects has led to explore safer therapeutic modalities. The aim of our work was to evaluate IgE cross-reactivity between DP and autochthonous palm (European fan palm, EFP) pollen extracts, to chemically modify DP extract with potassium cyanate in order to obtain an allergoid, and to characterize it. By radioallergosorbent test inhibition, immunoblotting (IB) and skin prick test, in vitro and in vivo allergenic activities of native and modified DP extracts were compared. By SDS-PAGE and IB, we compared the protein profile and IgE-binding capacity of both native and modified DP, as well as of EFP extracts. By IB inhibition, IgE cross-reactivity of native DP and EFP extracts was evaluated. By ELISA, the capacity of modified DP-induced IgG to react with native DP extract was determined. Radioallergosorbent test inhibition, IB and skin prick test results demonstrated that modified DP was significantly less allergenic than native DP extract. The SDS-PAGE profile showed that potassium cyanate treatment of DP extract did not alter the molecular weight of its components. In addition, no difference was observed between native DP and EFP extracts. Subsequent IB inhibition data evidenced the existence of a strong IgE cross-reactivity between native DP and EFP extracts. ELISA results indicated that the administration of modified DP in mice was able to induce specific IgG also recognizing native DP extract. Modified DP extract (allergoid) seems to be a good candidate for immunotherapy of patients affected by specific allergy. 2007 S. Karger AG, Basel

Measurement of Pyrethroids and Their Environmental Degradates in Fruits and Vegetables using a Modification of the Quick Easy Cheap Effective Rugged Safe (QuEChERS) Method

EPA Science Inventory

Pyrethroid insecticides are used extensively in agriculture and they, as well as their environmental degradates, may remain as residues on food products such as fruits and vegetables. Since pyrethroid degradates can be identical to the urinary markers used in human biomonitoring ...

Quantitative Multiclass Pesticide Residue Analysis in Apple, Pear, and Grape by Modified QuEChERS and Liquid Chromatography Coupled to High-Resolution Mass Spectrometry.

PubMed

Munaretto, Juliana S; Viera, Mariela de S; Martins, Manoel L; Adaime, Martha B; Zanella, Renato

2016-11-01

Most of the analytical methods currently applied in food control laboratories are focused on the determination of target compounds using LC coupled to tandem MS, which is an effective technique, but low-resolution MS is limited. Thus, a method for determination of pesticide multiresidues in fruits (pear, apple, and grape) using a modified quick, easy, cheap, effective, rugged, and safe method and LC coupled to quadrupole time-of-flight (Q-TOF) MS was developed and validated. The proposed method showed good linearity (r2 > 0.99) from 1 to 100 μg/L. Recoveries for blank samples spiked at 0.01, 0.04, and 0.10 mg/kg were between 66 and 122%, with RSDs <28%. Respective LOQs for apple, pear, and grape matrixes were 0.01 mg/kg for 112, 120, and 118 compounds, and 0.04 mg/kg for 22, 12, and 17 compounds, and average mass accuracy error was 3.2 ppm. LC with Q-TOF MS detection using protonated molecular ion and/or adducts and mass accuracy provided reliability for the method. The proposed method is effective for pesticide residue determination in apple, pear, and grape samples, proving that high-resolution MS using full scan mode can be a powerful and reliable technique for quantification purposes, being adequate for application in the surveillance of maximum residue limits set by different legislations.

Magnetic graphene oxide modified by imidazole-based ionic liquids for the magnetic-based solid-phase extraction of polysaccharides from brown alga.

PubMed

Wang, Xiaoqin; Li, Guizhen; Row, Kyung Ho

2017-08-01

Magnetic graphene oxide was modified by four imidazole-based ionic liquids to synthesize materials for the extraction of polysaccharides by magnetic solid-phase extraction. Fucoidan and laminarin were chosen as the representative polysaccharides owing to their excellent pharmaceutical value and availability. Fourier transform infrared spectroscopy, field-emission scanning electron microscopy, and thermogravimetric analysis were applied to characterize the synthesized materials. Single-factor experiments showed that the extraction efficiency of polysaccharides was affected by the amount of ionic liquids for modification, solid-liquid ratio of brown alga and ethanol, the stirring time of brown alga and ionic liquid-modified magnetic graphene oxide materials, and amount of 1-(3-aminopropyl)imidazole chloride modified magnetic graphene oxide materials added to the brown alga sample solution. The results indicated that 1-(3-aminopropyl)imidazole chloride modified magnetic graphene oxide possessed better extraction ability than graphene oxide, magnetic graphene oxide, and other three ionic-liquid-modified magnetic graphene oxide materials. The highest extraction recoveries of fucoidan and laminarin extracted by 1-(3-aminopropyl)imidazole chloride modified magnetic graphene oxide were 93.3 and 87.2%, respectively. In addition, solid materials could be separated and reused easily owing to their magnetic properties. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multiclass analytical method for the determination of natural/synthetic steroid hormones, phytoestrogens, and mycoestrogens in milk and yogurt.

PubMed

Socas-Rodríguez, Bárbara; Lanková, Darina; Urbancová, Kateřina; Krtková, Veronika; Hernández-Borges, Javier; Rodríguez-Delgado, Miguel Ángel; Pulkrabová, Jana; Hajšlová, Jana

2017-07-01

Within this study, a new method enabling monitoring of various estrogenic substances potentially occurring in milk and dairy products was proposed. Groups of compounds fairly differing in physico-chemical properties and biological activity were analyzed: four natural estrogens, four synthetic estrogens, five mycoestrogens, and nine phytoestrogens. Since they may pass into milk mainly in glucuronated and sulfated forms, an enzymatic hydrolysis was involved prior to the extraction based on the QuEChERS methodology. For the purification of the organic extract, a dispersive solid-phase extraction (d-SPE) with sorbent C18 was applied. The final analysis was performed by ultra-high-performance liquid chromatography (UHPLC) coupled with triple quadrupole tandem mass spectrometry (MS/MS). Method recovery ranged from 70 to 120% with a relative standard deviation (RSD) value lower than 20% and limits of quantification (LOQs) in the range of 0.02-0.60 μg/L (0.2-6.0 μg/kg dry weight) and 0.02-0.90 μg/kg (0.2-6.0 μg/kg dry weight) for milk and yogurt, respectively. The new procedure was applied for the investigation of estrogenic compounds in 11 milk samples and 13 yogurt samples from a Czech retail market. Mainly phytoestrogens were found in the studied samples. The most abundant compounds were equol and enterolactone representing 40-90% of all estrogens. The total content of phytoestrogens (free and bound) was in the range of 149-3870 μg/kg dry weight. This amount is approximately 20 times higher compared to non-bound estrogens.

Analysis of nitrosamines in cooked bacon by QuEChERS sample preparation and gas chromatography – tandem mass spectrometry with backflushing

USDA-ARS?s Scientific Manuscript database

Nitrites are added as a preservative to a variety of cured meats, including bacon, to kill bacteria, extend shelf-life, and improve quality. During cooking, nitrites in the meat can be converted to carcinogenic nitrosamines (NAs), the formation of which are mitigated by the addition of anti-oxidant...

Measurement of pyrethroids and their environmental degradation products in fresh fruits and vegetables using a modification of the quick easy cheap effective rugged safe (QuEChERS) method

EPA Science Inventory

Pyrethroid insecticides are used extensively in agriculture, and they, as well as their environmental degradates, may remain as residues on foods such as fruits and vegetables. Since pyrethroid degradates can be identical to the urinary markers used in human biomonitoring, it is ...

Tebuconazole and Azoxystrobin Residue Behaviors and Distribution in Field and Cooked Peanut.

PubMed

Hou, Fan; Teng, Peipei; Liu, Fengmao; Wang, Wenzhuo

2017-06-07

Residue behaviors of tebuconazole and azoxystrobin in field condition and the variation of their residue levels during the boiling process were evaluated. The terminal residues of peanut kernels were determined by using a modified QuEChERS method (quick, easy, cheap, effective, rugged, and safe) by means of the optimization of the novel purification procedure with multiwalled carbon nanotubes (MWCNTs) and Fe 3 O 4 -magnetic nanoparticle (Fe 3 O 4 -MNP) in the presence of an external magnetic field, and the terminal residues were all at trace level at harvest time. The residues in shells were detected as well to investigate the distribution in peanuts. Tebuconazole and azoxystrobin residue levels varied before/after boiling in kernels and shells to different degrees due to various factors, such as the modes of action and physicochemical properties of pesticides. The residues have been transferred from peanut into the infusion during boiling with the higher percentage of azoxystrobin as its lower logK ow . The processing factors (PFs) for tebuconazole and azoxystrobin after processing were <1, indicating that home cooking in this study could reduce the residue levels in peanut. Risk assessment showed there was no health risk for consumers.

Dissipation kinetics of emamectin benzoate and lufenuron residues in cabbage grown under field conditions.

PubMed

Dong, Bizhang; Zhao, Qing; Hu, Jiye

2015-12-01

Residue analysis of emamectin benzoate and lufenuron in cabbage matrices and soil was developed using a quick, easy, cheap, effective, rugged, and safe (QuEChERS) method and ultra high-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS). The samples were extracted with 1% acetic acid in acetonitrile (v/v) or 1% acetic acid in acetonitrile/water (5:1, v/v) and cleaned up by dispersive solid-phase extraction. Mean recoveries and relative standard deviations (RSDs) in all samples ranged 87.8-100.0 % and 3.6-12.6% for emamectin benzoate and 87.8-104.8 % and 6.2-11.5% for lufenuron, respectively. The validated method was used to evaluate the dissipation rate of emamectin benzoate and lufenuron in cabbage and soil as well as the residual levels in harvested cabbage and soil at different preharvest intervals (PHI). The half-lives of emamectin benzoate and lufenuron were 1.08-2.70 and 1.74-5.04 days in cabbage, and 1.42-4.01 and 0.94-6.18 days in soil, respectively. The terminal residues were below the China maximum residue limits (MRLs) at 3 days for emamectin benzoate (0.1 mg kg(-1)) and European Union MRLs at 5 days for lufenuron (0.5 mg kg(-1)), which suggested that 5 days could be recommended as the PHI for the commercial formulation of emamectin benzoate and lufenuron application in the Chinese cabbage field.

Application of ultra-high pressure liquid chromatography linear ion-trap orbitrap to qualitative and quantitative assessment of pesticide residues.

PubMed

Farré, M; Picó, Y; Barceló, D

2014-02-07

The analysis of pesticides residues using a last generation high resolution and high mass accuracy hybrid linear ion trap-Orbitrap mass spectrometer (LTQ-Orbitrap-MS) was explored. Pesticides were extracted from fruits, fish, bees and sediments by QuEChERS and from water by solid-phase with Oasis HLB cartridges. Ultra-high pressure liquid chromatography (UHPLC)-LTQ-Orbitrap mass spectrometer acquired full scan MS data for quantification, and data dependent (dd) MS(2) and MS(3) product ion spectra for identification and/or confirmation. The regression coefficients (r(2)) for the calibration curves (two order of magnitude up to the lowest calibration level) in the study were ≥0.99. The LODs for 54 validated compounds were ≤2ngmL(-1) (analytical standards). The relative standard deviation (RSD), which was used to estimate precision, was always lower than 22%. The recovery of extraction and matrix effects ranged from 58 to 120% and from -92 to 52%, respectively. Mass accuracy was always ≤4ppm, corresponding to a maximum mass error of 1.6millimass units (mmu). This procedure was then successfully applied to pesticide residues in a set of the above-mentioned food and environmental samples. In addition to target analytes, this method enables the simultaneous detection/identification of non-target pesticides, pharmaceuticals, drugs of abuse, mycotoxins, and their metabolites. Copyright © 2013 Elsevier B.V. All rights reserved.

The challenges of developing a generic extraction procedure to analyze multi-class veterinary drug residues in milk and honey using ultra-high pressure liquid chromatography quadrupole time-of-flight mass spectrometry.

PubMed

Wang, Jian; Leung, Daniel

2012-08-01

This paper discusses the analytical challenges to develop a generic extraction procedure to analyze or screen multi-class veterinary drugs in milk and honey using ultra-high pressure liquid chromatography quadrupole time-of-flight mass spectrometry (UHPLC QqTOF MS). The veterinary drugs in this study included aminoglycosides, endectocides, fluoroquinolones, ionophores, β-lactams or penicillins, macrolides, NSAIDs, phenicols, sulfonamides and tetracyclines. Veterinary drugs were extracted using a QuEChERS (quick, easy, cheap, effective, rugged, and safe) method, which entailed the use of acetonitrile containing 1% acetic acid, sodium acetate, ethylenediaminetetra acetic acid disodium (EDTA) and magnesium sulfate, and no clean-up was performed. Chromatographic separation was achieved on a reversed-phase Acquity UPLC BEH C(18) , 100 × 2.1 mm, 1.7 µm column with 0.1% formic acid and 10 mM ammonium formate in water, and acetonitrile as mobile phases. Due to poor chromatographic retention, aminoglycosides were first dropped from the list, and because of poor extractability, β-lactams and tetracyclines were also excluded from the method. The method was able to quantify 31 or screen up to 54 drugs (unbound) in honey, and to quantify 34 or screen up to 59 drugs in milk. UHPLC QqTOF data were acquired in TOF MS full-scan mode that allowed both quantification and confirmation of veterinary drugs and identification of their degradation products in samples. The method could achieve detection limits as low as 1 µg/kg with analytical range from 1 to 100 µg/kg. The developed method was intended to be used for screening of as many analytes as possible in one single analysis, or unequivocal confirmation of positive findings and degradation product identification based on accurate mass measurement and isotopic patterns. © Her Majesty the Queen in Right of Canada 2012. Reproduced with the permission of the Minister of Agriculture.

Application of zirconium dioxide nanoparticle sorbent for the clean-up step in post-harvest pesticide residue analysis.

PubMed

Uclés, Ana; Herrera López, Sonia; Dolores Hernando, Maria; Rosal, Roberto; Ferrer, Carmen; Fernández-Alba, Amadeo R

2015-11-01

The use of yttria-stabilized zirconium dioxide nanoparticles as d-SPE clean-up sorbent for a rapid and sensitive liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) method for the determination of post-harvest fungicides (carbaryl, carbendazim, chlorpropham, diphenylamine, ethoxyquin, flutriafol, imazalil, iprodione, methomyl, myclobutanil, pirimiphos-methyl, prochloraz, pyrimethanil, thiabendazole, thiophanate-methyl and tolclofos-methyl) in orange and pear samples has been evaluated and validated. The sample preparation was a modification of the QuEChERS extraction method using yttria-stabilized zirconium dioxide and multi-walled carbon nanotubes (MWCNTs) nanoparticles as the solid phase extraction (d-SPE) clean-up sorbents prior to injecting the ten-fold diluted extracts into the LC system. By using the yttria-stabilized zirconium dioxide extraction method, more recoveries in the 70-120% range were obtained - thus this method was used for the validation. Quantification was carried out using a matrix-matched calibration curve which was linear in the 1-500 µg kg(-1) range for almost all the pesticides studied. The validated limit of quantification was 10 µg kg(-1) for most of the studied compounds, except chlorpropham, ethoxyquin and thiophanate-methyl. Pesticide recoveries at the 10 and 100 µg kg(-1) concentration levels were satisfactory, with values between 77% and 120% and relative standard deviations (RSD) lower than 10% (n=5). The developed method was applied for the determination of selected fungicides in 20 real orange and pear samples. Four different pesticide residues were detected in 10 of these commodities; 20% of the samples contained pesticide residues at a quantifiable level (equal to or above the LOQs) for at least one pesticide residue. The most frequently-detected pesticide residues were: carbendazim, thiabendazole and imazalil-all were below the MRL. The highest concentration found was imazalil at 1175 µg kg(-1) in a pear sample. Copyright © 2015 Elsevier B.V. All rights reserved.

Determination and Safety Assessment of Residual Spirotetramat and Its Metabolites in Amaranth (Amaranthus tricolor) and Soil by Liquid Chromatography Triple-Quadrupole Tandem Mass Spectrometry.

PubMed

Chen, Xiao-Jun; Meng, Zhi-Yuan; Ren, Li; Song, Yue-Yi; Ren, Ya-Jun; Chen, Jian-Shu; Guan, Ling-Jun

2018-05-01

With the purpose of guaranteeing the safe use of spirotetramat and preventing its potential health threats to consumers, a QuEChERS extraction method coupled with LC triple-quadrupole tandem MS was applied in this study to determine residual spirotetramat metabolites in different tissues of amaranth (Amaranthus tricolor) and in soil. The results indicate that the spirotetramat degraded into different types of metabolites that were located in different tissues of amaranth and in soil. B-keto, B-glu, and B-enol were the three most representative degradation products in the leaf of amaranth, and B-glu and B-enol were the two major degradation products found in the stem of amaranth; however, only B-enol was detected in the root of amaranth. B-keto and B-mono were the two products detected in the soil in which the amaranth grew. The cytotoxicity results demonstrate that spirotetramat and its metabolite B-enol inhibited cellular growth, and the toxicity of spirotetramat and its metabolite B-enol exceeded than that of the metabolites B-keto, B-mono, and B-glu. This investigation is of great significance to the safe use of spirotetramat in agriculture.

Synthetic musk in seafood products from south Europe using a quick, easy, cheap, effective, rugged and safe extraction method.

PubMed

Saraiva, M; Cavalheiro, J; Lanceleur, L; Monperrus, M

2016-06-01

This study aims at developing a method for the determination of 9 synthetic musk compounds in seafood products by combining the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method and determination by gas chromatography mass spectrometry (GC-EI-MS). Method detection limits (MDL) ranging between 0.001 and 1.94 ng g(-1) were obtained. The linearity is higher than 0.9899 in the range MDL - 100 ng g(-1) with precision below 18% and recoveries between 46% and 120% were obtained. The method was applied to quantify musk compounds in seafood products from the European southwest coast (oysters, mussels, salmon organs, glass eels). Galaxolide and Tonalide exhibited the highest concentration levels ranging between MDL - 96.4 ng g(-1) and MDL - 6.85 ng g(-1), respectively. Contamination levels observed for the two nitro musks (musk xylene and musk ketone) are significantly lower ranging between MDL - 0.6 ng g(-1) and MDL - 0.09 ng g(-1), respectively. Analysis of different organs of salmons showed higher concentrations in liver and gonad than in muscle tissues. Copyright © 2016 Elsevier Ltd. All rights reserved.

Pyraclostrobin wash-off from sugarcane leaves and aerobic dissipation in agricultural soil.

PubMed

Fulcher, James M; Wayment, Darcey G; White, Paul M; Webber, Charles L

2014-03-12

To mitigate damage from the fungal sugarcane pathogen brown rust (Puccinia melanocephala), a Section 18 Emergency Use Label was put in place by the United States Environmental Protection Agency (U.S. EPA) for the application of pyraclostrobin (trade name Headline SC, produced by BASF, Research Triangle Park, NC) on sugarcane in 2008. To assess the dynamics of this fungicide in Louisiana soil, samples (n = 24) from a non-treated field were spiked with pyraclostrobin (3.1 μg g(-1)) and analyzed in laboratory conditions over the course of 63 days using quick, easy, cheap, effective, rugged, and safe (QuEChERS) dispersive solid-phase extraction/high-performance liquid chromatography with ultraviolet-visible detection (dSPE/HPLC-UV). Modeling was performed using Microsoft Excel to predict DTx values. Pyraclostrobin was found to follow biphasic kinetics with DT50 and DT90 values of 60 and 282 days, suggesting that it is moderately persistent to persistent in soils. Wash-off studies on sugarcane indicate that very little fungicide is in the wash-off after 48 h. If applied to sugarcane according to label recommendations, the fungicide should have minimal dissipation from rainfall events.

Fast determination of alkylphenol ethoxylates in leafy vegetables using a modified quick, easy, cheap, effective, rugged, and safe method and ultra-high performance supercritical fluid chromatography-tandem mass spectrometry.

PubMed

Jiang, Ze-Jun; Cao, Xiao-Lin; Li, Hui; Zhang, Chan; Abd El-Aty, A M; Jin, Fen; Shao, Hua; Jin, Mao-Jun; Wang, Shan-Shan; She, Yong-Xin; Wang, Jing

2017-11-24

In the present study, a quick and sensitive method was developed for simultaneous determination of nonylphenol ethoxylates (NPxEOs) and octylphenol ethoxylates (OPxEOs) (x=2-20) in three leafy vegetables, including cabbage, lettuce, and spinach using a modified "QuEChERS" method and ultra-high performance supercritical fluid chromatography-tandem mass spectrometry (UHPSFC-MS/MS) with scheduled multiple reaction monitoring (MRM). Under optimized conditions, the 38 target analytes were analyzed within a short period of time (5 min). The linearities of the matrix-matched standard calibrations were satisfactory with coefficients of determination (R 2 )>0.99 and the limits of detection (LOD) and quantification (LOQ) were in between 0.02-0.27 and 0.18-1.75μgkg -1 , respectively. The recovery of all target analytes spiked at three (low, medium, and high) fortification levels in various leafy vegetables were ranged from 72.8-122.6% with relative standard deviation (RSD) ≤18.3%. The method was successfully applied to market samples and the target analytes were found in all monitored samples, with total concentrations of 0-8.67μgkg -1 and 15.75-95.75μgkg -1 for OPxEOs and NPxEOs (x=2-20), respectively. In conclusion, the newly developed UHPSFC-ESI-MS/MS method is rapid and versatile and could be extrapolated for qualitative and quantitative analysis of APxEOs in other leafy vegetables. Copyright © 2017 Elsevier B.V. All rights reserved.

Improvement on the Repair Effect of Electrochemical Chloride Extraction Using a Modified Electrode Configuration

PubMed Central

Feng, Wei; Xu, Jinxia; Jiang, Linhua; Song, Yingbin; Cao, Yalong; Tan, Qiping

2018-01-01

To improve the repair effect of electrochemical chloride extraction, a modified electrode configuration is applied in this investigation. In this configuration, two auxiliary electrodes placed in the anodic and cathodic electrolytes were used as the anode and cathode, respectively. Besides this, the steel in the mortar was grounded to protect it from corrosion. By a comparative experiment, the potential evolution, various ions concentrations (Cl−, OH−, Na+, and K+) in different mortar depths, the corrosion potential, and the current density of the steel were measured. The results indicate that compared to electrochemical chloride extraction with the traditional electrode configuration, this electrochemical chloride extraction method with a modified electrode configuration has a similar chloride removal ratio. Besides this, potential of steel is just about 800 mV for a saturated calomel electrode (SCE) during the treatment, which did not reach the hydrogen evolution potential. The phenomenon of the accumulation of OH−, Na+, and K+ did not occur when the modified electrode configuration is applied. Additionally, higher corrosion potentials and lower corrosion current rates were measured after performing electrochemical chloride extraction with the modified electrode configuration. Additionally, it is a short period of time for the steel to go from activation to passivation. On this basis, the modified electrode configuration may overcome the drawbacks of electrochemical chloride extraction. PMID:29389855

Comparative impact of genetically modified and non modified maize (Zea mays L.) on succeeding crop and associated weed.

PubMed

Ibrahim, Muhammad; Ahmed, Naseer; Ullah, Faizan; Shinwari, Zabta Khan; Bano, Asghari

2016-04-01

This research work documents the comparative impact of genetically modified (GM) (insect resistance) and non modified maize (Zea mays L.) on growth and germination of succeeding crop wheat (Triticum aestivum L.) and associated weed (Avena fatua L.). The aqueous extracts of both the GM and non-GM maize exhibited higher phenolic content than that of methanolic extracts. Germination percentage and germination index of wheat was significantly decreased by GM methanolic extract (10%) as well as that of non-GM maize at 3% aqueous extract. Similarly germination percentage of weed (Avena fatua L.) was significantly reduced by application of 3% and 5% methanolic GM extracts. All extracts of GM maize showed non-significant effect on the number of roots, root length and shoot length per plant but 5% and 10% methanolic extracts of non-GM maize significantly increased the number of roots per plant of wheat seedling. Similarly, 10% methanolic extract of GM maize significantly increased the number of roots per plant of weed seedling. Methanolic extracts of GM and non-GM maize (3% and 5%) significantly decreased the protease activity in wheat as compared to untreated control. © The Author(s) 2013.

Effects of processing parameters on the caffeine extraction yield during decaffeination of black tea using pilot-scale supercritical carbon dioxide extraction technique.

PubMed

Ilgaz, Saziye; Sat, Ihsan Gungor; Polat, Atilla

2018-04-01

In this pilot-scale study supercritical carbon dioxide (SCCO 2 ) extraction technique was used for decaffeination of black tea. Pressure (250, 375, 500 bar), extraction time (60, 180, 300 min), temperature (55, 62.5, 70 °C), CO 2 flow rate (1, 2, 3 L/min) and modifier quantity (0, 2.5, 5 mol%) were selected as extraction parameters. Three-level and five-factor response surface methodology experimental design with a Box-Behnken type was employed to generate 46 different processing conditions. 100% of caffeine from black tea was removed under two different extraction conditions; one of which was consist of 375 bar pressure, 62.5 °C temperature, 300 min extraction time, 2 L/min CO 2 flow rate and 5 mol% modifier concentration and the other was composed of same temperature, pressure and extraction time conditions with 3 L/min CO 2 flow rate and 2.5 mol% modifier concentration. Results showed that extraction time, pressure, CO 2 flow rate and modifier quantity had great impact on decaffeination yield.

Multi-contaminant analysis of organophosphate and halogenated flame retardants in food matrices using ultrasonication and vacuum assisted extraction, multi-stage cleanup and gas chromatography-mass spectrometry.

PubMed

Xu, Fuchao; García-Bermejo, Ángel; Malarvannan, Govindan; Gómara, Belén; Neels, Hugo; Covaci, Adrian

2015-07-03

A multi-residue analytical method was developed for the determination of a range of flame retardants (FRs), including polybrominated diphenyl ethers (PBDEs), emerging halogenated FRs (EFRs) and organophosphate FRs (PFRs), in food matrices. An ultrasonication and vacuum assisted extraction (UVAE), followed by a multi-stage clean-up procedure, enabled the removal of up to 1g of lipid from 2.5 g of freeze-dried food samples and significantly reduce matrix effects. UVAE achieves a waste factor (WF) of about 10%, while the WFs of classical QuEChERS methods range usually between 50 and 90%. The low WF of UVAE leads to a dramatic improvement in the sensitivity along with saving up to 90% of spiking (internal) standards. Moreover, a two-stage clean-up on Florisil and aminopropyl silica was introduced after UVAE, for an efficient removal of pigments and residual lipids, which led to cleaner extracts than normally achieved by dispersive solid phase extraction (d-SPE). In this way, the extracts could be concentrated to low volumes, e.g. <100 μL and the equivalent matrix concentrations were up to 100g ww/mL. The final analysis of PFRs was performed on GC-EI-MS, while PBDEs and EFRs were measured by GC-ECNI-MS. Validation tests were performed with three food matrices (lean beef, whole chicken egg and salmon filet), obtaining acceptable recoveries (66-135%) with good repeatability (RSD 1-24%, mean 7%). Method LOQs ranged between 0.008 and 0.04 ng/g dw for PBDEs, between 0.08 and 0.20 ng/g dw for EFRs, and between 1.4 and 3.6 ng/g dw for PFRs. The method was further applied to eight types of food samples (including meat, eggs, fish, and seafood) with lipid contents ranging from 0.1 to 22%. Various FRs were detected above MLOQ levels, demonstrating the wide-range applicability of our method. To the best of our knowledge, this is the first method reported for simultaneous analysis of brominated and organophosphate FRs in food matrices. Copyright © 2015 Elsevier B.V. All rights reserved.

Matrix interference evaluation employing GC and LC coupled to triple quadrupole tandem mass spectrometry.

PubMed

Uclés, S; Lozano, A; Sosa, A; Parrilla Vázquez, P; Valverde, A; Fernández-Alba, A R

2017-11-01

Gas and liquid chromatography coupled to triple quadrupole tandem mass spectrometry are currently the most powerful tools employed for the routine analysis of pesticide residues in food control laboratories. However, whatever the multiresidue extraction method, there will be a residual matrix effect making it difficult to identify/quantify some specific compounds in certain cases. Two main effects stand out: (i) co-elution with isobaric matrix interferents, which can be a major drawback for unequivocal identification, and therefore false negative detections, and (ii) signal suppression/enhancement, commonly called the "matrix effect", which may cause serious problems including inaccurate quantitation, low analyte detectability and increased method uncertainty. The aim of this analytical study is to provide a framework for evaluating the maximum expected errors associated with the matrix effects. The worst-case study contrived to give an estimation of the extreme errors caused by matrix effects when extraction/determination protocols are applied in routine multiresidue analysis. Twenty-five different blank matrices extracted with the four most common extraction methods used in routine analysis (citrate QuEChERS with/without PSA clean-up, ethyl acetate and the Dutch mini-Luke "NL" methods) were evaluated by both GC-QqQ-MS/MS and LC-QqQ-MS/MS. The results showed that the presence of matrix compounds with isobaric transitions to target pesticides was higher in GC than under LC in the experimental conditions tested. In a second study, the number of "potential" false negatives was evaluated. For that, ten matrices with higher percentages of natural interfering components were checked. Additionally, the results showed that for more than 90% of the cases, pesticide quantification was not affected by matrix-matched standard calibration when an interferent was kept constant along the calibration curve. The error in quantification depended on the concentration level. In a third study, the "matrix effect" was evaluated for each commodity/extraction method. Results showed 44% of cases with suppression/enhancement for LC and 93% of cases with enhancement for GC. Copyright © 2017 Elsevier B.V. All rights reserved.

98 Specific IGE and IGG Binding to Allergoids of Phleum pratense

PubMed Central

Cases, Barbara; Fernandez-Caldas, Enrique; Tudela, Jose Ignacio; Fernandez, Eva Abel; Sanchez-Garcia, Silvia; Ibañez, M. Dolores; Escudero, Carmelo; Casanovas, Miguel

2012-01-01

Background Allergoids were first used in the decades of the 60s and 70s of the last century as an effective treatment of allergic respiratory diseases. Allergoids can be modified with formaldehyde or glutaraldehyde. Modified allergens, or allergoids, decrease the risk of adverse reactions while administering higher allergen doses. The objective of this study was to analyse specific IgE and IgG binding to glutaraldehyde modified and non-modified allergen extracts of Phleum pratense. Methods The sera of 69 patients sensitized to P. pratense were tested. All these patients had signs and symptoms of rhinoconjunctivitis with, or without, asthma in May and June of 2011. All these patients had positive skin prick tests to a standardized extract of P. pratense, and other grass species. Most patients were also sensitized to olive pollen. Specific IgE and IgG binding were analysed by direct ELISA against P. pratense native (non-modified) and allergoid extracts. Relative potencies were evaluated through ELISA inhibition assays, and the protein composition of non-modified and allergoid samples was determined by Mass Spectrometry (MS/MS). Results Mean Specific IgE levels against the native extract was 16.68 ± 11.65 Units (U) and against the allergoid: 7.26 ± 8.24 U (P < 0.0001; Mann-Whitney). On the other hand, mean specific IgG binding against the non-modified extract was 90.34 ± 75.57 U versus 76.19 ± 70.31 U against the allergoid (P = 0.16; Mann-Whitney). Linear regression coefficients obtained between immunoglobulin reactivity against both extracts were: r2 = 0.51 for specific IgE and r2 = 0.83 for specific IgG. An important decrease in the allergenic activity, measured by inhibition ELISA, was clearly observed. The MS/MS assay revealed the presence of the mayor allergen, and some isoforms, in non-modified and allergoid extracts. Conclusions Results obtained demonstrate that the glutaraldehyde polymerization process induces an important decrease in specific IgE binding to allergoids of P. pratense while there are no significant differences in specific IgG binding. The allergenic composition of the P. pratense allergoid was equivalent to the non-modified pollen extract.

Determination of quaternary ammonium compounds in oranges and cucumbers using QuEChERS extraction and ultra-performance liquid chromatography/tandem mass spectrometry.

PubMed

Arrebola-Liébanas, Francisco Javier; Abdo, María Angeles Herrera; Moreno, José Luis Fernandez; Martínez-Vidal, José L; Frenich, Antonia Garrido

2014-01-01

A simple and fast method has been developed for determining relevant quaternary ammonium compounds in cucumber and orange samples. The target compounds were benzoalkonium chloride (BAC-10, BAC-12, BAC-14, and BAC-16), didecyldimethylammonium chloride, and benzethonium chloride, all frequently used biocides in the agrifood industry. An extraction based on the buffered Quick, Easy, Cheap, Effective, Rugged, and Safe method and determination by ultra-performance LC/MS/MS that eluted the biocides in less than 5 min were used. The method was fully validated and implemented in a UNE-EN-ISO/IEC 17025 accredited laboratory for its application to the analysis of real samples. Performance characteristics of the method are reported, including an estimation of measurement uncertainty. Calibration curves were set between 0.01 and 0.150 mg/kg, LOD values were always between 0.4 and 1.0 microg/kg, LOQ values were in the range 1-4 microg/kg, recovery was between 81 and 115%, intraday and interday precision were always lower than 17% (expressed as RSD), and expanded uncertainty was always lower than 40%. The validation was accomplished for the two studied matrixes at spiking concentrations of 0.011 and 0.050 mg/kg. The method has been applied to the analysis of 30 cucumber and orange samples that were found to contain concentrations of BAC-12 that ranged between 0.015 and 0.210 mg/kg and of BAC-14 between 0.018 and 0.081 mg/kg.

UV-filters and musk fragrances in seafood commercialized in Europe Union: Occurrence, risk and exposure assessment.

PubMed

Cunha, S C; Trabalón, L; Jacobs, S; Castro, M; Fernandez-Tejedor, M; Granby, K; Verbeke, W; Kwadijk, C; Ferrari, F; Robbens, J; Sioen, I; Pocurull, E; Marques, A; Fernandes, J O; Domingo, J L

2018-02-01

In the framework of the FP7 ECsafeSeafood project, 62 seafood samples commercialized in Europe Union from several representative species - mackerel, tuna, salmon, seabream, cod, monkfish, crab, shrimp, octopus, perch and plaice - were analysed for residues of 21 personal care products (PCPs), including 11 UV-filters (UV-Fs) and 10 musk fragrances (musks). PCPs analysis were performed by Quick, Easy, Cheap, Effective Rugged, Safe (QuEChERS), combined with liquid-liquid extraction (LLE) or dispersive solid-phase extraction (dSPE), followed by gas chromatography-tandem mass spectrometry (GC-MS/MS). The results showed the presence in a wide range of samples of nine out of eleven UV-Fs compounds analysed, namely 2-ethylhexyl salicylate (EHS), 2-ethylhexyl,4-methoxycinnamate (EHMC), 4-methylbenzylidenecamphor (4-MBC), benzophenone-1 (BP1), benzophenone-3 (BP3), isoamyl-4-methoxycinnamate (IMC), 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (DHMB), homosalate (HS), and octocrylene (OC), whereas galaxolide (HHCB), galaxolide lactone (HHCB-lactone), and tonalide (AHTN) were the most found musks. The potential risks to human health associated with the exposure to eight of the more prevalent PCPs - EHS, EHMC, 4-MBC, BP1, BP3, IMC, HHCB, and AHTN - through seafood consumption were assessed for consumers from five European countries (Belgium, Ireland, Italy, Portugal and Spain). Results showed that the human exposure to UV-Fs and musks estimated from the concentration values found in seafood and the daily consumption of concerned seafood species, were far below toxicological reference values. Copyright © 2017 Elsevier Inc. All rights reserved.

Automated DNA extraction from genetically modified maize using aminosilane-modified bacterial magnetic particles.

PubMed

Ota, Hiroyuki; Lim, Tae-Kyu; Tanaka, Tsuyoshi; Yoshino, Tomoko; Harada, Manabu; Matsunaga, Tadashi

2006-09-18

A novel, automated system, PNE-1080, equipped with eight automated pestle units and a spectrophotometer was developed for genomic DNA extraction from maize using aminosilane-modified bacterial magnetic particles (BMPs). The use of aminosilane-modified BMPs allowed highly accurate DNA recovery. The (A(260)-A(320)):(A(280)-A(320)) ratio of the extracted DNA was 1.9+/-0.1. The DNA quality was sufficiently pure for PCR analysis. The PNE-1080 offered rapid assay completion (30 min) with high accuracy. Furthermore, the results of real-time PCR confirmed that our proposed method permitted the accurate determination of genetically modified DNA composition and correlated well with results obtained by conventional cetyltrimethylammonium bromide (CTAB)-based methods.

Petroselinum crispum extract attenuates hepatic steatosis in rats fed with fructose enriched diet.

PubMed

Nair, V Yuneesha; Balakrishanan, N; Antony Santiago, J Victor

2015-01-01

Non alcoholic fatty liver disease (NAFLD) is the most common chronic liver disease and ongoing research efforts are focused on understanding the underlying pathophysiology of hepatic steatosis with the anticipation that these efforts will identify novel therapeutic targets. This study investigated the Petroselinum crispum extract in hepatic steatosis in rats fed with fructose enriched diet. Rats were divided into the 4 groups: Group 1 rats received standard pellet diet with corn starch for the entire experimental period of 8 weeks. Group 2 rats received standard pellet diet and 2 gm/kg body weight crude Parsley leaf ethanol extract for the entire experimental period of 8 weeks. Group 3 rats received modified fructose diet. Group 4 rats received modified fructose diet and 2gm/kg crude Parsley leaf ethanol extract. Hepatic function and structure was evaluated in these rats. Modified fructose diet produced dyslipidemia, hepatic steatosis and infiltration of inflammatory cells in the liver and higher plasma hepatic markers. Petroselinum crispum extract reversed metabolic changes such as abnormal crispum extract attenuated chronic changes in modified fructose diet induced NAFLD (Tab. 2, Fig. 3, Ref. 43).

Modified sugar beet pectin induces apoptosis of colon cancer cells via interaction with the neutral sugar side-chains

USDA-ARS?s Scientific Manuscript database

Pectins extracted from a variety of sources and modified with heat and/or pH have previously been shown to exhibit activity towards several cancer cell lines. However, the structural basis for the anti-cancer activity of modified pectin requires clarification. Sugar beet and citrus pectin extracts h...

Characterization of modified allergen extracts by in vitro beta-hexosaminidase release from rat basophils.

PubMed

Gehlhar, Kirsten; Peters, Marcus; Brockmann, Kirsten; van Schijndel, Hans; Bufe, Albrecht

2005-04-01

To date, there is no well-established test available that can be used to measure functional properties of modified allergens (allergoids). Due to the cross-linking process, the IgE-binding capacity of the allergens, normally necessary for their characterization, is lost. The aim of this study was to test whether the rat basophilic leukaemia (RBL) cell assay (beta-hexosaminidase release by rat basophils upon allergen stimulation) can be adopted to characterize allergoids and to evaluate the assay for testing allergoids and native allergens as well. Mice were immunized with native and modified Phleumpratense extracts in the presence of alum. Their sera were used to sensitize RBL-2H3 cells and measure basophil stimulation induced by different allergen extracts in the presence or absence of various additives. Sera containing specific IgE against both extract formulations were obtained. Native as well as modified extracts induced dose-dependent beta-hexosaminidase release from RBL cells. Both extracts were used to evaluate the characteristics of the assay, which showed high precision. Storage conditions were chosen to enhance extract degradation, which could be read directly from the altered stimulatory capacity of the extracts. Additives turned out to have diverse effects on the assay, whereas phenol had no measurable effect, alum had an inhibitory effect and glycerol elevated basophil activation. For the first time, a reliable, precise in vitro assay is available that is able to directly measure the properties of modified allergen extracts after their production process. The test is well evaluated and its advantages and limitations are discussed in this report. Copyright (c) 2005 S. Karger AG, Basel

[Study on process and principle of lactose grinding modification to decrease hygroscopic of Rhodiolae Crenulatae Radix et Rhizoma extract].

PubMed

Zhang, Ding-Kun; Zhang, Fang; Lin, Jun-Zhi; Han, Li; Wu, Zhen-Feng; Yang, Ying-Guang; Yang, Ming

2014-04-01

In this paper, Rhodiolae Crenulatae Radix et Rhizoma extract,with high hygroscopic,was selected as research model, while lactose was selected as modifiers to study the effect of the grinding modification method on the hygroscopic. Subsequently, particle size distribution, scannin electron microscopy, infrared spectroscopy and surface properties were adopted for a phase analysis. The results showed that the modified extract, prepared by Rhodiolae Crenulatae Radix et Rhizoma extract grinding 5 min with the same amount of lactose UP2, which hygroscopic initial velocity, acceleration, and critical relative humidity moisture were less than that of Rhodiolae Crenulatae Radix et Rhizoma extract and the mixture dramatically. In addition, compared with the mixture, the size distribution of modified extract was much less, the microstructure was also difference, while the infrared spectroscopy and surface properties were similar with that of lactose. It is the main principle that lactose particle adhered to the surface of Rhodiolae Crenulatae Radix et Rhizoma extract after grinding mofication to decress the moisture obviously.

Extractant composition including crown ether and calixarene extractants

DOEpatents

Meikrantz, David H.; Todd, Terry A.; Riddle, Catherine L.; Law, Jack D.; Peterman, Dean R.; Mincher, Bruce J.; McGrath, Christopher A.; Baker, John D.

2009-04-28

An extractant composition comprising a mixed extractant solvent consisting of calix[4] arene-bis-(tert-octylbenzo)-crown-6 ("BOBCalixC6"), 4',4',(5')-di-(t-butyldicyclo-hexano)-18-crown-6 ("DtBu18C6"), and at least one modifier dissolved in a diluent. The DtBu18C6 may be present at from approximately 0.01M to approximately 0.4M, such as at from approximately 0.086 M to approximately 0.108 M. The modifier may be 1-(2,2,3,3-tetrafluoropropoxy)-3-(4-sec-butylphenoxy)-2-propanol ("Cs-7SB") and may be present at from approximately 0.01M to approximately 0.8M. In one embodiment, the mixed extractant solvent includes approximately 0.15M DtBu18C6, approximately 0.007M BOBCalixC6, and approximately 0.75M Cs-7SB modifier dissolved in an isoparaffinic hydrocarbon diluent. The extractant composition further comprises an aqueous phase. The mixed extractant solvent may be used to remove cesium and strontium from the aqueous phase.

Degradation studies of quizalofop-p and related compounds in soils using liquid chromatography coupled to low and high resolution mass analyzers.

PubMed

López-Ruiz, Rosalía; Romero-González, Roberto; Martínez Vidal, José Luis; Fernández-Pérez, Manuel; Garrido Frenich, Antonia

2017-12-31

A comprehensive degradation study of quizalofop-p, quizalofop-p-ethyl, quizalofop-p-tefuryl and propaquizafop in soil samples have been firstly performed using ultra high performance liquid chromatography coupled to Orbitrap mass spectrometry (UHPLC-Orbitrap-MS). Thus, metabolites or degradation products, such as CHHQ (dihydroxychloroquinoxalin), CHQ (6-chloroquinoxalin-2-ol), PPA ((R)-2-(4-hydroxyphenoxy)propionic acid) and 2,3-dihydroxyquinoxaline were also monitored. An extraction procedure based on QuEChERS procedure was used. Acidified water (0.1M hydrochloric acid) and acidified acetonitrile (1% acetic acid, (v/v)) were used as extraction solvents, and magnesium sulfate and sodium chloride were used as salts. Dispersive solid phase extraction with C 18 as sorbent, was needed as a clean-up step. Several commercial products (Panarex®, Master-D® and Dixon®) were used to evaluate the degradation of the target compounds into their metabolites. The concentration of the main active substances (quizalofop-p-tefuryl, quizalofop-p-ethyl and propaquizafop) decreased during the degradation studies, whereas the concentration of quizalofop-p increased. Dissipation rates of half-live of quizalofop-p were also evaluated, and it was observed that this compound is easily degraded, obtaining values lower than 1day. Taking into account that quizalofop-p is the R enantiomer of quizalofop, a chiral separation was performed by liquid chromatography coupled to tandem mass spectrometry, concluding that in samples containing quizalofop-p-tefuryl, there was a 15% contribution from the S enantiomer and a 85% contribution from the R enantiomer. Metabolites such as PPA, CHHQ and CHQ were detected in soil samples after 15days of application commercial product at concentrations between the limits of detection (LOD) and the limits of quantification (LOQ). CHQ and CHHQ were detected at concentrations higher than the LOQ in samples after 50 and 80days of application, with their concentration increasing during this time up to 500%. Copyright © 2017 Elsevier B.V. All rights reserved.

Cocoa extracts reduce oligomerization of amyloid-β: implications for cognitive improvement in Alzheimer's disease.

PubMed

Wang, Jun; Varghese, Merina; Ono, Kenjiro; Yamada, Masahito; Levine, Samara; Tzavaras, Nikos; Gong, Bing; Hurst, William J; Blitzer, Robert D; Pasinetti, Giulio Maria

2014-01-01

Alzheimer's disease (AD) is the most common age-related neurodegenerative disorder, characterized by pathological aggregates of amyloid peptide-β (Aβ) and tau protein. Currently available therapies mediate AD symptoms without modifying disease progression. Polyphenol-rich diets are reported to reduce the risk for AD. In the present study, we investigated the AD disease-modifying effects of cocoa, a rich source of flavanols, which are a class of polyphenols. We hypothesized that cocoa extracts interfere with amyloid-β oligomerization to prevent synaptic deficits. We tested the effects of three different cocoa extracts, viz. Natural, Dutched, and Lavado extracts, on Aβ42 and Aβ40 oligomerization, using photo-induced cross-linking of unmodified proteins technique. To assess the effects of cocoa extracts on synaptic function, we measured long term potentiation in mouse brain hippocampal slices exposed to oligomeric Aβ. Our results indicate that cocoa extracts are effective in preventing the oligomerization of Aβ, with Lavado extract being most effective. Lavado extract, but not Dutched extract, was effective in restoring the long term potentiation response reduced by oligomeric Aβ. Our findings indicate that cocoa extracts have multiple disease-modifying properties in AD and present a promising route of therapeutic and/or preventative initiatives.

The utilization of modified BCR three-step sequential extraction procedure for the fractionation of Cd, Cr, Cu, Ni, Pb and Zn in soil reference materials of different origins.

PubMed

Zemberyová, Mária; Barteková, Jana; Hagarová, Ingrid

2006-12-15

A modified three-step sequential extraction procedure for the fractionation of heavy metals, proposed by the Commission of the European Communities Bureau of Reference (BCR) has been applied to the Slovak reference materials of soils (soil orthic luvisols, soil rendzina and soil eutric cambisol), which represent pedologically different types of soils in Slovakia. Analyses were carried out by flame or electrothermal atomic absorption spectrometry (FAAS or ETAAS). The fractions extracted were: exchangeable (extraction step 1), reducible-iron/manganese oxides (extraction step 2), oxidizable-organic matter and sulfides (extraction step 3). The sum of the element contents in the three fractions plus aqua-regia extractable content of the residue was compared to the aqua-regia extractable content of the elements in the origin soils. The accuracy obtained by comparing the determined contents of the elements with certified values, using BCR CRM 701, certified for the extractable contents (mass fractions) of Cd, Cr, Cu, Ni, Pb and Zn in sediment following a modified BCR-three step sequential extraction procedure, was found to be satisfactory.

Development of a QuEChERS-Based Stable-Isotope Dilution LC-MS/MS Method To Quantitate Ferulic Acid and Its Main Microbial and Hepatic Metabolites in Milk.

PubMed

Waterstraat, Martin; Hildebrand, Andreas; Rosler, Margit; Bunzel, Mirko

2016-11-16

Forage plants of the Poaceae family are grown as pasturage or used for the production of hay, straw, corn stover, etc. Although ferulic acid contents of grasses are generally high, the amount of ingested ferulic acid differs depending on the type of forage, resulting in varying contents of ferulic acid and its microbial and hepatic metabolites in milk. Concentrations and patterns of these metabolites may be used as markers to track different forages in livestock feeding. Therefore, we developed a stable isotope dilution assay to quantitate ferulic acid, 12 ferulic acid-based metabolites, p-coumaric acid, and cinnamic acid in milk. Because most analytes were not commercially available as stable isotope labeled standard compounds, they were synthesized as 13 C- or deuterium-labeled standard compounds. A modification of the QuEChERS method, a Quick, Easy, Cheap, Effective, Rugged, and Safe approach usually applied to analyze pesticides in plant-based products, was used to extract the phenolic acids from milk. Determination was carried out by LC-ESI-MS/MS in scheduled multiple reaction monitoring modus. By using three different milk samples, the applicability of the validated approach was demonstrated.

Effect of processing on the disappearance of pesticide residues in fresh-cut lettuce: Bioavailability and dietary risk.

PubMed

Camara, Miguel A; Barba, Alberto; Cermeño, Sandra; Martinez, Gracia; Oliva, Jose

2017-12-02

The aim of this research is to establish the processing factors of six pesticides durong the preparation of fresh-cut lettuce and to assess the risk of ingestion of pesticide residues associated with the consumption of the same. A field study was carried out on the dissipation of three insecticides (imidacloprid, tebufenozide, cypermethrin) and three fungicides (metalaxyl, tebuconazole, azoxystrobin) during treatment conditions simulating those used for commercial fresh-cut lettuce. A simultaneous residue analysis method is validated using QuEChERS extraction with acetonitrile and CG-MS and LC-MS/MS analysis. The residues detected after field application never exceed the established Maximum Residue Limits. The processing factors were generally less than 1 (between 0.34 for tebufenozide and 0.53 for imidacloprid), indicating that the process, as a whole, considerably reduces residue levels in processed lettuce compared to fresh lettuce. It is confirmed that cutting, followed by washing and drying, considerably reduces the residues. A matrix effect in the dialyzation of the pesticides is observed and the in vitro study of bioavailability establishes a low percentage of stomach absorption capacity (<15%). The EDI/ADI ratios found in all cases were well below their ADI values, and the dietary exposure assessed (EDI) in fresh-cut lettuce showed no concerns for consumer health.

Evaluation of a Fast and Simple Sample Preparation Method for Polybrominated Diphenyl Ether (PBDE) Flame Retardants and Dichlorodiphenyltrichloroethane (DDT) Pesticides in Fish for Analysis by ELISA Compared with GC-MS/MS.

PubMed

Sapozhnikova, Yelena; Simons, Tawana; Lehotay, Steven J

2015-05-13

A simple, fast, and cost-effective sample preparation method, previously developed and validated for the analysis of organic contaminants in fish using low-pressure gas chromatography-tandem mass spectrometry (LPGC-MS/MS), was evaluated for the analysis of polybrominated diphenyl ethers (PBDEs) and dichlorodiphenyltrichloroethane (DDT) pesticides using enzyme-linked immunosorbent assay (ELISA). The sample preparation technique was based on the quick, easy, cheap, rugged, effective, and safe (QuEChERS) approach with filter-vial dispersive solid phase extraction (d-SPE). Incurred PBDEs and DDTs were analyzed in three types of fish with 3-10% lipid content: Pacific croaker, salmon, and National Institute of Standards and Technology (NIST) Standard Reference Material 1947 (Lake Michigan fish tissue). LPGC-MS/MS and ELISA results were in agreement: 108-111 and 65-82% accuracy ELISA versus LPGC-MS/MS results for PBDEs and DDTs, respectively. Similar detection limits were achieved for ELISA and LPGC-MS/MS. Matrix effects (MEs) were significant (e.g., -60%) for PBDE measurement in ELISA, but not a factor in the case of DDT pesticides. This study demonstrated that the sample preparation method can be adopted for semiquantitative screening analysis of fish samples by commercial kits for PBDEs and DDTs.

Supercritical Carbon Dioxide Extraction of Bioactive Compounds from Ampelopsis grossedentata Stems: Process Optimization and Antioxidant Activity

PubMed Central

Wang, Yuefei; Ying, Le; Sun, Da; Zhang, Shikang; Zhu, Yuejin; Xu, Ping

2011-01-01

Supercritical carbon dioxide (SC-CO2) extraction of bioactive compounds including flavonoids and phenolics from Ampelopsis grossedentata stems was carried out. Extraction parameters such as pressure, temperature, dynamic time and modifier, were optimized using an orthogonal array design of L9 (34), and antioxidant activities of the extracts were evaluated by 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical scavenging assay and ferrous ion chelating (FIC) assay. The best conditions obtained for SC-CO2 extraction of flavonoids was 250 bar, 40 °C, 50 min, and with a modifier of methanol/ethanol (1:3, v/v), and that for phenolics extraction was 250 bar, 40 °C, 50 min, and with a modifier of methanol/ethanol (1:1, v/v). Meantime, flavonoids and phenolics were found to be mainly responsible for the DPPH scavenging activity of the extracts, but not for the chelating activity on ferrous ion according to Pearson correlation analysis. Furthermore, several unreported flavonoids such as apigenin, vitexin, luteolin, etc., have been detected in the extracts from A. grossedentata stems. PMID:22072923

Ammonium chloride salting out extraction/cleanup for trace-level quantitative analysis in food and biological matrices by flow injection tandem mass spectrometry.

PubMed

Nanita, Sergio C; Padivitage, Nilusha L T

2013-03-20

A sample extraction and purification procedure that uses ammonium-salt-induced acetonitrile/water phase separation was developed and demonstrated to be compatible with the recently reported method for pesticide residue analysis based on fast extraction and dilution flow injection mass spectrometry (FED-FI-MS). The ammonium salts evaluated were chloride, acetate, formate, carbonate, and sulfate. A mixture of NaCl and MgSO4, salts used in the well-known QuEChERS method, was also tested for comparison. With thermal decomposition/evaporation temperature of <350°C, ammonium salts resulted in negligible ion source residual under typical electrospray conditions, leading to consistent method performance and less instrument cleaning. Although all ammonium salts tested induced acetonitrile/water phase separation, NH4Cl yielded the best performance, thus it was the preferred salting out agent. The NH4Cl salting out method was successfully coupled with FI/MS/MS and tested for fourteen pesticide active ingredients: chlorantraniliprole, cyantraniliprole, chlorimuron ethyl, oxamyl, methomyl, sulfometuron methyl, chlorsulfuron, triflusulfuron methyl, azimsulfuron, flupyrsulfuron methyl, aminocyclopyrachlor, aminocyclopyrachlor methyl, diuron and hexazinone. A validation study was conducted with nine complex matrices: sorghum, rice, grapefruit, canola, milk, eggs, beef, urine and blood plasma. The method is applicable to all analytes, except aminocyclopyrachlor. The method was deemed appropriate for quantitative analysis in 114 out of 126 analyte/matrix cases tested (applicability rate=0.90). The NH4Cl salting out extraction/cleanup allowed expansion of FI/MS/MS for analysis in food of plant and animal origin, and body fluids with increased ruggedness and sensitivity, while maintaining high-throughput (run time=30s/sample). Limits of quantitation (LOQs) of 0.01mgkg(-1) (ppm), the 'well-accepted standard' in pesticide residue analysis, were achieved in >80% of cases tested; while limits of detection (LODs) were typically in the range of 0.001-0.01mgkg(-1) (ppm). A comparison to a well-established HPLC/MS/MS method was also conducted, yielding comparable results, thus confirming the suitability of NH4Cl salting out FI/MS/MS for pesticide residue analysis. Copyright © 2013 Elsevier B.V. All rights reserved.

High-throughput method based on quick, easy, cheap, effective, rugged and safe followed by liquid chromatography-multi-wavelength detection for the quantification of multiclass polyphenols in wines.

PubMed

Fontana, Ariel R; Bottini, Rubén

2014-05-16

In this work, a reliable, simple, fast, inexpensive and robust sample preparation approach for the determination of multiclass polyphenols in wine samples is proposed. The polyphenols selected for this work were gallic acid, (+)-catechin, (-)-epicatechin, caffeic acid, syringic acid, coumaric acid, ferulic acid, trans-resveratrol, quercetin and cinnamic acid. The method is based on QuEChERS (quick, easy, cheap, effective, rugged and safe) extraction technique coupled with dispersive solid-phase extraction (d-SPE) clean-up. Under optimized conditions, the analytes were extracted from 5mL wine samples (previously acidified with 1% formic acid) using 2.5mL acetonitrile. For phase separation, 1.5g NaCl and 4g anhydrous MgSO4 were added. Then, a 1mL aliquot of the partitioned supernatant was cleaned-up using d-SPE with a combination of 150mg CaCl2, 50mg primary-secondary amine (PSA) and 50mgC18 as sorbents. A 250μL aliquot of the obtained cleaned extract was concentrated to dryness and taken up with the initial mobile phase previous to liquid chromatography-multi-wavelength detection (LC-MWD). The proposed method provided limits of detection (LODs) ranging from 0.004 to 0.079μgmL(-1) and an inter-day variability below 12% RSD for all analytes in red and white wine samples. Considering external calibration (red wines) and matrix-matched calibration (white wines) as quantification techniques, the overall recoveries (accuracy) of the method ranged between 75.0% and 119.6% for red and white wine samples, respectively. The developed method was applied for the determination of polyphenols in 10 wines produced in Argentina. Nine phenolic compounds were determined, at concentrations above detectable levels in the method. The maximum concentrations corresponded to (-)-epicatechin in white wines, while gallic acid and (+)-catechin were the most abundant in red wines. Copyright © 2014 Elsevier B.V. All rights reserved.

Method of modifying a volume mesh using sheet extraction

DOEpatents

Borden, Michael J [Albuquerque, NM; Shepherd, Jason F [Albuquerque, NM

2007-02-20

A method and machine-readable medium provide a technique to modify a hexahedral finite element volume mesh using dual generation and sheet extraction. After generating a dual of a volume stack (mesh), a predetermined algorithm may be followed to modify the volume mesh of hexahedral elements. The predetermined algorithm may include the steps of determining a sheet of hexahedral mesh elements, generating nodes for merging, and merging the nodes to delete the sheet of hexahedral mesh elements and modify the volume mesh.

Cesium and strontium extraction using a mixed extractant solvent including crown ether and calixarene extractants

DOEpatents

Meikrantz, David H.; Todd, Terry A.; Riddle, Catherine L.; Law, Jack D.; Peterman, Dean R.; Mincher, Bruce J.; McGrath, Christopher A.; Baker, John D.

2007-11-06

A mixed extractant solvent including calix[4]arene-bis-(tert-octylbenzo)-crown-6 ("BOBCalixC6"), 4',4',(5')-di-(t-butyldicyclo-hexano)-18-crown-6 ("DtBu18C6"), and at least one modifier dissolved in a diluent. The mixed extractant solvent may be used to remove cesium and strontium from an acidic solution. The DtBu18C6 may be present from approximately 0.01 M to approximately 0.4M, such as from approximately 0.086 M to approximately 0.108 M. The modifier may be 1-(2,2,3,3-tetrafluoropropoxy)-3-(4-sec-butylphenoxy)-2-propanol ("Cs-7SB") and may be present from approximately 0.01M to approximately 0.8M. In one embodiment, the mixed extractant solvent includes approximately 0.15M DtBu18C6, approximately 0.007M BOBCalixC6, and approximately 0.75M Cs-7SB modifier dissolved in an isoparaffinic hydrocarbon diluent. The mixed extractant solvent may form an organic phase in an extraction system that also includes an aqueous phase. Methods of extracting cesium and strontium as well as strontium alone are also disclosed.

Microbial process for the preparation of acetic acid, as well as solvent for its extraction from the fermentation broth

DOEpatents

Gaddy, James L.; Clausen, Edgar C.; Ko, Ching-Whan; Wade, Leslie E.; Wikstrom, Carl V.

2007-03-27

A modified water-immiscible solvent useful in the extraction of acetic acid from aqueous streams is a substantially pure mixture of isomers of highly branched di-alkyl amines. Solvent mixtures formed of such a modified solvent with a desired co-solvent, preferably a low boiling hydrocarbon, are useful in the extraction of acetic acid from aqueous gaseous streams. An anaerobic microbial fermentation process for the production of acetic acid employs such solvents, under conditions which limit amide formation by the solvent and thus increase the efficiency of acetic acid recovery. Methods for the direct extraction of acetic acid and the extractive fermentation of acetic acid also employ the modified solvents and increase efficiency of acetic acid production. Such increases in efficiency are also obtained where the energy source for the microbial fermentation contains carbon dioxide and the method includes a carbon dioxide stripping step prior to extraction of acetic acid in solvent.

Microbial process for the preparation of acetic acid, as well as solvent for its extraction from the fermentation broth

DOEpatents

Gaddy, James L.; Clausen, Edgar C.; Ko, Ching-Whan; Wade, Leslie E.; Wikstrom, Carl V.

2004-06-22

A modified water-immiscible solvent useful in the extraction of acetic acid from aqueous streams is a substantially pure mixture of isomers of highly branched di-alkyl amines. Solvent mixtures formed of such a modified solvent with a desired co-solvent, preferably a low boiling hydrocarbon, are useful in the extraction of acetic acid from aqueous gaseous streams. An anaerobic microbial fermentation process for the production of acetic acid employs such solvents, under conditions which limit amide formation by the solvent and thus increase the efficiency of acetic acid recovery. Methods for the direct extraction of acetic acid and the extractive fermentation of acetic acid also employ the modified solvents and increase efficiency of acetic acid production. Such increases in efficiency are also obtained where the energy source for the microbial fermentation contains carbon dioxide and the method includes a carbon dioxide stripping step prior to extraction of acetic acid in solvent.

Variability of pesticide residues in cauliflower units collected from a field trial and market places in Greece.

PubMed

Prodhan, M D H; Papadakis, Emmanouil-N; Papadopoulou-Mourkidou, Euphemia

2016-09-01

To estimate the variability of pesticide residue levels present in cauliflower units, a total of 142 samples were collected from a field trial of a cooperative farmer, and 120 samples were collected from different market places in Thessaloniki, Greece. The collected samples were extracted using the quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction technique, and the residues were determined by liquid chromatography-tandem mass spectrometry. The developed method was validated by evaluating the accuracy, precision, linearity, limit of detection (LOD), and limit of quantification (LOQ). The average recoveries for all the analytes, derived from the data of control samples fortified at 0.01, 0.05, 0.1, and 0.2 mg/kg, ranged from 74 to 110% with a relative standard deviation of ≤8%. The correlation coefficient (R(2)) was ≥0.997 for all the analytes using matrix-matched calibration standards. The LOD values ranged from 0.001 to 0.003 mg/kg, and the LOQ was determined at 0.01 mg/kg for all the sought analytes. The matrix effect was found to be at a considerable level, especially for cypermethrin and deltamethrin, amounting to +90% and +145%, respectively. For the field samples, the unit-to-unit variability factors (VFs) calculated for cypermethrin and deltamethrin were 2.38 and 2.32, respectively, while the average VF for the market basket samples was 5.11. In the market basket samples, residues of cypermethrin, deltamethrin, chlorpyrifos, and indoxacarb were found at levels ≥LOQ and their respective VFs were 7.12, 5.67, 5.28, and 2.40.

Multi-class, multi-residue analysis of pesticides, polychlorinated biphenyls, polycyclic aromatic hydrocarbons, polybrominated diphenyl ethers and novel flame retardants in fish using fast, low-pressure gas chromatography-tandem mass spectrometry.

PubMed

Sapozhnikova, Yelena; Lehotay, Steven J

2013-01-03

A multi-class, multi-residue method for the analysis of 13 novel flame retardants, 18 representative pesticides, 14 polychlorinated biphenyl (PCB) congeners, 16 polycyclic aromatic hydrocarbons (PAHs), and 7 polybrominated diphenyl ether (PBDE) congeners in catfish muscle was developed and evaluated using fast low pressure gas chromatography triple quadrupole tandem mass spectrometry (LP-GC/MS-MS). The method was based on a QuEChERS (quick, easy, cheap, effective, rugged, safe) extraction with acetonitrile and dispersive solid-phase extraction (d-SPE) clean-up with zirconium-based sorbent prior to LP-GC/MS-MS analysis. The developed method was evaluated at 4 spiking levels and further validated by analysis of NIST Standard Reference Materials (SRMs) 1974B and 1947. Sample preparation for a batch of 10 homogenized samples took about 1h/analyst, and LP-GC/MS-MS analysis provided fast separation of multiple analytes within 9min achieving high throughput. With the use of isotopically labeled internal standards, recoveries of all but one analyte were between 70 and 120% with relative standard deviations less than 20% (n=5). The measured values for both SRMs agreed with certified/reference values (72-119% accuracy) for the majority of analytes. The detection limits were 0.1-0.5ng g(-1) for PCBs, 0.5-10ng g(-1) for PBDEs, 0.5-5ng g(-1) for select pesticides and PAHs and 1-10ng g(-1) for flame retardants. The developed method was successfully applied for analysis of catfish samples from the market. Published by Elsevier B.V.

Improved sensitivity of ochratoxin A analysis in coffee using high-performance liquid chromatography with hybrid triple quadrupole-linear ion trap mass spectrometry (LC-QqQLIT-MS/MS).

PubMed

Kokina, Aija; Pugajeva, Iveta; Bartkevics, Vadims

2016-01-01

A novel and sensitive method utilising high-performance liquid chromatography coupled to triple quadrupole-linear ion trap mass spectrometry (LC-QqQLIT-MS/MS) was developed in order to analyse the content of ochratoxin A (OTA) in coffee samples. The introduction of the triple-stage MS scanning mode (MS(3)) has been shown to increase greatly sensitivity and selectivity by eliminating the high chromatographic baseline caused by interference of complex coffee matrices. The analysis included the sample preparation procedure involving extraction of OTA using a methanol-water mixture and clean-up by immunoaffinity columns and detection using the MS(3) scanning mode of LC-QqQLIT-MS/MS. The proposed method offered a good linear correlation (r(2) > 0.998), excellent precision (RSD < 2.9%) and recovery (94%). The limit of quantification (LOQ) for coffee beans and espresso beverages was 0.010 and 0.003 µg kg(-1), respectively. The developed procedure was compared with traditional methods employing liquid chromatography coupled to fluorescent and tandem quadrupole detectors in conjunction with QuEChERS and solid-phase extraction. The proposed method was successfully applied to the determination of OTA in 15 samples of coffee beans and in 15 samples of espresso coffee beverages obtained from the Latvian market. OTA was found in 10 samples of coffee beans and in two samples of espresso in the ranges of 0.018-1.80 µg kg(-1) and 0.020-0.440 µg l(-1), respectively. No samples exceeded the maximum permitted level of OTA in the European Union (5.0 µg kg(-1)).

An Innovative Rapid Method for Analysis of 10 Organophosphorus Pesticide Residues in Wheat by HS-SPME-GC-FPD/MSD.

PubMed

Du, Xin; Ren, YongLin; Beckett, Stephen J

2016-01-01

The rapid detection of pesticide residues in wheat has become a top food security priority. A solvent-free headspace solid-phase microextraction (HS-SPME) has been evaluated for rapid screening of organophosphorus pesticide (OPP) residues in wheat with high sensitivity. Individual wheat samples (1.7 g), spiked with 10 OPPs, were placed in a 4 mL sealed amber glass vial and heated at 60°C for 45 min. During this time, the OPP residues were extracted with a 50 μm/30 μm divinylbenzene (DVB)/carboxen (CAR)/plasma desorption mass spectroscopy polydimethylsiloxane (PDMS) fiber from the headspace above the sample. The fiber was then removed and injected into the GC injection port at 250°C for desorption of the extracted chemicals. The multiple residues were identified by a GC mass spectrometer detector (GC-MSD) and quantified with a GC flame photometric detector (GC-FPD). Seven spiked levels of 10 OPPs on wheat were analyzed. The GC responses for a 50 μm/30 μm DVB/CAR/PDMS fiber increased with increasing spiking levels, yielding significant (R(2) > 0.98) linear regressions. The lowest LODs of the multiple pesticide standards were evaluated under the conditions of the validation study in a range of levels from 0 (control) to 100 ng of pesticide residue per g of wheat that separated on a low-polar GC capillary column (Agilent DB-35UI). The results of the HS-SPME method were compared with the QuEChERS AOAC 2007.01 method and they showed several advantages over the latter. These included improved sensitivity, selectivity, and simplicity.

Multiresidue analytical method using dispersive solid-phase extraction and gas chromatography/ion trap mass spectrometry to determine pharmaceuticals in whole blood.

PubMed

Plössl, Florian; Giera, Martin; Bracher, Franz

2006-11-24

A convenient analytical method for the simultaneous determination of more than 40 pharmaceuticals belonging to various therapeutic categories in whole blood has been developed. Exemplarily, the method was fully validated for eight different pharmaceuticals. The procedure entails addition of acetonitrile, magnesium sulfate and sodium chloride to a small amount of blood, then the mixture is shaken intensively and centrifuged for phase separation. An aliquot of the organic layer is cleaned up by dispersive solid-phase extraction employing bulk sorbents as well as magnesium sulfate for the removal of residual water. This method was based on the QuEChERS approach developed for pesticide residue analysis in food. Gas chromatography/ion trap mass spectrometry (GC/MS) with electron (EI) and chemical (CI) ionisation was then used for qualitative and quantitative determination of the pharmaceuticals. The dispersive SPE with PSA (sorbent functionalized with primary and secondary amines) was found more suitable than aminopropyl and a styrene-divinylbenzene sorbent for sample clean-up before drug level determination in whole blood and plasma, as it was found that most of endogenous matrix components were removed and the analytes were isolated from spiked samples with recoveries above 80%. Variation coefficients of the repeatability typically smaller than 10% have been achieved for a wide range of the investigated substances. The used analytical conditions allowed to separate successively a variety of drugs and poisons with the typical limit of detection at <20 ng mL(-1) levels using 1 microL injection of equivalent blood sample in whole blood. The method is simple, rapid, cheap and very effective for therapeutic drug monitoring and forensic chemistry.

Screening of agrochemicals in foodstuffs using low-temperature plasma (LTP) ambient ionization mass spectrometry.

PubMed

Wiley, Joshua S; García-Reyes, Juan F; Harper, Jason D; Charipar, Nicholas A; Ouyang, Zheng; Cooks, R Graham

2010-05-01

Low-temperature plasma (LTP) permits direct ambient ionization and mass analysis of samples in their native environment with minimal or no prior preparation. LTP utilizes dielectric barrier discharges (DBDs) to create a low power plasma which is guided by gas flow onto the sample from which analytes are desorbed and ionized. In this study, the potential of LTP-MS for the detection of pesticide residues in food is demonstrated. Thirteen multi-class agricultural chemicals were studied (ametryn, amitraz, atrazine, buprofezin, DEET, diphenylamine, ethoxyquin, imazalil, isofenphos-methyl, isoproturon, malathion, parathion-ethyl and terbuthylazine). To evaluate the potential of the proposed approach, LTP-MS experiments were performed directly on fruit peels as well as on fruit/vegetable extracts. Most of the agrochemicals examined displayed remarkable sensitivity in the positive ion mode, giving limits of detection (LOD) for the direct measurement in the low picogram range. Tandem mass spectrometry (MS/MS) was used to confirm identification of selected pesticides by using for these experiments spiked fruit/vegetable extracts (QuEChERS, a standard sample treatment protocol) at levels as low as 1 pg, absolute, for some of the analytes. Comparisons of the data obtained by direct LTP-MS were made with the slower but more accurate conventional LC-MS/MS procedure. Herbicides spiked in aqueous solutions were detectable at LODs as low as 0.5 microg L(-1) without the need for any sample preparation. The results demonstrate that ambient LTP-MS can be applied for the detection and confirmation of traces of agrochemicals in actual market-purchased produce and in natural water samples. Quantitative analysis was also performed in a few selected cases and displayed a relatively high degree of linearity over four orders of magnitude.

Simultaneous quantification of vitamin E, γ-oryzanols and xanthophylls from rice bran essences extracted by supercritical CO2.

PubMed

Sookwong, Phumon; Suttiarporn, Panawan; Boontakham, Pittayaporn; Seekhow, Pattawat; Wangtueai, Sutee; Mahatheeranont, Sugunya

2016-11-15

Since the nutrition value of rice is diminished during rice processing, technology that can preserve and sustain functional compounds is necessary. In this study, supercritical carbon dioxide (SC-CO2) extraction was optimized for operational conditions (time, temperature, pressure and modifier) to extract vitamin E, γ-oryzanols and xanthophylls from rice bran. The simultaneous quantification of the compounds was developed using high-performance liquid chromatography with diode array and fluorescence detectors. Central composite design and respond surface methodology were applied to achieve optimum extraction conditions. The optimized conditions were 60min, 43°C, 5420psi with 10% ethanol as a modifier. Pigmented rice bran extracts contained greater amounts of functional phytochemicals than non-pigmented rice bran extracts (0.68, 1410, and non-detectable μg/g compared with 16.65, 2480, and 0.10μg/g of vitamin E, γ-oryzanols and xanthophylls in pigmented and non-pigmented ones, respectively). SC-CO2 extraction with modifier would be promising for preparation of phytochemical essences for therapeutic purpose. Copyright © 2016 Elsevier Ltd. All rights reserved.

Modified extraction procedure for gas-liquid chromatography applied to the identification of anaerobic bacteria.

PubMed Central

Thomann, W R; Hill, G B

1986-01-01

Chloroform and ether commonly are used as solvents to extract metabolic organic acids for analysis by gas-liquid chromatography in the identification of anaerobic bacteria. Because these solvents are potentially hazardous to personnel, modified extraction procedures involving the use of a safer solvent, methyl tert-butyl ether were developed which remained both simple to perform and effective for organism identification. PMID:3700623

Depigmented-polymerised allergoids favour regulatory over effector T cells: enhancement by 1α, 25-dihydroxyvitamin D3.

PubMed

Urry, Zoe L; Richards, David F; Black, Cheryl; Morales, Maria; Carnés, Jerónimo; Hawrylowicz, Catherine M; Robinson, Douglas S

2014-05-29

Allergen immunotherapy (SIT) is the only treatment for allergic disease capable of modifying disease long term. To reduce the risk of anaphylaxis from SIT, allergen-extracts have been modified by polymerisation with glutaraldehyde to reduce IgE binding. It is suggested that these allergoid extracts also have reduced T cell activity, which could compromise clinical efficacy. Effective SIT is thought to act through regulatory T cells (Tregs) rather than activation of effector T cells. There is no published data on the activity of modified extracts on Tregs. We compared the capacity of modified (depigmented-polymerised) versus unmodified (native) allergen extracts of grass pollen and house dust mite to stimulate proliferation/cytokine production and to modulate Treg/effector T cell frequency in cultures of peripheral blood mononuclear cells (PBMC), from volunteers sensitised to both allergens in vitro. Depigmented-polymerised allergen extracts stimulated less proliferation of PBMC, and reduced effector cell numbers after 7 days in culture than did native extracts. However, the frequency of Foxp3+ Tregs in cultures were similar to those seen with native extract so that ratios of regulatory to effector T cells were significantly increased in cultures stimulated with depigmented-polymerised extracts. Addition of 1α, 25-dihydroxyvitamin D3 further favoured Treg, and reduced effector cytokine production, but not interleukin-10. Depigmented-polymerised allergen extracts appear to favour Treg expansion over activation of effector T cells and this may relate to their demonstrated efficacy and safety in SIT. 1α, 25-dihydroxyvitamin D3 further reduces effector T cell activation by allergen extracts and may be a useful adjuvant for SIT.

Depigmented-polymerised allergoids favour regulatory over effector T cells: enhancement by 1α, 25-dihydroxyvitamin D3

PubMed Central

2014-01-01

Background Allergen immunotherapy (SIT) is the only treatment for allergic disease capable of modifying disease long term. To reduce the risk of anaphylaxis from SIT, allergen-extracts have been modified by polymerisation with glutaraldehyde to reduce IgE binding. It is suggested that these allergoid extracts also have reduced T cell activity, which could compromise clinical efficacy. Effective SIT is thought to act through regulatory T cells (Tregs) rather than activation of effector T cells. There is no published data on the activity of modified extracts on Tregs. Results We compared the capacity of modified (depigmented-polymerised) versus unmodified (native) allergen extracts of grass pollen and house dust mite to stimulate proliferation/cytokine production and to modulate Treg/effector T cell frequency in cultures of peripheral blood mononuclear cells (PBMC), from volunteers sensitised to both allergens in vitro. Depigmented-polymerised allergen extracts stimulated less proliferation of PBMC, and reduced effector cell numbers after 7 days in culture than did native extracts. However, the frequency of Foxp3+ Tregs in cultures were similar to those seen with native extract so that ratios of regulatory to effector T cells were significantly increased in cultures stimulated with depigmented-polymerised extracts. Addition of 1α, 25-dihydroxyvitamin D3 further favoured Treg, and reduced effector cytokine production, but not interleukin-10. Conclusions Depigmented-polymerised allergen extracts appear to favour Treg expansion over activation of effector T cells and this may relate to their demonstrated efficacy and safety in SIT. 1α, 25-dihydroxyvitamin D3 further reduces effector T cell activation by allergen extracts and may be a useful adjuvant for SIT. PMID:24884430

Solid-phase extraction using bis(indolyl)methane-modified silica reinforced with multiwalled carbon nanotubes for the simultaneous determination of flavonoids and aromatic organic acid preservatives.

PubMed

Wang, Na; Liao, Yuan; Wang, Jiamin; Tang, Sheng; Shao, Shijun

2015-12-01

A novel bis(indolyl)methane-modified silica reinforced with multiwalled carbon nanotubes sorbent for solid-phase extraction was designed and synthesized by chemical immobilization of nitro-substituted 3,3'-bis(indolyl)methane on silica modified with multiwalled carbon nanotubes. Coupled with high-performance liquid chromatography analysis, the extraction properties of the sorbent were evaluated for flavonoids and aromatic organic acid compounds. Under optimum conditions, the sorbent can simultaneously extract five flavonoids and two aromatic organic acid preservatives in aqueous solutions in a single-step solid-phase extraction procedure. Wide linear ranges were obtained with correlation coefficients (R(2) ) ranging from 0.9843 to 0.9976, and the limits of detection were in the range of 0.5-5 μg/L for the compounds tested. Compared with the silica modified with multiwalled carbon nanotubes sorbent and the nitro-substituted 3,3'-bis(indolyl)methane-modified silica sorbent, the developed sorbent exhibited higher extraction efficiency toward the selected analytes. The synergistic effect of nitro-substituted 3,3'-bis(indolyl)methane and multiwalled carbon nanotubes not only improved the surface-to-volume ratio but also enhanced multiple intermolecular interactions, such as hydrogen bonds, π-π, and hydrophobic interactions, between the new sorbent and the selected analytes. The as-established solid-phase extraction with high-performance liquid chromatography and diode array detection method was successfully applied to the simultaneous determination of flavonoids and aromatic organic acid preservatives in grape juices with recoveries ranging from 83.9 to 112% for all the selected analytes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemically modified cellulose paper as a thin film microextraction phase.

PubMed

Saraji, Mohammad; Farajmand, Bahman

2013-11-01

In this paper, chemically modified cellulose paper was introduced as a novel extracting phase for thin film microextraction (TFME). Different reagents (Octadecyltrichlorosilane, diphenyldichlorosilane, cyclohexyl isocyanate and phenyl isocyanate) were used to modify the cellulose papers. The modified papers were evaluated as a sorbent for the extraction of some synthetic and natural estrogenic hormones (17α-ethynylestradiol, estriol and estradiol) from aqueous samples. Liquid chromatography-fluorescence detection was used for the quantification of the extracted compounds. The cellulose paper modified with phenyl isocyanate showed the best affinity to the target compounds. TEME parameters such as desorption condition, shaking rate, sample ionic strength and extraction time were investigated and optimized. Limit of detections were between 0.05 and 0.23μgL(-1) and relative standard deviations were less than 11.1% under the optimized condition. The calibration curves were obtained in the range of 0.2-100μgL(-1) with a good linearity (r(2)>0.9935). Wastewater, human urine, pool and river water samples were studied as real samples for the evaluation of the method. Relative recoveries were found to be between 75% and 101%. Copyright © 2013 Elsevier B.V. All rights reserved.

[Application of DNA extraction kit, 'GM quicker' for detection of genetically modified soybeans].

PubMed

Sato, Noriko; Sugiura, Yoshitsugu; Tanaka, Toshitsugu

2012-01-01

Several DNA extraction methods have been officially introduced to detect genetically modified soybeans, but the choice of DNA extraction kits depend on the nature of the samples, such as grains or processed foods. To overcome this disadvantage, we examined whether the GM quicker kit is available for both grains and processed foods. We compared GM quicker with four approved DNA extraction kits in respect of DNA purity, copy numbers of lectin gene, and working time. We found that the DNA quality of GM quicker was superior to that of the other kits for grains, and the procedure was faster. However, in the case of processed foods, GM quicker was not superior to the other kits. We therefore investigated an unapproved GM quicker 3 kit, which is available for DNA extraction from processed foods, such as tofu and boiled soybeans. The GM quicker 3 kit provided good DNA quality from both grains and processed foods, so we made a minor modification of the GM quicker-based protocol that was suitable for processed foods, using GM quicker and its reagents. The modified method enhanced the performance of GM quicker with processed foods. We believe that GM quicker with the modified protocol is an excellent tool to obtain high-quality DNA from grains and processed foods for detection of genetically modified soybeans.

Feasibility of ion-pair/supercritical fluid extraction of an ionic compound--pseudoephedrine hydrochloride.

PubMed

Eckard, P R; Taylor, L T

1997-02-01

The supercritical fluid extraction (SFE) of an ionic compound, pseudoephedrine hydrochloride, from a spiked-sand surface was successfully demonstrated. The effect of carbon dioxide density (CO2), supercritical fluid composition (pure vs. methanol modified), and the addition of a commonly used reversed-phase liquid chromatographic ion-pairing reagent, 1-heptanesulfonic acid, sodium salt, on extraction efficiency was examined. The extraction recoveries of pseudoephedrine hydrochloride with the addition of the ion-pairing reagent from a spiked-sand surface were shown to be statistically greater than the extraction recoveries without the ion-pairing reagent with both pure and methanol-modified carbon dioxide.

PRE-TREATMENT WITH DIESEL EXHAUST EXTRACT ALTERS INFLUENZA VIRUS REPLICATION IN LUNG EPITHELIAL CELLS

EPA Science Inventory

Diesel Exhaust (DE) has been demonstrated to generate inflammatory responses in the lung and modify immune responses to allergens. However, little is known about the effects of DE on common respiratory viral infections. We examined whether exposure to DE extracts (DEE) modifies i...

Monitoring of pesticide residues in market basket samples of vegetable from Lucknow City, India: QuEChERS method.

PubMed

Srivastava, Ashutosh K; Trivedi, Purushottam; Srivastava, M K; Lohani, M; Srivastava, Laxman Prasad

2011-05-01

The study was conducted on 20 vegetables including leafy, root, modified stem, and fruity vegetables like bitter gourd, jack fruit, french-bean, onion, colocassia, pointed gourd, capsicum, spinach, potato, fenugreek seeds, carrot, radish, cucumber, beetroot, brinjal, cauliflower, cabbage, tomato, okra, and bottle gourd. Forty-eight pesticides including 13 organochlorines (OCs), 17 organophosphates (OPs), 10 synthetic pyrethriods (SPs), and eight herbicides (H) pesticides were analyzed. A total number of 60 samples, each in triplicates, were analyzed using Quick, Easy, Cheap, Effective, Rugged, and Safe method. The quantification was done by GC-ECD/NPD. The recovery varies from 70.22% to 96.32% with relative standard deviation (RSD) of 15%. However the limit of detection ranged from 0.001-0.009 mg kg(-1)for OCs, SPs, OPs, and H, respectively. Twenty-three pesticides were detected from total 48 analyzed pesticides in the samples with the range of 0.005-12.35 mg kg(-1). The detected pesticides were: Σ-HCH, Dicofol, Σ-Endosulfan, Fenpropathrin, Permethrin-II, β-cyfluthrin-II, Fenvalerate-I, Dichlorvos, Dimethoate, Diazinon, Malathion, Chlorofenvinfos, Anilophos, and Dimethachlor. In some vegetables like radish, cucumber, cauliflower, cabbage, and okra, the detected pesticides (Σ-HCH, Permethrin-II, Dichlorvos, and Chlorofenvinfos) were above maximum residues limit (MRL) (PFA 1954). However, in other vegetables the level of pesticide residues was either below detection limit or MRL.

Magnetic molecularly imprinted polymers based on silica modified by deep eutectic solvents for the rapid simultaneous magnetic-based solid-phase extraction of Salvia miltiorrhiza bunge, Glycine max (Linn.) Merr and green tea.

PubMed

Li, Guizhen; Wang, Xiaoqin; Row, Kyung Ho

2018-04-01

Novel magnetic molecularly imprinted polymers (MMIPs) with multiple-template based on silica were modified by four types of deep eutectic solvents (DESs) for the rapid simultaneous magnetic solid-phase extraction (MSPE) of tanshinone Ⅰ, tanshinone ⅡA, and cryptotanshinone from Salvia miltiorrhiza bunge; glycitein, genistein, and daidzein from Glycine max (Linn.) Merr; and epicatechin, epigallocatechin gallate, and epicatechin gallate from green tea, respectively. The synthesized materials were characterized by Fourier transform infrared spectroscopy and field emission scanning electron microscopy. Single factor experiments were to explore the relationship between the extraction efficiency and four factors (the sample solution pH, amount of DESs for modification, amount of adsorbent, and extraction time). It was showed that the DES4-MMIPs have better extraction ability than the MMIPs without DESs and the other three DESs-modified MMIPs. The best extraction recoveries with DES4-MMIP were tanshinone Ⅰ (85.57%), tanshinone ⅡA (80.58%), cryptotanshinone (92.12%), glycitein (81.65%), genistein (87.72%), daidzein (92.24%), epicatechin (86.43%), epigallocatechin gallate (80.92%), and epicatechin gallate (93.64%), respectively. The novel multiple-template MMIPs materials modified by DES for the rapid simultaneous MSPE of active compounds were proved to reduce the experimental steps than single-template technique, and increase the extraction efficiency. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microbial process for the preparation of acetic acid as well as solvent for its extraction from the fermentation broth

DOEpatents

Gaddy, James L.; Clausen, Edgar C.; Ko, Ching-Whan; Wade, Leslie E.; Wikstrom, Carl V.

2006-07-11

A modified water-immiscible solvent useful in the extraction of acetic acid from aqueous streams is a substantially pure mixture of isomers of highly branched di-alkyl amines. This solvent is substantially devoid of mono-alkyl amines and alcohols. Solvent mixtures formed of such a modified solvent with a desired cosolvent, preferably a low boiling hydrocarbon which forms an azeotrope with water are useful in the extraction of acetic acid from aqueous gaseous streams. An anaerobic microbial fermentation process for the production of acetic acid employs such solvents, under conditions which limit amide formation by the solvent and thus increase the efficiency of acetic acid recovery. Methods for the direct extraction of acetic acid and the extractive fermentation of acetic acid also employ the modified solvents and increase efficiency of acetic acid production. Such increases in efficiency are also obtained where the energy source for the microbial fermentation contains carbon dioxide and the method includes a carbon dioxide stripping step prior to extraction of acetic acid in solvent.

Microbial process for the preparation of acetic acid as well as solvent for its extraction from the fermentation broth

DOEpatents

Gaddy, James L.; Clausen, Edgar C.; Ko, Ching-Whan; Wade, Leslie E.; Wikstrom, Carl V.

2002-01-01

A modified water-immiscible solvent useful in the extraction of acetic acid from aqueous streams is a substantially pure mixture of isomers of highly branched di-alkyl amines. This solvent is substantially devoid of mono-alkyl amines and alcohols. Solvent mixtures formed of such a modified solvent with a desired cosolvent, preferably a low boiling hydrocarbon which forms an azeotrope with water are useful in the extraction of acetic acid from aqueous gaseous streams. An anaerobic microbial fermentation process for the production of acetic acid employs such solvents, under conditions which limit amide formation by the solvent and thus increase the efficiency of acetic acid recovery. Methods for the direct extraction of acetic acid and the extractive fermentation of acetic acid also employ the modified solvents and increase efficiency of acetic acid production. Such increases in efficiency are also obtained where the energy source for the microbial fermentation contains carbon dioxide and the method includes a carbon dioxide stripping step prior to extraction of acetic acid in solvent.

Inclusion of 1-naphthylacetic acid and 2-(1-naphthyl)acetamide into three typical multiresidue methods for LC/MS/MS analysis of tomatoes and zucchini.

PubMed

Lozano, Ana; Pérez-Parada, Andrés; Heinzen, Horacio; Fernández-Alba, Amadeo R

2012-01-01

In spite of high plant growth regulator application rates, little has been reported in the literature on determination of their residues in fruits and vegetables. This would be useful in monitoring good manufacturing practices and overall safety through the enforcement of maximum residue levels (MRLs). The present work describes method validation for the determination of 1-naphthylacetic acid (NAA) and 2(1-naphthyl)acetamide (NAAm) in tomato and zucchini using the mini-Luke, ethyl acetate (EtOAc) and acetate-buffered quick, easy, cheap, effective, rugged, and safe (QuEChERS) methods. Samples were spiked at two different levels: 50 and 100 pg/kg for NAA and 20 and 100 pg/kg for NAAm. These compounds were analyzed within the same chromatographic run with LC coupled to triple quadrupole MS (LC/(QqQ)MS/MS) in positive and negative electrospray ionization [ESI(+) and ESI(-)] modes for NAAm and NAA, respectively. For analyte confirmation, LC/ESI(-)QTOF-MS was also investigated given that NAA has only one multiple reaction monitoring transition (185.1-*140.9 m/z). These three common methods were used to determine linearity, recoveries, precision (RSD), matrix effects, repeatability, and reproducibility (n = 5) for the selected matrixes. In terms of the Directorate-General for Health and Consumers (DG-SANCO) guidelines, only insignificant differences were found for the multiresidue methods tested, regardless of the commodity. Matrix-matched calibration was used, and LODs were below 10.1 pg/kg for NAA and 6.0 pg/kg for NAAm, which were lower than the MRLs established in current European Union legislation for these compounds. Obtained recoveries for NAA ranged from 87 to 107% with RSD values below 10% for mini-Luke, 83 to 107% with RSD <11% for EtOAc, and 76 to 85% with RSD <7% for QuEChERS. NAAm recoveries ranged from 74 to 102% with RSD 5 15% for mini-Luke, 76 to 97% with RSD <4% for EtOAc, and 76 to 93% with RSD < 5% for QuEChERS. The linearity of the response over two orders of magnitude was demonstrated (r2 > 0.996) for all methods used. Good repeatability and reproducibility in terms of RSD were obtained (11.3-17.8%) for these analytical methods. The results were acceptable within the studied ranges for both analytes in all methods. As these multiresidue methods are used at the present time in many laboratories, this survey indicates that these analytes should be included in their monitoring scope.

Supercritical Fluid Extraction and Separation of Uranium from Other Actinides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Donna L. Quach; Bruce J. Mincher; Chien M. Wai

2014-06-01

This paper investigates the feasibility of separating uranium from other actinides by using supercritical fluid carbon dioxide (sc-CO2) as a solvent modified with tri-n-butylphosphate (TBP) for the development of an extraction and counter current stripping technique, which would be a more efficient and environmentally benign technology for used nuclear fuel reprocessing compared to traditional solvent extraction. Several actinides (U(VI), Np(VI), Pu(IV), and Am(III)) were extracted in sc-CO2 modified with TBP over a range of nitric acid concentrations and then the actinides were exposed to reducing and complexing agents to suppress their extractability. According to this study, the separation of uraniummore » from plutonium in sc-CO2 modified with TBP was successful at nitric acid concentrations of less than 3 M in the presence of acetohydroxamic acid or oxalic acid, and the separation of uranium from neptunium was successful at nitric acid concentrations of less than 1 M in the presence of acetohydroxamic acid, oxalic acid, or sodium nitrite.« less

Fluoro-alcohol phase modifiers and process for cesium solvent extraction

DOEpatents

Bonnesen, Peter V.; Moyer, Bruce A.; Sachleben, Richard A.

2003-05-20

The invention relates to a class of phenoxy fluoro-alcohols, their preparation, and their use as phase modifiers and solvating agents in a solvent composition for the extraction of cesium from alkaline solutions. These phenoxy fluoro-alcohols comply with the formula: ##STR1## in which n=2 to 4; X represents a hydrogen or a fluorine atom, and R.sup.2 -R.sup.6 are hydrogen or alkyl substituents. These phenoxy fluoro-alcohol phase modifiers are a necessary component to a robust solvent composition and process useful for the removal of radioactive cesium from alkaline nuclear waste streams. The fluoro-alcohols can also be used in solvents designed to extract other cesium from acidic or neutral solutions.

Characterization of cobalt(II) chloride-modified condensation polyimide films

NASA Technical Reports Server (NTRS)

Rancourt, J. D.; Taylor, L. T.

1988-01-01

The effect of solvent extraction on the properties of cobalt(II) chloride-modified polyimide films was investigated. Solvent-cast films were prepared from solutions of cobalt chloride in poly(amide acid)/N,N-dimethylacetamide (DMAc) and were subsequently dried and cured in static air, forced air, or inert gas ovens with controlled humidity. The films were extracted by either of the three processes (1) soaking in a tray with distilled water at room temperature, (2) soxhlett extraction with distilled water, or (3) soxhell extraction with DMAc. Extraction with DMAc was found to remove both cobalt and chlorine from the films and to slightly increase bulk thermal stability and both surface resistivity and electrical resistivity.

Determination of arsenic species in solid matrices utilizing supercritical fluid extraction coupled with gas chromatography after derivatization with thioglycolic acid n-butyl ester.

PubMed

Wang, Zhifeng; Cui, Zhaojie

2016-12-01

A method using derivatization and supercritical fluid extraction coupled with gas chromatography was developed for the analysis of dimethylarsinate, monomethylarsonate and inorganic arsenic simultaneously in solid matrices. Thioglycolic acid n-butyl ester was used as a novel derivatizing reagent. A systematic discussion was made to investigate the effects of pressure, temperature, flow rate of the supercritical CO 2 , extraction time, concentration of the modifier, and microemulsion on extraction efficiency. The application for real environmental samples was also studied. Results showed that thioglycolic acid n-butyl ester was an effective derivatizing reagent that could be applied for arsenic speciation. Using methanol as modifier of the supercritical CO 2 can raise the extraction efficiency, which can be further enhanced by adding a microemulsion that contains Triton X-405. The optimum extraction conditions were: 25 MPa, 90°C, static extraction for 10 min, dynamic extraction for 25 min with a flow rate of 2.0 mL/min of supercritical CO 2 modified by 5% v/v methanol and microemulsion. The detection limits of dimethylarsinate, monomethylarsonate, and inorganic arsenic in solid matrices were 0.12, 0.26, and 1.1 mg/kg, respectively. The optimized method was sensitive, convenient, and reliable for the extraction and analysis of different arsenic species in solid samples. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct analysis of in-gel proteins by carbon nanotubes-modified paper spray ambient mass spectrometry.

PubMed

Han, Feifei; Yang, Yuhan; Ouyang, Jin; Na, Na

2015-02-07

The in situ and direct extraction, desorption and ionization of in-gel intact proteins after electrophoresis has been achieved by carbon nanotubes (CNTs)-modified paper spray mass spectrometry at ambient conditions. Characteristics of CNTs (including larger surface area, smaller pore diameter and enhanced conductivity) were endowed to the porous filter paper substrate by uniformly dispersing the CNTs on the filter paper. Upon applying electric potential to the CNTs-modified paper, the in-gel proteins were extracted from the gel and subsequently migrated to the tip of the filter paper by electrophoresis-like behavior for paper spray ionization, which was monitored by extracted ion chronograms. The characterizations of modified filter papers and CNTs nanoparticles further confirmed the role of CNTs in in-gel protein extraction, protein migration as well as spray ionization at the paper tip. Under optimized conditions, a mixture of cytochrome c, lysozyme and myoglobin was successfully separated by native electrophoresis and subsequently analysed by the present method, showing a limit of detection of 10 ng per gel band. The present strategy offers a new pathway for the direct detection of in-gel intact proteins at ambient conditions without any pre-treatment (e.g. digestion, chemical extraction and desalting), which exhibits potential applications in top-down proteomics.

Statistical evaluation of fatty acid profile and cholesterol content in fish (common carp) lipids obtained by different sample preparation procedures.

PubMed

Spiric, Aurelija; Trbovic, Dejana; Vranic, Danijela; Djinovic, Jasna; Petronijevic, Radivoj; Matekalo-Sverak, Vesna

2010-07-05

Studies performed on lipid extraction from animal and fish tissues do not provide information on its influence on fatty acid composition of the extracted lipids as well as on cholesterol content. Data presented in this paper indicate the impact of extraction procedures on fatty acid profile of fish lipids extracted by the modified Soxhlet and ASE (accelerated solvent extraction) procedure. Cholesterol was also determined by direct saponification method, too. Student's paired t-test used for comparison of the total fat content in carp fish population obtained by two extraction methods shows that differences between values of the total fat content determined by ASE and modified Soxhlet method are not statistically significant. Values obtained by three different methods (direct saponification, ASE and modified Soxhlet method), used for determination of cholesterol content in carp, were compared by one-way analysis of variance (ANOVA). The obtained results show that modified Soxhlet method gives results which differ significantly from the results obtained by direct saponification and ASE method. However the results obtained by direct saponification and ASE method do not differ significantly from each other. The highest quantities for cholesterol (37.65 to 65.44 mg/100 g) in the analyzed fish muscle were obtained by applying direct saponification method, as less destructive one, followed by ASE (34.16 to 52.60 mg/100 g) and modified Soxhlet extraction method (10.73 to 30.83 mg/100 g). Modified Soxhlet method for extraction of fish lipids gives higher values for n-6 fatty acids than ASE method (t(paired)=3.22 t(c)=2.36), while there is no statistically significant difference in the n-3 content levels between the methods (t(paired)=1.31). The UNSFA/SFA ratio obtained by using modified Soxhlet method is also higher than the ratio obtained using ASE method (t(paired)=4.88 t(c)=2.36). Results of Principal Component Analysis (PCA) showed that the highest positive impact to the second principal component (PC2) is recorded by C18:3 n-3, and C20:3 n-6, being present in a higher amount in the samples treated by the modified Soxhlet extraction, while C22:5 n-3, C20:3 n-3, C22:1 and C20:4, C16 and C18 negatively influence the score values of the PC2, showing significantly increased level in the samples treated by ASE method. Hotelling's paired T-square test used on the first three principal components for confirmation of differences in individual fatty acid content obtained by ASE and Soxhlet method in carp muscle showed statistically significant difference between these two data sets (T(2)=161.308, p<0.001). Copyright 2010 Elsevier B.V. All rights reserved.

Comparison of supercritical fluid extraction and ultrasound-assisted extraction of fatty acids from quince (Cydonia oblonga Miller) seed using response surface methodology and central composite design.

PubMed

Daneshvand, Behnaz; Ara, Katayoun Mahdavi; Raofie, Farhad

2012-08-24

Fatty acids of Cydonia oblonga Miller cultivated in Iran were obtained by supercritical (carbon dioxide) extraction and ultrasound-assisted extraction methods. The oils were analyzed by capillary gas chromatography using mass spectrometric detections. The compounds were identified according to their retention indices and mass spectra (EI, 70eV). The experimental parameters of SFE such as pressure, temperature, modifier volume, static and dynamic extraction time were optimized using a Central Composite Design (CCD) after a 2(5) factorial design. Pressure and dynamic extraction time had significant effect on the extraction yield, while the other factors (temperature, static extraction time and modifier volume) were not identified as significant factors under the selected conditions. The results of chemometrics analysis showed the highest yield for SFE (24.32%), which was obtained at a pressure of 353bar, temperature of 35°C, modifier (methanol) volume of 150μL, and static and dynamic extraction times of 10 and 60min, respectively. Ultrasound-assisted extraction (UAE) of Fatty acids from C. oblonga Miller was optimized, using a rotatable central composite design. The optimum conditions were as follows: solvent (n-hexane) volume, 22mL; extraction time, 30min; and extraction temperature, 55°C. This resulted in a maximum oil recovery of 19.5%. The extracts with higher yield from both methods were subjected to transesterification and GC-MS analysis. The results show that the oil obtained by SFE with the optimal operating conditions allowed a fatty acid composition similar to the oil obtained by UAE in optimum condition and no significant differences were found. The major components of oil extract were Linoleic, Palmitic, Oleic, Stearic and Eicosanoic acids. Copyright © 2012 Elsevier B.V. All rights reserved.

Screening of pesticide residues in honeybee wax comb by LC-ESI-MS/MS. A pilot study.

PubMed

Herrera López, Sonia; Lozano, Ana; Sosa, Alexis; Hernando, M Dolores; Fernández-Alba, Amadeo R

2016-11-01

A developed multi-residue method using microflow-LC-ESI-QqQ-MS provided a wide-scope analysis for medium-polar and polar pesticide residues (120 compounds including breakdown products). Honeybee wax comb samples were extracted using a generic QuEChERS based procedure. Acceptable recoveries at concentration levels of 5 and 50 μg kg(-1) were within the 70-120% range with an associated precision RSD <20%. The LOQ values were mostly 5 μg kg(-1) for almost all pesticides. Aprox. 31 of 120 LC-amenable pesticides tested (25.8%) were detected in a pilot study of 60 samples. Pesticide residues detected using the proposed method were: the breakdown products of amitraz, DMPF and DMF, an acaricide used for Varroa mite control, with a range of concentration from 5 to 464 μg kg(-1) (sum of DMPF + DMF), organophosphate insecticides from 1 to 464 μg kg(-1), acaricides at concentrations > 9 μg kg(-1); fungicides at concentrations ranging from 1 to 23 μg kg(-1.) The number of positive detections due to herbicides was lower as expected and at a lower level of concentration, from 1 to 5.9 μg kg(-1). Copyright © 2016 Elsevier Ltd. All rights reserved.

Multi-residue method for the determination of antibiotics and some of their metabolites in seafood.

PubMed

Serra-Compte, Albert; Álvarez-Muñoz, Diana; Rodríguez-Mozaz, Sara; Barceló, Damià

2017-06-01

The presence of antibiotics in seafood for human consumption may pose a risk for consumers. A methodology for the analysis of antibiotics in seafood based on QuEChERS (quick, easy, cheap, effective, rugged, and safe) extraction, followed by detection and quantification using liquid chromatography coupled to mass spectrometry was developed. The analytical method was evaluated for the determination of 23 antibiotics (including parent compounds and some metabolites) in fish, mussels and clams. Recoveries ranged between 30% and 70% for most of the compounds and method detection and quantification limits (MDLs and MQLs) were between 0.01 and 0.31 ng/g dry weigh (dw) and 0.02-1.03 ng/g (dw) respectively. Real seafood samples were analysed using this method. Nine antibiotics were found at levels above MDLs; however none of them exceed the maximum residue limits (MRL) established by the authorities. Tetracycline was the most ubiquitous compound, presenting also the highest concentration: 5.63 ng/g (dw) in fish from Netherlands. In addition, an alternative technique based on microbial growth inhibition was explored as semiquantitative detection method of antibiotics in seafood. This methodology could be applied as a fast screening technique for the detection of macrolides and β-lactams in seafood but further research is needed for other antibiotics families. Copyright © 2016 Elsevier Ltd. All rights reserved.

A simultaneous screening and quantitative method for the multiresidue analysis of pesticides in spices using ultra-high performance liquid chromatography-high resolution (Orbitrap) mass spectrometry.

PubMed

Goon, Arnab; Khan, Zareen; Oulkar, Dasharath; Shinde, Raviraj; Gaikwad, Suresh; Banerjee, Kaushik

2018-01-12

A novel screening and quantitation method is reported for non-target multiresidue analysis of pesticides using ultra-HPLC-quadrupole-Orbitrap mass spectrometry in spice matrices, including black pepper, cardamom, chili, coriander, cumin, and turmeric. The method involved sequential full-scan (resolution = 70,000), and variable data independent acquisition (vDIA) with nine consecutive fragmentation events (resolution = 17,500). Samples were extracted by the QuEChERS method. The introduction of an SPE-based clean-up step through hydrophilic-lipophilic-balance (HLB) cartridges proved advantageous in minimizing the false negatives. For coriander, cumin, chili, and cardamom, the screening detection limit was largely at 2 ng/g, while it was 5 ng/g for black pepper, and turmeric. When the method was quantitatively validated for 199 pesticides, the limit of quantification (LOQ) was mostly at 10 ng/g (excluding black pepper, and turmeric with LOQ = 20 ng/g) with recoveries within 70-120%, and precision-RSDs <20%. Furthermore, the method allowed the identification of suspected non-target analytes through retrospective search of the accurate mass of the compound-specific precursor and product ions. Compared to LC-MS/MS, the quantitative performance of this Orbitrap-MS method had agreements in residue values between 78-100%. Copyright © 2017 Elsevier B.V. All rights reserved.

Screening of the presence organophosphates and organochlorines pesticide residues in vegetables and fruits using gas chromatography-mass spectrometry

NASA Astrophysics Data System (ADS)

Putri, Dillani; Aryana, Nurhani; Aristiawan, Yosi; Styarini, Dyah

2017-01-01

Pesticides is commonly used to improve the quality of agricultural product, especially in vegetables and fruits. Due to pesticide residues in the product become a concern to consumer health, monitoring and analysis of pesticide residues in agriculture product need to be established. The certified reference material (CRM) is often benefited to obtain accurate results in analysis. It is required as the quality control to improve quality assurance of the testing results. Unfortunately in Indonesia, the development of matrix CRM for the analysis of pesticide residues in vegetables and fruits is still limited. This study is aimed to determine the type of commodity and target analyte to be employed in the development of CRM for pesticides in vegetables and fruits. As the preliminary study, the screening of 11 commodities of fresh vegetables and fruits has been conducted to review the information about the presence of organophosphates (OPs) and organochlorines (OCs) in the sample. In this analysis, QuEChERS technique was used in the extraction process and the qualitative analysis was evaluated by using GC-MS. The results showed that strawberry and celery contain residues of pesticide chlorpyrifos. Further analysis of the commodity celery from seven different places has been conducted, resulting that from 3 of all 7 samples (43%) were positive containing chlorpyrifos. Therefore, the development of CRM for chlorpyrifos in celery will be our next research project.

A new approach in sample treatment combined with UHPLC-MS/MS for the determination of multiclass mycotoxins in edible nuts and seeds.

PubMed

Arroyo-Manzanares, Natalia; Huertas-Pérez, José F; Gámiz-Gracia, Laura; García-Campaña, Ana M

2013-10-15

A sensitive, simple and rapid method for the determination of fourteen mycotoxins in nuts and seeds (including almonds, peanuts, sunflower seeds, pumpkin seeds, walnuts, macadamia nuts, pistachios, hazelnuts and pine nuts) has been developed using ultra-high performance liquid chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS). The sample treatment comprises a first step based on QuEChERS procedure for the determination of fumonisin B1, fumonisin B2, deoxynivalenol, fusarenon-X, T-2 and HT-2 toxin, citrinin, sterigmatocystin, zearalenone and ochratoxin A. A subsequent clean-up step based on the dispersive liquid-liquid microextraction (DLLME) was necessary for the determination of aflatoxins (B1, B2, G1 and G2), since their determination was not possible applying only the QuEChERS-based extraction. The method was validated for peanuts as representative matrix and was subsequently evaluated for the other eight matrices. Quantification limits obtained for aflatoxins, the unique mycotoxins legislated on these matrices, were lower than the maximum levels allowed by the current legislation, while quantification limits obtained for the other mycotoxins were lower than the limits usually permitted by the legislation in other food matrices. Precision of the method was always lower than 11%, and recoveries ranged between 60.7% and 104.3%. © 2013 Elsevier B.V. All rights reserved.

Determination of phthalic acid esters in different baby food samples by gas chromatography tandem mass spectrometry.

PubMed

Socas-Rodríguez, Bárbara; González-Sálamo, Javier; Herrera-Herrera, Antonio V; Santana-Mayor, Álvaro; Hernández-Borges, Javier

2018-03-09

In this work, a new method has been developed for the determination of 14 phthalic acid esters (i.e., benzylbutyl phthalate (BBP), bis-2-n-butoxyethyl phthalate (DBEP), dibutyl phthalate (DBP), dicyclohexyl phthalate (DCHP), bis-2-ethoxyethyl phthalate (DEEP), diethyl phthalate (DEP), diisodecyl phthalate (DIDP), diisononyl phthalate (DINP), bis-isopentyl phthalate (DIPP), bis (2-methoxyethyl) phthalate (DMEP), dimethyl phthalate (DMP), di-n-octyl phthalate (DNOP), bis-n-pentyl phthalate (DNPP), dipropyl phthalate (DPP)) and one adipate (bis (2-ethylhexyl) adipate (DEHA)) in different baby foods. Separation was carried out by gas chromatography triple quadrupole tandem mass spectrometry while the previous extraction of the samples was carried out using the QuEChERS method. The methodology was validated for four baby food samples (two fruit compotes of different compositions and two meat and fish purees with vegetables) using dibutyl phthalate-3,4,5,6-d 4 (DBP-d 4 ) as internal standard. Determination coefficients (R 2 ) of matrix-matched calibration curves were above 0.9922 in all cases while relative recovery values ranged between 70 and 120%, with relative standard deviation values below 19%. The limits of quantification of the method ranged between 0.03 and 1.11 μg/kg. Finally, the analysis of commercially available samples was carried out finding the presence of BBP, DEHA, DEP, DIDP, and DPP in some of the studied samples.

A Method for Simultaneous Determination of 20 Fusarium Toxins in Cereals by High-Resolution Liquid Chromatography-Orbitrap Mass Spectrometry with a Pentafluorophenyl Column

PubMed Central

Tamura, Masayoshi; Mochizuki, Naoki; Nagatomi, Yasushi; Harayama, Koichi; Toriba, Akira; Hayakawa, Kazuichi

2015-01-01

A high-resolution liquid chromatography-Orbitrap mass spectrometry (LC-Orbitrap MS) method was developed for simultaneous determination of 20 Fusarium toxins (nivalenol, fusarenon-X, deoxynivalenol, 3-acetyl deoxynivalenol, 15-acetyl deoxynivalenol, HT-2 toxin, T-2 toxin, neosolaniol, diacetoxyscirpenol, fumonisin B1, fumonisin B2, fumonisin B3, fumonisin A1, fumonisin A2, fumonisin A3, zearalenone, α-zearalenol, β-zearalenol, α-zearalanol, and β-zearalanol) in cereals. The separation of 20 Fusarium toxins with good peak shapes was achieved using a pentafluorophenyl column, and Orbitrap MS was able to detect accurately from cereal matrix components within ±0.77 ppm. The samples were prepared using a QuEChERS kit for extraction and a multifunctional cartridge for purification. The linearity, repeatability, and recovery of the method were >0.9964, 0.8%–14.7%, and 71%–106%, respectively. Using this method, an analysis of 34 commercially available cereals detected the presence of deoxynivalenol, 15-acetyl deoxynivalenol, fumonisin B1, fumonisin B2, fumonisin B3, fumonisn A1, fumonisin A2, fumonisin A3, and zearalenone in corn samples with high concentration and frequency. Trichothecenes was detected from wheat samples with high frequency; in particular, the concentration of deoxynivalenol was high. Conversely, α-zearalenol, β-zearalenol, α-zearalanol, and β-zearalanol were not detected in any of the samples. PMID:26008230

Variability of pesticide residues in eggplant units collected from a field trial and marketplaces in Greece.

PubMed

Prodhan, Mohammad Dalower Hossain; Papadakis, Emmanouil-Nikolaos; Papadopoulou-Mourkidou, Euphemia

2018-04-01

Variability of pesticide residues among food items is very important when assessing the risks and food safety for the consumers. Therefore, the present study was undertaken to estimate the unit-to-unit residue variability factors for eggplant. In total, 120 samples from a trial field and 142 samples from different marketplaces in Thessaloniki, Greece, were collected to estimate the variability of pesticide residues in eggplant units. They were extracted by the QuEChERS method and the residues were determined by LC-MS/MS. For the field samples, the unit-to-unit variability factors (VFs) obtained for cypermethrin and deltamethrin residues were 2.54 and 2.51, respectively. The mean residue levels of both pesticides were higher in the composite samples than in the individual samples. The average VFs for the marketplace samples was 3.89. The eggplant units exposed to pesticides were higher in residues than the non-exposed units. The variability factors obtained in the marketplace samples were higher than those in the samples collected from the field trial. A default VF value of 3 for field trials is appropriate for use when assessing the acute dietary intake but a VF for the marketplace samples should be reconsidered with a larger data. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Total lipid extraction of homogenized and intact lean fish muscles using pressurized fluid extraction and batch extraction techniques.

PubMed

Isaac, Giorgis; Waldebäck, Monica; Eriksson, Ulla; Odham, Göran; Markides, Karin E

2005-07-13

The reliability and efficiency of pressurized fluid extraction (PFE) technique for the extraction of total lipid content from cod and the effect of sample treatment on the extraction efficiency have been evaluated. The results were compared with two liquid-liquid extraction methods, traditional and modified methods according to Jensen. Optimum conditions were found to be with 2-propanol/n-hexane (65:35, v/v) as a first and n-hexane/diethyl ether (90:10, v/v) as a second solvent, 115 degrees C, and 10 min of static time. PFE extracts were cleaned up using the same procedure as in the methods according to Jensen. When total lipid yields obtained from homogenized cod muscle using PFE were compared yields obtained with original and modified Jensen methods, PFE gave significantly higher yields, approximately 10% higher (t test, P < 0.05). Infrared and NMR spectroscopy suggested that the additional material that inflates the gravimetric results is rather homogeneous and is primarily consists of phospholipid with headgroups of inositidic and/or glycosidic nature. The comparative study demonstrated that PFE is an alternative suitable technique to extract total lipid content from homogenized cod (lean fish) and herring (fat fish) muscle showing a precision comparable to that obtained with the traditional and modified Jensen methods. Despite the necessary cleanup step, PFE showed important advantages in the solvent consumption was cut by approximately 50% and automated extraction was possible.

One simple DNA extraction device and its combination with modified visual loop-mediated isothermal amplification for rapid on-field detection of genetically modified organisms.

PubMed

Zhang, Miao; Liu, Yinan; Chen, Lili; Quan, Sheng; Jiang, Shimeng; Zhang, Dabing; Yang, Litao

2013-01-02

Quickness, simplicity, and effectiveness are the three major criteria for establishing a good molecular diagnosis method in many fields. Herein we report a novel detection system for genetically modified organisms (GMOs), which can be utilized to perform both on-field quick screening and routine laboratory diagnosis. In this system, a newly designed inexpensive DNA extraction device was used in combination with a modified visual loop-mediated isothermal amplification (vLAMP) assay. The main parts of the DNA extraction device included a silica gel membrane filtration column and a modified syringe. The DNA extraction device could be easily operated without using other laboratory instruments, making it applicable to an on-field GMO test. High-quality genomic DNA (gDNA) suitable for polymerase chain reaction (PCR) and isothermal amplification could be quickly isolated from plant tissues using this device within 15 min. In the modified vLAMP assay, a microcrystalline wax encapsulated detection bead containing SYBR green fluorescent dye was introduced to avoid dye inhibition and cross-contaminations from post-LAMP operation. The system was successfully applied and validated in screening and identification of GM rice, soybean, and maize samples collected from both field testing and the Grain Inspection, Packers, and Stockyards Administration (GIPSA) proficiency test program, which demonstrated that it was well-adapted to both on-field testing and/or routine laboratory analysis of GMOs.

Cellulose membrane modified with polypyrrole as an extraction device for the determination of emerging contaminants in river water with GC-MS.

PubMed

de Noronha, Bárbara Viero; Bergamini, Márcio Fernando; Marcolino Junior, Luiz Humberto; da Silva, Bruno José Gonçalves

2018-05-21

In this study, a simple, efficient, and reusable device based on cellulose membranes modified with polypyrrole was developed to extract 14 emerging contaminants from aqueous matrices. For chemical polymerization, a low-cost cellulose membrane was immersed in 0.1 mol L -1 pyrrole and 0.5 mol L -1 ammonium persulfate for 40 min in an ice/water bath. The cellulose membranes modified with polypyrrole were accommodated in a polycarbonate holder suitable for solid-phase extraction disks. Solid-phase extraction parameters that affect extraction efficiency, such as sample volume, pH, flow-rate, and desorption were optimized. Subsequently, determination of target compounds was performed by gas chromatography with mass spectrometry. The linear range for analytes ranged from 0.05 to 500 μg L -1 , with coefficients of determination above 0.990. The limits of quantification varied between 0.05 and 10 μg L -1 , with relative standard deviations lower than 17%. The performance of the proposed cellulose membranes modified with polypyrrole device for real samples was evaluated after extraction of emerging contaminants from a river water sample from the city of Curitiba-Brazil. Bisphenol A (6.39 μg L -1 ), caffeine (17.83 μg L -1 ), and paracetamol (19.28 μg L -1 ) were found in these samples. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

High throughput screening and antioxidant assay of dibenzo[a,c]cyclooctadiene lignans in modified-ultrasonic and supercritical fluid extracts of Schisandra chinensis Baill by liquid chromatography--mass spectrometry and a free radical-scavenging method.

PubMed

Wang, Ming-Chih; Lai, Yih-Cherng; Chang, Chia-Lin

2008-05-01

Dibenzo[a,c]cyclooctadiene lignans of Schisandra chinensis Baill are well known because of their hepatoprotective activity, antioxidant activity, and anticancer effect. For the isolation of the dibenzo[a,c]cyclooctadiene lignans of Schisandra chinensis Baill two extraction methods were used: modified-ultrasonic extraction and supercritical fluid extraction. A specific and fast analytical method for structure identification is established for quality control because structure elucidation could be accomplished by means of liquid chromatography-mass spectrometry (LC-MS) technologies. The separation and identification of the compounds were completed by: (i) a water-acetonitrile gradient system using a C18 reversed-phase column; (ii) UV detection at 225 nm; (iii) MS/MS experiments with electrospray ionization interface (ESI) ion trap mass spectrometry in the positive mode. Normalized collision energy was used to obtain fragment ions of structural relevance in the LC-MS/MS. These results provided a reliable LC-MS/MS method for the determination of the dibenzo[a,c]cyclooctadiene lignans from Schisandra chinensis Baill. Finally, we also detected 1,1-diphenyl-2-picrylhydrazyl (DPPH) scavenging effects (%) of the modified-ultrasonic and supercritical fluid extracts of Schisandra chinensis Baill compared with 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox). The antioxidant activities of the modified-ultrasonic and supercritical fluid extracts were lower than that of trolox.

A novel star extraction method based on modified water flow model

NASA Astrophysics Data System (ADS)

Zhang, Hao; Niu, Yanxiong; Lu, Jiazhen; Ouyang, Zibiao; Yang, Yanqiang

2017-11-01

Star extraction is the essential procedure for attitude measurement of star sensor. The great challenge for star extraction is to segment star area exactly from various noise and background. In this paper, a novel star extraction method based on Modified Water Flow Model(MWFM) is proposed. The star image is regarded as a 3D terrain. The morphology is adopted for noise elimination and Tentative Star Area(TSA) selection. Star area can be extracted through adaptive water flowing within TSAs. This method can achieve accurate star extraction with improved efficiency under complex conditions such as loud noise and uneven backgrounds. Several groups of different types of star images are processed using proposed method. Comparisons with existing methods are conducted. Experimental results show that MWFM performs excellently under different imaging conditions. The star extraction rate is better than 95%. The star centroid accuracy is better than 0.075 pixels. The time-consumption is also significantly reduced.

Multiresidue Method for Quantification of Sulfonamides and Trimethoprim in Tilapia Fillet by Liquid Chromatography Coupled to Quadrupole Time-of-Flight Mass Spectrometry Using QuEChERS for Sample Preparation.

PubMed

Nunes, Kátia S D; Assalin, Márcia R; Vallim, José H; Jonsson, Claudio M; Queiroz, Sonia C N; Reyes, Felix G R

2018-01-01

A multiresidue method for detecting and quantifying sulfonamides (sulfapyridine, sulfamerazine, sulfathiazole, sulfamethazine, sulfadimethoxine, sulfamethoxazole, and sulfamethoxypyridazine) and trimethoprim in tilapia fillet ( Oreochromis niloticus ) using liquid chromatography coupled to mass spectrometry was developed and validated. The sample preparation was optimized using the QuEChERS approach. The chromatographic separation was performed using a C18 column and 0.1% formic acid in water and acetonitrile as the mobile phase in the isocratic elution mode. Method validation was performed based on the Commission Decision 2002/657/EC and Brazilian guideline. The validation parameters evaluated were linearity ( r  ≥ 0.99); limits of detection (LOD) and quantification (LOQ), 1 ng·g -1 and 5 ng·g -1 , respectively; intraday and interdays precision (CV lower than 19.4%). The decision limit (CC α 102.6-120.0 ng·g -1 and 70 ng·g -1 for sulfonamides and trimethoprim, respectively) and detection capability (CC β 111.7-140.1 ng·g -1 and 89.9 ng·g -1 for sulfonamides and trimethoprim, respectively) were determined. Analyses of tilapia fillet samples from fish exposed to sulfamethazine through feed (incurred samples) were conducted in order to evaluate the method. This new method was demonstrated to be fast, sensitive, and suitable for monitoring sulfonamides and trimethoprim in tilapia fillet in health surveillance programs, as well as to be used in pharmacokinetics and residue depletion studies.

Multiresidue Method for Quantification of Sulfonamides and Trimethoprim in Tilapia Fillet by Liquid Chromatography Coupled to Quadrupole Time-of-Flight Mass Spectrometry Using QuEChERS for Sample Preparation

PubMed Central

Nunes, Kátia S. D.; Assalin, Márcia R.; Vallim, José H.; Jonsson, Claudio M.; Queiroz, Sonia C. N.

2018-01-01

A multiresidue method for detecting and quantifying sulfonamides (sulfapyridine, sulfamerazine, sulfathiazole, sulfamethazine, sulfadimethoxine, sulfamethoxazole, and sulfamethoxypyridazine) and trimethoprim in tilapia fillet (Oreochromis niloticus) using liquid chromatography coupled to mass spectrometry was developed and validated. The sample preparation was optimized using the QuEChERS approach. The chromatographic separation was performed using a C18 column and 0.1% formic acid in water and acetonitrile as the mobile phase in the isocratic elution mode. Method validation was performed based on the Commission Decision 2002/657/EC and Brazilian guideline. The validation parameters evaluated were linearity (r ≥ 0.99); limits of detection (LOD) and quantification (LOQ), 1 ng·g−1 and 5 ng·g−1, respectively; intraday and interdays precision (CV lower than 19.4%). The decision limit (CCα 102.6–120.0 ng·g−1 and 70 ng·g−1 for sulfonamides and trimethoprim, respectively) and detection capability (CCβ 111.7–140.1 ng·g−1 and 89.9 ng·g−1 for sulfonamides and trimethoprim, respectively) were determined. Analyses of tilapia fillet samples from fish exposed to sulfamethazine through feed (incurred samples) were conducted in order to evaluate the method. This new method was demonstrated to be fast, sensitive, and suitable for monitoring sulfonamides and trimethoprim in tilapia fillet in health surveillance programs, as well as to be used in pharmacokinetics and residue depletion studies. PMID:29686929

21 CFR 177.1050 - Acrylonitrile/styrene copoly-mer modified with butadiene/styrene elastomer.

Code of Federal Regulations, 2013 CFR

2013-04-01

... chapter as Type VI-B under conditions for use E, F, or G described in table 2 of § 176.170(c) of this... copol-ymer is extracted with 250 milliliters spectral grade n-heptane at reflux temperature for 2 hours. (e) Accelerated extraction end test. The modified copolymer shall yield acrylonitrile monomer not in...

21 CFR 177.1050 - Acrylonitrile/styrene copoly-mer modified with butadiene/styrene elastomer.

Code of Federal Regulations, 2011 CFR

2011-04-01

... chapter as Type VI-B under conditions for use E, F, or G described in table 2 of § 176.170(c) of this... copol-ymer is extracted with 250 milliliters spectral grade n-heptane at reflux temperature for 2 hours. (e) Accelerated extraction end test. The modified copolymer shall yield acrylonitrile monomer not in...

21 CFR 177.1050 - Acrylonitrile/styrene copoly-mer modified with butadiene/styrene elastomer.

Code of Federal Regulations, 2012 CFR

2012-04-01

... chapter as Type VI-B under conditions for use E, F, or G described in table 2 of § 176.170(c) of this... copol-ymer is extracted with 250 milliliters spectral grade n-heptane at reflux temperature for 2 hours. (e) Accelerated extraction end test. The modified copolymer shall yield acrylonitrile monomer not in...

Effect of Plant Antimicrobial Agents Containing Marinades on Storage Stability and Microbiological Quality of Broiler Chicken Cuts Packed with Modified Atmosphere Packaging.

PubMed

Alakomi, H-L; Maukonen, J; Honkapää, K; Storgårds, E; Quirin, K-W; Yang, B; Saarela, M

2017-10-01

The food industry, including the meat industry, is currently looking for natural preservatives to prevent the growth of harmful microbes in foods. The potential of plant-derived antimicrobial extracts to increase the shelf life and to delay the microbiological spoilage of marinated broiler chicken cuts in modified atmosphere packages during cold storage was investigated in this study. We evaluated the impact of aqueous ethanolic extracts of Finnish sea buckthorn berries and lingonberries and supercritical CO 2 -extracted herbal extracts from an antimicrobial blend and oregano leaves on the shelf life of broiler meat. The commercial antimicrobial blend extract and the oregano extract inhibited the growth of lactic acid bacteria (LAB) and Brochothrix thermosphacta in the marinated samples. The antimicrobial blend extract also reduced the growth of psychrotrophic aerobic bacteria, whereas the sea buckthorn and lingonberry extracts did not. Only minor antimicrobial activity against Enterobacteriaceae by all the extracts was observed. Plate count analysis, denaturing gradient gel electrophoresis, and quantitative real-time PCR indicated that LAB, which are the major spoilage group in marinated modified atmosphere-packaged poultry products, were not significantly affected by the berry extracts studied. During this shelf-life study, LAB isolates of Lactobacillus and Leuconostoc were identified in the marinated samples. Antimicrobial blends and oregano leaf extracts can act as antimicrobial agents in marinade blends, although tailoring of the dose is needed because of their strong taste. Further studies for exploiting synergistic effects of plant extracts could contribute to the development of potential and more effective antimicrobial blends. Studies are needed in meat matrices and in product applications to demonstrate the efficacy of these compounds.

Application of a simple column-switching ion chromatography technique for removal of matrix interferences and sensitive fluorescence determination of acidic compounds (pharmaceutical drugs) in complex samples.

PubMed

Muhammad, Nadeem; Subhani, Qamar; Wang, Fenglian; Guo, Dandan; Zhao, Qiming; Wu, Shuchao; Zhu, Yan

2017-09-15

This work illustrates the introduction of a simple, rugged and flexible column-switching ion chromatography (IC) technique for an automated on-line QuEChERS extracted samples extracts washing followed by sensitive fluorescence (FLD) determination of five acidic pharmaceutical drugs namely; clofibric acid (CLO), ibuprofen (IBU), aspirin (ASP), naproxen (NAP) and flurobrofen (FLU) in three complex samples (spinach, apple and hospital sewage sludge). An old anion exchange column IonPac ® AS11-HC was utilized as a pre-treatment column for on-line washing of inorganic and organic interferences followed by isocratic separation of five acidic drugs with another anion exchange IonPac ® AS12A analytical column by exploiting the column-switching technique. This novel method exhibited good linearity with correlation coefficients (r 2 ) for all drugs were in the range 0.976-0.996. The limit of detection and quantification of all five acidic drugs were in the range 0.024μg/kg to 8.70μg/kg and 0.082μg/kg to 0.029mg/kg, respectively, and better recoveries in the range 81.17-112.5% with percentage relative standard deviations (RSDs) less than 17.8% were obtained. This on-line sample pre-treatment method showed minimum matrix effect in the range of 0.87-1.25 except for aspirin. This simple rugged and flexible column-switching system required only 28min for maximum elimination of matrices and interferences in three complex samples extracts, isocratic separation of five acidic drugs and for the continuous regeneration of pre-treatment column prior to every subsequent analysis. Finally, this simple automated IC system was appeared so rugged and flexible, which can eliminate and wash out most of interference, impurities and matrices in complex samples, simply by adjusting the NaOH and acetonitrile concentration in washing mobile phase with maximum recoveries of acidic analytes of interest. Copyright © 2017. Published by Elsevier B.V.

Human dermal exposure to galaxolide from personal care products.

PubMed

Correia, P; Cruz, A; Santos, L; Alves, A

2013-06-01

Musks are synthetic fragrances applied on personal care and household products as fixatives, by retarding the release of other fragrances with higher volatility. Galaxolide is the most used polycyclic musk since the 90th decade, and it has been detected in several environmental and biological matrices, particularly in human tissues and fluids. For exposure assessment purposes, large-monitoring data need to be obtained and rapid but reliable analytical techniques are requested. The main objective of this study is to develop and validate a new and fast analytical methodology to quantify galaxolide in personal care products and to apply this method to real matrices like skin care products (creams and lotions), shower products (soap bar), hair care products (shampoo and hair conditioner) and oral care products (toothpaste), to evaluate the human dermal exposure risk. A dispersive solid-phase extraction is proposed, using QuEChERS methodology, followed by HPLC with fluorescence detection. Some extraction parameters were studied, like the ratio of sample/solvent amounts, the homogenization time, the salt addition effect and the used sorbents. The validation parameters of the developed method were the following: a linearity range of 0.005-1.002 mg kg⁻¹ sample, a limit of detection of 0.001 mg kg⁻¹ sample, repeatability between 0.7% and 11.3% (variation coefficient of six standard injections), an intermediate precision of 2.5% (variation coefficient of six independent analysis of the same sample), mean recoveries ranging from 65% (soap bar) to 95% (body cream) and 3% of global uncertainty in most of the working range. The time of analysis, including the extraction steps, is 60 min, allowing a throughput of 4 samples h⁻¹ . Galaxolide was detected in all of the seven analysed products in concentrations ranging from 0.04 ± 0.01 mg kg⁻¹ sample (toothpaste) to 280.78 ± 8.19 mg kg⁻¹ sample (perfumed body cream), which may correspond to a significant estimated daily human dermal exposure of 904 μg day⁻¹. © 2013 Society of Cosmetic Scientists and the Société Française de Cosmétologie.

Comparison of leaching characteristics of heavy metals in APC residue from an MSW incinerator using various extraction methods.

PubMed

Chiang, Kung-Yuh; Tsai, Chen-Chiu; Wang, Kuen-Sheng

2009-01-01

This study investigates four extraction methods (water extraction, toxicity characteristics leaching procedure (TCLP), modified TCLP with pH control, and sequential chemical extraction (SCE)), each representing different liquid-to-solid (L/S) ratios, pH controls, and types of leachant, and their effects on the leaching concentration of heavy metals in municipal solid waste (MSW) incinerator air pollution control (APC) residue. The results indicated that for extraction with distilled water, the heavy metal leaching concentration (mg/l) decreased with L/S ratio, but the amount of heavy metal released (AHMR), defined as the leached amount of heavy metals to the weight of the tested sample (mg/kg), increased with an increase in L/S ratio, in the range of 2-100. The results also showed that both the leaching concentration and the amount of released metals were strongly pH-dependent in the TCLP and modified TCLP tests. In the case of pHs lower than 6.5, the leaching concentrations of Cd, Pb, Cu, Zn, and Cr decreased with an increase in pH. As pH increased higher than 6.5, Cr and Zn were almost insoluble. Meanwhile, Cd and Cu also showed a similar trend but at pHs of 8.5 and 7.5, respectively. Due to the nature of amphoteric elements, in the case of pHs higher than 7, the Pb leaching concentration increased with increasing pH. In modified TCLP tests with the pH value controlled at the same level as in the SCE test, the heavy metal speciation approached the extractable carbonate bound fraction by the SCE. Both amounts of targeted metals leached from the SCE and modified TCLP tests were much higher than those for the regular TCLP and water extraction tests.

In Vitro Antibacterial and Antibiotic Resistance Modifying Effect of Bioactive Plant Extracts on Methicillin-Resistant Staphylococcus epidermidis

PubMed Central

Chovanová, Romana; Vaverková, Štefánia

2013-01-01

The crude extracts of plants from Asteraceae and Lamiaceae family and essential oils from Salvia officinalis and Salvia sclarea were studied for their antibacterial as well as antibiotic resistance modifying activity. Using disc diffusion and broth microdilution assays we determined higher antibacterial effect of three Salvia spp. and by evaluating the leakage of 260 nm absorbing material we detected effect of extracts and, namely, of essential oils on the disruption of cytoplasmic membrane. The evaluation of in vitro interactions between plant extracts and oxacillin described in terms of fractional inhibitory concentration (FIC) indices revealed synergistic or additive effects of plant extracts and clearly synergistic effects of essential oil from Salvia officinalis with oxacillin in methicillin-resistant Staphylococcus epidermidis. PMID:24222768

Nonthermal plasma processor utilizing additive-gas injection and/or gas extraction

DOEpatents

Rosocha, Louis A.

2006-06-20

A device for processing gases includes a cylindrical housing in which an electrically grounded, metal injection/extraction gas supply tube is disposed. A dielectric tube surrounds the injection/extraction gas supply tube to establish a gas modification passage therearound. Additionally, a metal high voltage electrode circumscribes the dielectric tube. The high voltage electrode is energizable to create nonthermal electrical microdischarges between the high voltage electrode and the injection/extraction gas supply tube across the dielectric tube within the gas modification passage. An injection/extraction gas and a process gas flow through the nonthermal electrical microdischarges within the gas modification passage and a modified process gas results. Using the device contaminants that are entrained in the process gas can be destroyed to yield a cleaner, modified process gas.

[Specific immunotherapy with depigmented allergoids].

PubMed

Klimek, L; Thorn, C; Pfaar, O

2010-01-01

Specific immunotherapy is the only available causative treatment for IgE-mediated allergic conditions. The state of the art is treatment via the subcutaneous route with crude extracts in a water solution, with physically linked (semidepot) extracts or chemically modified semidepot extracts (allergoids). A relatively new purification method combines depigmentation followed by polymerization with glutaraldehyde. This modification results in increased tolerance with a reduction in both local and systemic adverse effects. As controlled clinical trials have shown, the effectiveness is comparable to that of specific immunotherapy with crude allergen extracts. Recent data suggest that the modified polymerized allergoids allow a safe rush titration in a few days or even in 1 day (ultra-rush titration).

Ultrarush schedule of subcutaneous immunotherapy with modified allergen extracts is safe in paediatric age.

PubMed

Morais-Almeida, Mário; Arêde, Cristina; Sampaio, Graça; Borrego, Luis Miguel

2016-01-01

Traditional subcutaneous immunotherapy up dosing with allergenic extracts has been shown to be associated with frequent adverse reactions. In recent studies it has been demonstrated that using modified extracts, namely allergoids, it is a safe and effective procedure particularly on accelerated schedules. However data assessing its safety in paediatric age is scarce. To evaluate the safety profile in paediatric population of using modified allergen extracts, in an ultrarush schedule, to reach the maintenance dose in the first day. We included children undergoing treatment with subcutaneous immunotherapy during a five-year period, using modified aeroallergen extracts, depigmented, polymerized with glutaraldehyde and adsorbed on aluminium hydroxide using an ultrarush induction phase. The type of adverse reactions during the ultrarush protocol was recorded. We studied 100 paediatric patients (57 males) with a mean age of 11.6 years (5 to 18 years; standard deviation, 3.3), all with moderate to severe persistent rhinitis, with or without allergic conjunctivitis, asthma and atopic eczema, sensitized to mites and/or pollens. All reached the maintenance dose of 0.5 mL in the first day, except 1 child. During the ultrarush protocol the total number of injections was 199. There were 21 local adverse reactions in 11 patients, 11 immediate and 10 delayed; from those, had clinical relevance 1 immediate and 4 delayed. Systemic reactions were recorded in 2 cases, both immediate and mild. The ultrarush protocol, without premedication, was a safe alternative to be used in paediatric age during the induction phase of subcutaneous immunotherapy using allergoid depigmented extracts.

Ultrarush schedule of subcutaneous immunotherapy with modified allergen extracts is safe in paediatric age

PubMed Central

Arêde, Cristina; Sampaio, Graça; Borrego, Luis Miguel

2016-01-01

Background Traditional subcutaneous immunotherapy up dosing with allergenic extracts has been shown to be associated with frequent adverse reactions. In recent studies it has been demonstrated that using modified extracts, namely allergoids, it is a safe and effective procedure particularly on accelerated schedules. However data assessing its safety in paediatric age is scarce. Objective To evaluate the safety profile in paediatric population of using modified allergen extracts, in an ultrarush schedule, to reach the maintenance dose in the first day. Methods We included children undergoing treatment with subcutaneous immunotherapy during a five-year period, using modified aeroallergen extracts, depigmented, polymerized with glutaraldehyde and adsorbed on aluminium hydroxide using an ultrarush induction phase. The type of adverse reactions during the ultrarush protocol was recorded. Results We studied 100 paediatric patients (57 males) with a mean age of 11.6 years (5 to 18 years; standard deviation, 3.3), all with moderate to severe persistent rhinitis, with or without allergic conjunctivitis, asthma and atopic eczema, sensitized to mites and/or pollens. All reached the maintenance dose of 0.5 mL in the first day, except 1 child. During the ultrarush protocol the total number of injections was 199. There were 21 local adverse reactions in 11 patients, 11 immediate and 10 delayed; from those, had clinical relevance 1 immediate and 4 delayed. Systemic reactions were recorded in 2 cases, both immediate and mild. Conclusion The ultrarush protocol, without premedication, was a safe alternative to be used in paediatric age during the induction phase of subcutaneous immunotherapy using allergoid depigmented extracts. PMID:26844218

Recovery of oil components of okara by ethanol-modified supercritical carbon dioxide extraction.

PubMed

Quitain, Armando T; Oro, Kazuyuki; Katoh, Shunsaku; Moriyoshi, Takashi

2006-09-01

Recovery of the oil components of okara by ethanol-modified supercritical carbon dioxide extraction was investigated at 40-80 degrees C temperature and 12-30 MPa pressure. In a typical run (holding period of 2 h, continuous flow extraction of 5 h), results indicated that the oil component could be best obtained with a recovery of 63.5% at relatively low temperature of 40 degrees C and mild pressure of 20 MPa in the presence of 10 mol% EtOH as entrainer. Based on gas chromatography-mass spectrometry (GC-MS) analysis, the extracts consisted mainly of fatty acids and phytosterols, and traces of decadienal. Folin-Ciocalteau estimates of total phenols showed that addition of EtOH as entrainer increased the yield and the amount of phenolic compounds in the extracts. The amounts of two primary soy isoflavones, genistein and daidzein, in the extracts also increased with increasing amount of EtOH.

Optimization of supercritical fluid extraction and HPLC identification of wedelolactone from Wedelia calendulacea by orthogonal array design.

PubMed

Patil, Ajit A; Sachin, Bhusari S; Wakte, Pravin S; Shinde, Devanand B

2014-11-01

The purpose of this work is to provide a complete study of the influence of operational parameters of the supercritical carbon dioxide assisted extraction (SC CO2E) on yield of wedelolactone from Wedelia calendulacea Less., and to find an optimal combination of factors that maximize the wedelolactone yield. In order to determine the optimal combination of the four factors viz. operating pressure, temperature, modifier concentration and extraction time, a Taguchi experimental design approach was used: four variables (three levels) in L9 orthogonal array. Wedelolactone content was determined using validated HPLC methodology. Optimum extraction conditions were found to be as follows: extraction pressure, 25 MPa; temperature, 40 °C; modifier concentration, 10% and extraction time, 90 min. Optimum extraction conditions demonstrated wedelolactone yield of 8.01 ± 0.34 mg/100 g W. calendulacea Less. Pressure, temperature and time showed significant (p < 0.05) effect on the wedelolactone yield. The supercritical carbon dioxide extraction showed higher selectivity than the conventional Soxhlet assisted extraction method.

Optimization of supercritical fluid extraction and HPLC identification of wedelolactone from Wedelia calendulacea by orthogonal array design

PubMed Central

Patil, Ajit A.; Sachin, Bhusari S.; Wakte, Pravin S.; Shinde, Devanand B.

2013-01-01

The purpose of this work is to provide a complete study of the influence of operational parameters of the supercritical carbon dioxide assisted extraction (SC CO2E) on yield of wedelolactone from Wedelia calendulacea Less., and to find an optimal combination of factors that maximize the wedelolactone yield. In order to determine the optimal combination of the four factors viz. operating pressure, temperature, modifier concentration and extraction time, a Taguchi experimental design approach was used: four variables (three levels) in L9 orthogonal array. Wedelolactone content was determined using validated HPLC methodology. Optimum extraction conditions were found to be as follows: extraction pressure, 25 MPa; temperature, 40 °C; modifier concentration, 10% and extraction time, 90 min. Optimum extraction conditions demonstrated wedelolactone yield of 8.01 ± 0.34 mg/100 g W. calendulacea Less. Pressure, temperature and time showed significant (p < 0.05) effect on the wedelolactone yield. The supercritical carbon dioxide extraction showed higher selectivity than the conventional Soxhlet assisted extraction method. PMID:25687584

Polytetrafluoroethylene-jacketed stirrer modified with graphene oxide and polydopamine for the efficient extraction of polycyclic aromatic hydrocarbons.

PubMed

Zhang, Zinxin; Mwadini, Mwadini Ahmada; Chen, Zilin

2016-10-01

Steel stirrers jacketed with polytetrafluoroethylene can be regarded as an ideal substrate for stirrer bar sorptive extraction. However, it is still a great challenge to immobilize graphene onto a polytetrafluoroethylene stirrer due to the high chemical resistance of the surface of a polytetrafluoroethylene stirrer. We describe here a method to modify the surface of polytetrafluoroethylene stirrers with graphene. In this work, graphene was used as the sorbent due to its excellent adsorption capability for aromatic compounds, such as polycyclic aromatic compounds. Graphene was successfully immobilized onto polytetrafluoroethylene-stirrer by a bio-inspired polydopamine functionalization method. The graphene-modified polytetrafluoroethylene-stirrer shows good stability and tolerance to stirring, ultrasonication, strong acidic and basic solutions, and to organic solvents. The multilayer coating was characterized by scanning electronic microscopy and Fourier transform infrared spectroscopy. After the optimization of some experimental conditions, the graphene-modified polytetrafluoroethylene stirrer was used for the stirrer bar sorptive extraction of polycyclic aromatic hydrocarbons, in which the binding between the polycyclic aromatic hydrocarbons and the graphene layer was mainly based on π-π stacking and hydrophobic interactions. The graphene-modified polytetrafluoroethylene-stirrer-based stirrer bar sorptive extraction and high-performance liquid chromatography method was developed for the determination of polycyclic aromatic hydrocarbons with great extraction efficiency, with enrichment factors from 18 to 62. The method has low limits of detection of 1-5 pg/mL, wide linear range (5-100 and 10-200 pg/mL), good linearity (R ≥ 0.9957) and good reproducibility (RSD ≤ 6.45%). The proposed method has been applied to determine polycyclic aromatic hydrocarbons in real dust samples. Good recoveries were obtained, ranging from 88.53 to 109.43%. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rapid screening and quantification of residual pesticides and illegal adulterants in red wine by direct analysis in real time mass spectrometry.

PubMed

Guo, Tianyang; Fang, Pingping; Jiang, Juanjuan; Zhang, Feng; Yong, Wei; Liu, Jiahui; Dong, Yiyang

2016-11-04

A rapid method to screen and quantify multi-class analytic targets in red wine has been developed by direct analysis in real time (DART) coupled with triple quadruple tandem mass spectrometry (QqQ-MS). A modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) procedure was used for increasing analytical speed and reducing matrix effect, and the multiple reaction monitoring (MRM) in DART-MS/MS ensured accurate analysis. One bottle of wine containing 50 pesticides and 12 adulterants, i.e., preservatives, antioxidant, sweeteners, and azo dyes, could be totally determined less than 12min. This method exhibited proper linearity (R 2 ≥0.99) in the range of 1-1000ng/mL for pesticides and 10-5000ng/mL for adulterants. The limits of detection (LODs) were obtained in a 0.5-50ng/mL range for pesticides and 5-50ng/mL range for adulterants, and the limits of quantification (LOQs) were in a 1-100ng/mL range for pesticides and 10-250ng/mL range for adulterants. Three spiked levels for each analyte in wine were evaluated, and the recoveries were in a scope of 75-120%. The results demonstrated DART-MS/MS was a rapid and simple method, and could be applied to rapid analyze residual pesticides and illegal adulterants in a large quantities of red wine. Copyright © 2016 Elsevier B.V. All rights reserved.

ANALYSIS OF OUT OF DATE MCU MODIFIER LOCATED IN SRNL

DOE Office of Scientific and Technical Information (OSTI.GOV)

Crawford, C.

2014-10-22

SRNL recently completed density measurements and chemical analyses on modifier samples stored in drums within SRNL. The modifier samples date back to 2008 and are in various quantities up to 40 gallons. Vendor information on the original samples indicates a shelf life of 5 years. There is interest in determining if samples that have been stored for more than the 5 year shelf life are still acceptable for use. The Modular Caustic Side Solvent Extraction Unit (MCU) Solvent component Cs-7SB [(2,2,3,3- tetraflouropropoxy)-3-(4-sec-butylphenoxy)-2-propanol, CAS #308362-88-1] is used as a diluent modifier to increase extractant solubility and provide physical characteristics necessary formore » diluent trimming.« less

Soft Tissue Closure of Grafted Extraction Sockets in the Anterior Maxilla: A Modified Palatal Pedicle Connective Tissue Flap Technique.

PubMed

El Chaar, Edgard; Oshman, Sarah; Cicero, Giuseppe; Castano, Alejandro; Dinoi, Cinzia; Soltani, Leila; Lee, Yoonjung Nicole

Localized ridge resorption, the consequence of socket collapse, following tooth extraction in the anterior maxilla can adversely affect esthetics, function, and future implant placement. Immediate grafting of extraction sockets may help preserve natural ridge contours, but a lack of available soft tissue can compromise the final esthetic outcome. The presented modified rotated palatal pedicle connective tissue flap is a useful technique for simultaneous soft tissue coverage and augmentation of grafted sockets to improve esthetic outcome. This article delineates its advantages through the presentation of a four-case series using this new technique.

Determination of organochlorine pesticide and polychlorinated biphenyl residues in fatty fish by tandem solid-phase extraction cleanup.

PubMed

Schenck, F J; Calderon, L; Podhorniak, L V

1996-01-01

A rapid, multiresidue solid-phase extraction (SPE) technique for determination of organochlorine pesticide and polychlorinated biphenyl (PCB) residues in nonfatty fish was modified for use with fatty fish. In the modified procedures, samples are extracted with acetonitrile, and the extract is cleaned up with both C18 and Florisil SPE columns. Residues are determined by gas chromatography with electron capture detection. The original method was modified for use with fatty fish by reducing the amount of tissue extracted and by using an improved Florisil SPE cleanup. Recovery data are presented for 24 fortified organochlorine pesticide residues (0.12 ppm) and 3 fortified PCB residues (0.80 ppm) from flounder, bluefish, and shad samples, which contained 0.8, 5.4, and 22.6% fat, respectively. For the 3 types of fish, recoveries of 23 of 24 fortified organochlorine pesticide residues ranged from 55 to 129%, and recoveries of 3 fortified PCB residues ranged from 55 to 104%. There were no significant differences in recovery based on fish species and/or fat content for the majority of residues studied. This SPE method and the official AOAC method yielded comparable results for fish containing incurred organochlorine residues.

A magnet built on bronchoscopic suction for extraction of tracheobronchial headscarf pins: a novel technique and review of a tertiary centre experience†

PubMed Central

Elsayed, Hany H.; Mostafa, Ahmed M.; Soliman, Saleh; El-Bawab, Hatem Y.; Moharram, Adel A.; El-Nori, Ahmed A.

2016-01-01

OBJECTIVES Airway metal pins are one of the most commonly inhaled foreign bodies in Eastern societies in young females wearing headscarves. We innovated a modified bronchoscopic technique to extract tracheobronchial headscarf pins by the insertion of a magnet to allow an easy and non-traumatic extraction of the pins. The aim of this study was to assess the feasibility and safety of our new technique and compare it with our large previous experience with the classic bronchoscopic method of extraction of tracheobronchial headscarf pins. METHODS We performed a study comparing our retrospective experience of classic bronchoscopic extraction from February 2004 to January 2014 and prospective experience with our modified technique using the magnet from January 2014 to June 2015. An institutional review board and new device approval were obtained. RESULTS Three hundred and twenty-six procedures on 315 patients were performed during our initial 10-year experience. Of them, 304 patients were females. The median age of our group was 13 (0–62). The median time from inhalation to procedure was 1 day (0–1022). After introducing our modified new technique using the magnet, 20 procedures were performed. Nineteen were females. The median time of the procedure and the need to forcefully bend the pin for extraction were in favour of the new technique in comparison with our classic approach (2 vs 6 min; P < 0.001) (2 patients = 20% vs 192 = 58%; P < 0.001). The conversion rate to surgery was also in favour of the modified technique but did not reach statistical significance (0 = 0% vs 15 = 4.8%; P = 0.32). All patients who underwent the modified technique were discharged home on the same day of the procedure. No procedural complications were recorded. All remain well on a follow-up period of up to 14 months. CONCLUSIONS Bronchoscopic extraction of tracheobronchial inhaled headscarf pins using a novel technique using homemade magnets was safer and simpler in comparison with our large experience with the classic approach. We advise the use of this device (or concept) in selected patients in centres dealing with this problem. PMID:26850113

Immobilization of microalgae cells in alginate facilitates isolation of DNA and RNA.

PubMed

Lopez, Blanca R; Hernandez, Juan-Pablo; Bashan, Yoav; de-Bashan, Luz E

2017-04-01

Isolation of nucleic acids from Chlorella is difficult, given the chemically complex nature of their cell walls and variable production of metabolites. Immobilization of microalgae in polymers adds additional difficulty. Here, we modified, amended, and standardized methods for isolation of nucleic acids and compared the yield of DNA and RNA from free-living and encapsulated microalgae C. sorokiniana. Isolation of nucleic acids from immobilized cells required two steps in dissolving the alginate matrix, releasing the cells, and mechanical disruption with glass beads. For DNA extraction, we used modified versions of a commercial kit along with the hexadecyltrimethylammonium bromide (CTAB) method. For RNA extraction, we used the commercial TRI reagent procedure and the CTAB-dithiotreitol method. Quantity and quality of nucleic acids in extracts varied with growth conditions, isolation procedures, and time of incubation of the original culture. There were consistently higher amounts of DNA and RNA in extracts from immobilized cells. Quantitatively, the modified procedure with the commercial Promega kit was the most reliable procedure for isolating DNA and a modified commercial TRI reagent procedure was the choice for isolating RNA. All four procedures eliminated proteins efficiently and had low levels of contamination from residual polysaccharides from the matrices and/or metabolites naturally produced by the microalgae. All DNA extracts under both growth conditions, time of incubation, and two isolation methods successfully amplified the 18S ribosomal RNA by PCR and quantitative reverse transcription (RT-qPCR). Copyright © 2017 Elsevier B.V. All rights reserved.

A comparative analysis of modified binders : original asphalts and materials extracted from existing pavements.

DOT National Transportation Integrated Search

2010-01-18

This research demonstrated the application of gel permeation chromatography (GPC) as an analytical tool to : ascertain the amounts of polymer modifiers in polymer modified asphalt cements, which are soluble in eluting GPC : solvents. The technique wa...

A Comparative Analysis of Modified Binders : Original Asphalt and Material Extracted from Existing Pavement

DOT National Transportation Integrated Search

2010-01-18

This research demonstrated the application of gel permeation chromatography (GPC) as an analytical tool to ascertain the amounts of polymer modifiers in polymer modified asphalt cements, which are soluble in eluting GPC solvents. The technique was ap...

Supercritical Fluid Extraction of Aflatoxin B 1 from Soil

EPA Science Inventory

This research describes the development of a Supercritical Fluid Extraction (SFE) method to recover aflatoxin B1 from fortified soil. The effects of temperature, pressure, modifier (identity and percentage), and extraction type were assessed. Using the optimized SFE conditions, ...

Improved Detection of Norovirus and Hepatitis A Virus in Surface Water by Applying Pre-PCR Processing.

PubMed

Borgmästars, Emmy; Jazi, Mehrdad Mousavi; Persson, Sofia; Jansson, Linda; Rådström, Peter; Simonsson, Magnus; Hedman, Johannes; Eriksson, Ronnie

2017-12-01

Quantitative reverse transcriptase polymerase chain reaction (RT-qPCR) detection of waterborne RNA viruses generally requires concentration of large water volumes due to low virus levels. A common approach is to use dead-end ultrafiltration followed by precipitation with polyethylene glycol. However, this procedure often leads to the co-concentration of PCR inhibitors that impairs the limit of detection and causes false-negative results. Here, we applied the concept of pre-PCR processing to optimize RT-qPCR detection of norovirus genogroup I (GI), genogroup II (GII), and hepatitis A virus (HAV) in challenging water matrices. The RT-qPCR assay was improved by screening for an inhibitor-tolerant master mix and modifying the primers with twisted intercalating nucleic acid molecules. Additionally, a modified protocol based on chaotropic lysis buffer and magnetic silica bead nucleic acid extraction was developed for complex water matrices. A validation of the modified extraction protocol on surface and drinking waters was performed. At least a 26-fold improvement was seen in the most complex surface water studied. The modified protocol resulted in average recoveries of 33, 13, 8, and 4% for mengovirus, norovirus GI, GII, and HAV, respectively. The modified protocol also improved the limit of detection for norovirus GI and HAV. RT-qPCR inhibition with C q shifts of 1.6, 2.8, and 3.5 for norovirus GI, GII, and HAV, respectively, obtained for the standard nucleic acid extraction were completely eliminated by the modified protocol. The standard nucleic acid extraction method worked well on drinking water with no RT-qPCR inhibition observed and average recoveries of 80, 124, 89, and 32% for mengovirus, norovirus GI, GII, and HAV, respectively.

Multi-residue method for the determination of pesticides and pesticide metabolites in honeybees by liquid and gas chromatography coupled with tandem mass spectrometry--Honeybee poisoning incidents.

PubMed

Kiljanek, Tomasz; Niewiadowska, Alicja; Semeniuk, Stanisław; Gaweł, Marta; Borzęcka, Milena; Posyniak, Andrzej

2016-02-26

A method for the determination of 200 pesticides and pesticide metabolites in honeybee samples has been developed and validated. Almost 98% of compounds included in this method are approved to use within European Union, as active substances of plant protection products or veterinary medicinal products used by beekeepers to control mites Varroa destructor in hives. Many significant metabolites, like metabolites of imidacloprid, thiacloprid, fipronil, methiocarb and amitraz, are also possible to detect. The sample preparation was based on the buffered QuEChERS method. Samples of bees were extracted with acetonitrile containing 1% acetic acid and then subjected to clean-up by dispersive solid phase extraction (dSPE) using a new Z-Sep+ sorbent and PSA. The majority of pesticides, including neonicotionoids and their metabolites, were analyzed by liquid chromatography tandem mass spectrometry (LC-MS/MS) but some of pesticides, especially pyrethroid insecticides, were analyzed by gas chromatography tandem mass spectrometry (GC-MS/MS). The procedure was validated according to the Guidance document SANCO/12571/2013 at four concentration levels: 1, 5, 10 and 100 ng/g bees and verified in the international proficiency test. The analysis of bee samples spiked at the limit of quantification (LOQ) showed about 98% mean recovery value (trueness) and 97% of analytes showed recovery in the required range of 70-120% and RSDr (precision) below 20%. Linearity and matrix effects were also established. The LOQs of pesticides were in the range of 1-100 ng/g. The developed method allows determination of insecticides at concentrations of 10 ng/g or less, except abamectin and tebufenozide. LOQ values are lower than the median lethal doses LD50 for bees. The method was used to investigate more than 70 honeybee poisoning incidents. Data about detected pesticides and their metabolites are included. Copyright © 2016 Elsevier B.V. All rights reserved.

Development of a multi-residue enantiomeric analysis method for 9 pesticides in soil and water by chiral liquid chromatography/tandem mass spectrometry.

PubMed

Li, Yuanbo; Dong, Fengshou; Liu, Xingang; Xu, Jun; Chen, Xiu; Han, Yongtao; Liang, Xuyang; Zheng, Yongquan

2013-04-15

A novel and sensitive chiral liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) method was developed and validated for simultaneous measuring individual enantiomers of 9 pesticides including herbicides, insecticides, and fungicides in soil and water. The separation and determination were performed using reversed-phase chromatography on an amylose chiral stationary phase, a Chiralpak AD-RH column, under gradient elution using a mixture of ACN-2mM ammonium acetate in water as the mobile phase at 0.45 mL/min flow rate. The effects of three cellulose-based columns and three amylose-based columns on the separation were also investigated. The QuEChERS (acronym for Quick, Easy, Cheap, Effective, Rugged and Safe) method and solid-phase extraction (SPE) were used for the extraction and clean-up of the soil and water samples, respectively. Parameters including the matrix effect, linearity, precision, accuracy and stability were undertaken. Under optimal conditions, the mean recoveries for all enantiomers from the soil and water samples were ranged from 77.8% to 106.2% with the relative standard deviations (RSD) less than 14.2%. Good linearity (at least R(2) ≥ 0.9986) was obtained for all studied analytes in the soil and water matrix calibration curves over the range from 2.0 to 125 μg/L. The limits of detection (LOD) for all enantiomers in the soil and water were less than 1.8 μg/kg or μg/L, whereas the limit of quantification (LOQ) did not exceed 5.0 μg/kg or μg/L. The results of the method validation confirm that this proposed method is convenient and reliable for the enantioselective determination of the enantiomers of 9 chiral pesticides in soil and water. Copyright © 2013 Elsevier B.V. All rights reserved.

Validation of a method for the determination of 120 pesticide residues in apples and cucumbers by LC-MS/MS.

PubMed

Ramadan, Gouda; Al Jabir, Muna; Alabdulmalik, Najat; Mohammed, Ali

2016-05-01

Most countries have clearly defined regulations governing the use of pesticides in agricultural activity. The application of pesticides in agriculture usually leads to a residual amount of these pesticides on food products such as fruit and vegetables. The presence of pesticide residues on these foods destined for human consumption may pose food safety risks to consumers. To protect consumers, national authorities have established maximum limits for pesticide residues in foods. These limits can only be enforced if there are methods available to detect and monitor their concentrations in the applicable food products. To support the enforcement of this legislation, we have developed a multi-residue liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for the analysis of 120 pesticide residues in apples and cucumbers which has been validated and implemented in the routine monitoring and surveillance programme for these pesticides. In this method, apple and cucumber samples are extracted using the QuEChERS method (quick, easy, cheap, effective, rugged, and safe) and the extracts were analyzed directly by LC-MS/MS. The mean recoveries at three different concentrations of 0.01 µg/g , 0.05 µg/g, and 0.1 µg/g over the analytical range varied between 70 and 120%. The repeatability of the method expressed as %RSD was less than 20%. The limit of detection (LOD) of the method ranged between 0.0014 and 0.0110 µg/g for apples and between 0.0012 and 0.0075 µg/g for cucumbers. The limit of quantification (LOQ) of the method was 0.01 µg/g for apples and cucumbers. The method has been used for the analysis of over 600 apple and 550 cucumber samples over the past two years. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

SUPERCRITICAL FLUID EXTRACTION OF SEMI-VOLATILE ORGANIC COMPOUNDS FROM PARTICLES

EPA Science Inventory

A nitrogen oxide flux chamber was modified to measure the flux of semi-volatile organic compounds (SVOCs). Part of the modification involved the development of methods to extract SVOCs from polyurethane foam (PUF), sand, and soil. Breakthroughs and extraction efficiencies were ...

A new modification method of a Cetyl Trimethyl Ammonium Bromide/Nano-ZnO and Multi-walled Carbon Nanotubes Electrode for Determination of Anti Doping in Urine

NASA Astrophysics Data System (ADS)

Zhao, Zhiwei; Mu, Shuai; Zheng, Jie; Gu, Lingyan; Shen, Guijun; Shen, Yuan

2017-07-01

The preparation and application of Cetyl Trimethyl Ammonium Bromide/Nano-ZnO and Multi-walled Carbon Nanotubes (CTAB/ZnO-MWNTs) Modified Electrodes was studied, establishing a new electrochemical method for determination of carteolol hydrochloride in urine. After its pre-enrichment by adsorption and extraction on modified electrodes, electrochemical behaviors of carteolol hydrochloride on the modified electrodes were studied by CV and DPV. The response is linear at the range of 1×10-3 ∼ 2×10-1 g/L, with a detection limit of 2×10-4 g/L. Under appropriate conditions, the content of carteolol hydrochloride in urine can be determined directly by the method, which had strong anti-interference ability and the recovery is 96.5% - 110.5%. In addition, extraction and adsorption behaviors of the modified electrodes for carteolol hydrochloride were studied by chronocoulumetry, and the results showed that extraction during the enrichment process played a major role at low concentrations, and contribution of surface adsorption became greater with the increase of concentrations.

Dicationic polymeric ionic-liquid-based magnetic material as an adsorbent for the magnetic solid-phase extraction of organophosphate pesticides and polycyclic aromatic hydrocarbons.

PubMed

Jiang, Qiong; Liu, Qin; Chen, Qiliang; Zhao, Wenjie; Xiang, Guoqiang; He, Lijun; Jiang, Xiuming; Zhang, Shusheng

2016-08-01

Magnetic particles modified with a dicationic polymeric ionic liquid are described as a new adsorbent in magnetic solid-phase extraction. They were obtained through the copolymerization of a 1,8-di(3-vinylimidazolium)octane-based ionic liquid with vinyl-modified SiO2 @Fe3 O4 , and were characterized by FTIR spectroscopy, X-ray diffraction, and vibrating sample magnetometry. The modified magnetic particles are effective in the extraction of organophosphate pesticides and polycyclic aromatic hydrocarbons. Also, they can provide different extraction performance for the selected analytes including fenitrothion, parathion, fenthion, phoxim, phenanthrene, and fluoranthene, where the extraction efficiency is found to be in agreement with the hydrophobicity of analytes. Various factors influencing the extraction efficiency, such as, the amount of adsorbent, extraction, and desorption time, and type and volume of the desorption solvent, were optimized. Under the optimized conditions, a good linearity ranging from 1-100 μg/L is obtained for all analytes, except for parathion (2-200 μg/L), where the correlation coefficients varied from 0.9960 to 0.9998. The limits of detection are 0.2-0.8 μg/L, and intraday and interday relative standard deviations are 1.7-7.4% (n = 5) and 3.8-8.0% (n = 3), respectively. The magnetic solid-phase extraction combined with high-performance liquid chromatography can be applied for the detection of trace targets in real water samples with satisfactory relative recoveries and relative standard deviations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optimization of sample preparation variables for wedelolactone from Eclipta alba using Box-Behnken experimental design followed by HPLC identification.

PubMed

Patil, A A; Sachin, B S; Shinde, D B; Wakte, P S

2013-07-01

Coumestan wedelolactone is an important phytocomponent from Eclipta alba (L.) Hassk. It possesses diverse pharmacological activities, which have prompted the development of various extraction techniques and strategies for its better utilization. The aim of the present study is to develop and optimize supercritical carbon dioxide assisted sample preparation and HPLC identification of wedelolactone from E. alba (L.) Hassk. The response surface methodology was employed to study the optimization of sample preparation using supercritical carbon dioxide for wedelolactone from E. alba (L.) Hassk. The optimized sample preparation involves the investigation of quantitative effects of sample preparation parameters viz. operating pressure, temperature, modifier concentration and time on yield of wedelolactone using Box-Behnken design. The wedelolactone content was determined using validated HPLC methodology. The experimental data were fitted to second-order polynomial equation using multiple regression analysis and analyzed using the appropriate statistical method. By solving the regression equation and analyzing 3D plots, the optimum extraction conditions were found to be: extraction pressure, 25 MPa; temperature, 56 °C; modifier concentration, 9.44% and extraction time, 60 min. Optimum extraction conditions demonstrated wedelolactone yield of 15.37 ± 0.63 mg/100 g E. alba (L.) Hassk, which was in good agreement with the predicted values. Temperature and modifier concentration showed significant effect on the wedelolactone yield. The supercritical carbon dioxide extraction showed higher selectivity than the conventional Soxhlet assisted extraction method. Copyright © 2013 Elsevier Masson SAS. All rights reserved.

Effect of Extraction Method on the Oxidative Stability of Camelina Seed Oil Studied by Differential Scanning Calorimetry.

PubMed

Belayneh, Henok D; Wehling, Randy L; Cahoon, Edgar B; Ciftci, Ozan N

2017-03-01

Camelina seed is a new alternative omega-3 source attracting growing interest. However, it is susceptible to oxidation due to its high omega-3 content. The objective of this study was to improve the oxidative stability of the camelina seed oil at the extraction stage in order to eliminate or minimize the use of additive antioxidants. Camelina seed oil extracts were enriched in terms of natural antioxidants using ethanol-modified supercritical carbon dioxide (SC-CO 2 ) extraction. Oxidative stability of the camelina seed oils extracted by ethanol modified SC-CO 2 was studied by differential scanning calorimeter (DSC), and compared with cold press, hexane, and SC-CO 2 methods. Nonisothermal oxidation kinetics of the oils obtained by different extraction methods were studied by DSC at varying heating rates (2.5, 5, 10, and 15 °C/min). Increasing ethanol level in the ethanol-modified SC-CO 2 increased the oxidative stability. Based on oxidation onset temperatures (T on ), SC-CO 2 containing 10% ethanol yielded the most stable oil. Oxidative stability depended on the type and content of the polar fractions, namely, phenolic compounds and phospholipids. Phenolic compounds acted as natural antioxidants, whereas increased phospholipid contents decreased the stability. Study has shown that the oxidative stability of the oils can be improved at the extraction stage and this may eliminate the need for additive antioxidants. © 2017 Institute of Food Technologists®.

Analysis of additives in dairy products by liquid chromatography coupled to quadrupole-orbitrap mass spectrometry.

PubMed

Jia, Wei; Ling, Yun; Lin, Yuanhui; Chang, James; Chu, Xiaogang

2014-04-04

A new method combining QuEChERS with ultrahigh-performance liquid chromatography and electrospray ionization quadrupole Orbitrap high-resolution mass spectrometry (UHPLC/ESI Q-Orbitrap) was developed for the highly accurate and sensitive screening of 43 antioxidants, preservatives and synthetic sweeteners in dairy products. Response surface methodology was employed to optimize a quick, easy, cheap, effective, rugged, and safe (QuEChERS) sample preparation method for the determination of 42 different analytes in dairy products for the first time. After optimization, the maximum predicted recovery was 99.33% rate for aspartame under the optimized conditions of 10 mL acetionitrile, 1.52 g sodium acetate, 410 mg PSA and 404 mgC18. For the matrices studied, the recovery rates of the other 42 compounds ranged from 89.4% to 108.2%, with coefficient of variation <6.4%. UHPLC/ESI Q-Orbitrap Mass full scan mode acquired full MS data was used to identify and quantify additives, and data-dependent scan mode obtained fragment ion spectra for confirmation. The mass accuracy typically obtained is routinely better than 1.5ppm, and only need to calibrate once a week. The 43 compounds behave dynamic in the range 0.001-1000 μg kg(-1) concentration, with correlation coefficient >0.999. The limits of detection for the analytes are in the range 0.0001-3.6 μg kg(-1). This method has been successfully applied on screening of antioxidants, preservatives and synthetic sweeteners in commercial dairy product samples, and it is very useful for fast screening of different food additives. Copyright © 2014 Elsevier B.V. All rights reserved.

Fast determination of phenoxy acid herbicides in carrots and apples using liquid chromatography coupled triple quadrupole mass spectrometry.

PubMed

Santilio, Angela; Stefanelli, Patrizia; Dommarco, Roberto

2009-08-01

A fast, simple and inexpensive method has been developed for the analysis of phenoxy acid herbicides: 2,4-dichlorophenoxyacetic acid (2,4-D), 4-chloro-2-methylphenoxyacetic acid (MCPA), 2-(4-chloro-o-tolyloxy)propionic acid (MCPP), 2-(4-aryloxyphenoxy)propionic acid (Fluazifop) and 2-(4-aryloxyphenoxy)propionic acid (Haloxyfop) in carrots and apples by liquid chromatography coupled to triple quadrupole mass spectrometry (LC/MS/MS). The compounds were analyzed by QuEChERS (quick, easy, cheap, effective, rugged, safe) methodology without cleanup. The recoveries were performed at two spiked levels (0.05 and 0.5 mg/kg) for both matrices with six replicates for each level. The mean recoveries ranged from 70-92% for both apples and carrots. The precision of the method expressed as relative standard deviation (RSD%) was found to be in the range 3-15%. For all compounds, good linearity (r(2) > 0.99) was obtained over the range of concentration from 0.05 micro g/mL to 0.5 micro g/mL, corresponding to the pesticide concentrations of 0.05 mg/kg and 0.5 mg/kg, respectively. The determination limits (LOQs) ranged from 0.01 ng/mL to 1.3 ng/mL in solvent, whereas, the LOQs calculated in matrix ranged from 0.05 ng/g to 21.0 ng/g for apples and from 0.06 ng/g to 10.2 ng/g for carrots. The developed methodology combines the advantages of both QuEChERS and LC/MS/MS producing a very rapid, sensitive and cheap method useful for the routine analytical laboratories.

Miniaturized QuEChERS based methodology for multiresidue determination of pesticides in odonate nymphs as ecosystem biomonitors.

PubMed

Jesús, Florencia; Hladki, Ricardo; Gérez, Natalia; Besil, Natalia; Niell, Silvina; Fernández, Grisel; Heinzen, Horacio; Cesio, María Verónica

2018-02-01

The impacts of the modern, agrochemicals based agriculture that threatens the overall systems sustainability, need to be monitored and evaluated. Seeking for agroecosystems monitors, the present article focus in the occurrence and abundance of aquatic macroinvertebrates, that have been frequently used as bioindicators of water quality due to their relationship with land use. Some of these organisms are on the top of the food chain, where bioaccumulation and biomagnification processes can be observed, and they can turn into secondary pollution sources of systems and terrestrial organisms as well. Odonate nymphs, which belong to the functional group of predators, were selected for this study. A methodology to determine 73 pesticide residues in odonate nymphs by LC-MS/MS and GC-MS/MS was developed. A QuEChERS sample preparation strategy was adapted. As it is complex to obtain samples especially in disturbed ecosystems, the method was minimized to a sample size of 200mg of fresh nymphs. The method was validated and good recoveries (71-120%) with RSDs below 20% for the majority of the studied pesticides at least at two of the assayed levels 1, 10 and 50µgkg -1 were obtained. For 32 analytes the limit of quantitation was 1µgkg -1 and 10µgkg -1 for the others. The lineal range was observed between 1-100µgkg -1 in matrix-matched and solvent calibration curves for most of the assessed pesticides. LC-MS/MS matrix effects were evaluated, 40% of the analytes presented low or no signal suppression. Only flufenoxuron presented high matrix effects. The obtained methodology is adequate for pesticide multiresidue analysis in aquatic macroinvertebrates (odonates) aiming to contribute to the ecological state evaluation of freshwater ecosystems. Copyright © 2017 Elsevier B.V. All rights reserved.

Multiresidue determination of pesticides in crop plants by the quick, easy, cheap, effective, rugged, and safe method and ultra-high-performance liquid chromatography tandem mass spectrometry using a calibration based on a single level standard addition in the sample.

PubMed

Viera, Mariela S; Rizzetti, Tiele M; de Souza, Maiara P; Martins, Manoel L; Prestes, Osmar D; Adaime, Martha B; Zanella, Renato

2017-12-01

In this study, a QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method, optimized by a 2 3 full factorial design, was developed for the determination of 72 pesticides in plant parts of carrot, corn, melon, rice, soy, silage, tobacco, cassava, lettuce and wheat by ultra-high-performance liquid chromatographic tandem mass spectrometry (UHPLC-MS/MS). Considering the complexity of these matrices and the need of use calibration in matrix, a new calibration approach based on single level standard addition in the sample (SLSAS) was proposed in this work and compared with the matrix-matched calibration (MMC), the procedural standard calibration (PSC) and the diluted standard addition calibration (DSAC). All approaches presented satisfactory validation parameters with recoveries from 70 to 120% and relative standard deviations≤20%. SLSAS was the most practical from the evaluated approaches and proved to be an effective way of calibration. Method limit of detection were between 4.8 and 48μgkg -1 and limit of quantification were from 16 to 160μgkg -1 . Method application to different kinds of plants found residues of 20 pesticides that were quantified with z-scores values≤2 in comparison with other calibration approaches. The proposed QuEChERS method combined with UHPLC-MS/MS analysis and using an easy and effective calibration procedure presented satisfactory results for pesticide residues determination in different crop plants and is a good alternative for routine analysis. Copyright © 2017 Elsevier B.V. All rights reserved.

Contamination of Tea and Tea Infusion with Polycyclic Aromatic Hydrocarbons

PubMed Central

Zachara, Alicja; Gałkowska, Dorota; Juszczak, Lesław

2017-01-01

The aim of this work was to validate the method of determination of polycyclic aromatic hydrocarbons (PAHs), i.e., benzo(a)pyrene and sum of benzo(a)pyrene, benz(a)anthracene, benzo(b)fluoranthene and chrysene in different types of tea, as well as to assess the transfer of these contaminants from tea to tea infusion. The research materials were popular types of black, green, red and white tea. Quantitative and qualitative determination of PAHs was performed by High Performance Liquid Chromatography with fluorimetric detection (HPLC-FLD). The samples were prepared by QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) technique followed by cleaning-up by dispersion solid-phase extraction (d-SPE). Values of limit of detection and limit of quantification obtained in the validation of the method were lower than the respective maximum values given in Commission Regulation (EU) No. 836/2011. The level of contamination of popular teas commercially available on the Polish market with PAHs is similar to that of teas available in other countries, with a very large variation in the concentration of each of the compounds. The highest benzo(a)pyrene and Σ4PAHs contents (209 ± 42 μg/kg and 756 ± 151 μg/kg, respectively) were found for black tea leaves. The transfer of Σ4PAHs from black tea to tea infusions was 0.48%, while it was 1.55–1.72% for red, white and green teas. PMID:29283369

Monitoring of Pesticide Residues in Commonly Used Fruits and Vegetables in Kuwait.

PubMed

Jallow, Mustapha F A; Awadh, Dawood G; Albaho, Mohammed S; Devi, Vimala Y; Ahmad, Nisar

2017-07-25

The presence of pesticide residues in primary and derived agricultural products raises serious health concerns for consumers. The aim of this study was to assess the level of pesticide residues in commonly consumed fruits and vegetables in Kuwait. A total of 150 samples of different fresh vegetables and fruits were analyzed for the presence of 34 pesticides using the quick easy cheap effective rugged and safe (QuEChERS) multi-residue extraction, followed by gas chromatography-mass spectrometry (GC-MS) or liquid chromatography-tandem mass spectrometry (LC - MS / MS). Pesticide residues above the maximum residue limits (MRL) were detected in 21% of the samples and 79% of the samples had no residues of the pesticides surveyed or contained residues below the MRL. Multiple residues were present in 40% of the samples with two to four pesticides, and four samples were contaminated with more than four pesticide residues. Of the pesticides investigated, 16 were detected, of which imidacloprid, deltamethrin, cypermethrin, malathion, acetamiprid, monocrotophos, chlorpyrifos-methyl, and diazinon exceeded their MRLs. Aldrin, an organochlorine pesticide, was detected in one apple sample, with residues below the MRL. The results indicate the occurrence of pesticide residues in commonly consumed fruits and vegetables in Kuwait, and pointed to an urgent need to develop comprehensive intervention measures to reduce the potential health risk to consumers. The need for the regular monitoring of pesticide residues and the sensitization of farmers to better pesticide safety practices, especially the need to adhere to recommended pre-harvest intervals is recommended.

LC-MS/MS methods for albendazole analysis in feed and its metabolite residues in fish fillet and a leaching study in feed after an alternative procedure for drug incorporation.

PubMed

Busatto, Zenaís; da Silva, Agnaldo Fernando Baldo; de Freitas, Osvaldo; Paschoal, Jonas Augusto Rizzato

2017-04-01

This paper describes the development of analytical methods for the quantification of albendazole (ABZ) in fish feed and ABZ and its main known metabolites (albendazole sulfoxide, albendazole sulfone and albendazole aminosulfone) in fish fillet employing LC-MS/MS. In order to assess the reliability of the analytical methods, evaluation was undertaken as recommended by related guides proposed by the Brazilian Ministry of Agriculture for analytical method validation. The calibration curve for ABZ quantification in feed showed adequate linearity (r > 0.99), precision (CV < 1.03%) and trueness ranging from 99% to 101%. The method for ABZ residues in fish fillet involving the QuEChERS technique for sample extraction had adequate linearity (r > 0.99) for all analytes, precision (CV < 13%) and trueness around 100%, with CCα < 122 ng g - 1 and CCβ < 145 ng g - 1 . Besides, by aiming to avoid the risk of ABZ leaching from feed into the aquatic environment during fish medication via the oral route, a promising procedure for drug incorporation in the feed involving coating feed pellets with ethyl cellulose polymer containing ABZ was also evaluated. The medicated feed had good homogeneity (CV < 3%) and a lower release of ABZ (< 0.2%) from feed to water when the medicated feed stayed in the water for up to 15 min.

A modified protocol for RNA extraction from different peach tissues suitable for gene isolation and real-time PCR analysis.

PubMed

Tong, Zhaoguo; Qu, Shenchun; Zhang, Jiyu; Wang, Fei; Tao, Jianmin; Gao, Zhihong; Zhang, Zhen

2012-03-01

RNA extraction is the first step in the study of gene isolation and expression. However, it is difficult to extract high quantity and quality RNA from tissues containing large quantities of polysaccharides and polyphenols. Peach (Prunus persica), in addition to containing high levels of polysaccharides and polyphenols, is a challenging starting material for RNA isolation using a single method because of different amounts of those substances in diverse tissues. Based on three reported methods, we developed a modified RNA isolation protocol to solve this problem, leading to high quality and quantity of total RNA from peach mesocarp tissues of fruits which were sampled from all developmental stages and different storage periods, as well as from other tissues including flowers, leaves, stems, and roots. With our modified method, 28-650 μg of total RNA was routinely obtained from per gram of fresh material, gave at least a 1.16-fold improvement by compared with those isolated by other seven methods. The RNA extracts were successfully used in downstream applications such as RT-PCR, RACE, and real-time PCR.

General method to evaluate substrate surface modification techniques for light extraction enhancement of organic light emitting diodes

NASA Astrophysics Data System (ADS)

Krummacher, B. C.; Mathai, M. K.; Choong, V.; Choulis, S. A.; So, F.; Winnacker, A.

2006-09-01

The external light output of organic light emitting diodes (OLEDs) can be increased by modifying the light emitting surface. The apparent light extraction enhancement is given by the ratio between the efficiency of the unmodified device and the efficiency of the modified device. This apparent light extraction enhancement is dependent on the OLED architecture itself and is not the correct value to judge the effectiveness of a technique to enhance light outcoupling due to substrate surface modification. We propose a general method to evaluate substrate surface modification techniques for light extraction enhancement of OLEDs independent from the device architecture. This method is experimentally demonstrated using green electrophosphorescent OLEDs with different device architectures. The substrate surface of these OLEDs was modified by applying a prismatic film to increase light outcoupling from the device stack. It was demonstrated that the conventionally measured apparent light extraction enhancement by means of the prismatic film does not reflect the actual performance of the light outcoupling technique. Rather, by comparing the light extracted out of the prismatic film to that generated in the OLED layers and coupled into the substrate (before the substrate/air interface), a more accurate evaluation of light outcoupling enhancement can be achieved. Furthermore we show that substrate surface modification can change the output spectrum of a broad band emitting OLED.

Direct preparation of a graphene oxide modified monolith in a glass syringe as a solid-phase extraction cartridge for the extraction of quaternary ammonium alkaloids from Chinese patent medicine.

PubMed

Liang, Xiaojing; Wang, Licheng; Wang, Shuai; Li, Yijing; Guo, Yong

2017-11-01

Packed cartridges have been widely used in solid-phase extraction. However, there are still some drawbacks, such as they are blocked easily and the method is time-consuming. In view of the advantages of monoliths, a monolithic extraction material has been directly synthesized in a glass syringe without any gap between the monolith and syringe inner wall. The monolithic syringe was modified with graphene oxide by loading graphene oxide dispersion onto it. The content of graphene oxide and the surface topography of the monolith have been evaluated by elemental analysis and scanning electron microscopy, respectively, which confirmed the successful modification. This prepared graphene oxide-modified monolithic syringe was directly used as a traditional solid-phase extraction cartridge. As expected, it shows good permeability and excellent capability for the extraction of quaternary ammonium alkaloids. The sample loading velocity (1-6 mL/min) does not affect the recovery. Under the optimal conditions, good linearities (R = 0.9992-0.9998) were obtained for five quaternary ammonium alkaloids, and the limits of detection and quantification were 0.5-1 and 1-2 μg/L, respectively. The proposed method was successfully applied for the analysis of quaternary ammonium alkaloids in Chinese patent medicine. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A comparative analysis of modified binders : original asphalts and materials extracted from existing pavements : technical summary.

DOT National Transportation Integrated Search

2010-01-01

The initial objective of this research was to develop procedures and standards for applying GPC as an analytical tool to define the percentage amounts of polymer modifiers in polymer modified asphalt cements soluble in eluting GPC solvents. Quantific...

New Finger Biometric Method Using Near Infrared Imaging

PubMed Central

Lee, Eui Chul; Jung, Hyunwoo; Kim, Daeyeoul

2011-01-01

In this paper, we propose a new finger biometric method. Infrared finger images are first captured, and then feature extraction is performed using a modified Gaussian high-pass filter through binarization, local binary pattern (LBP), and local derivative pattern (LDP) methods. Infrared finger images include the multimodal features of finger veins and finger geometries. Instead of extracting each feature using different methods, the modified Gaussian high-pass filter is fully convolved. Therefore, the extracted binary patterns of finger images include the multimodal features of veins and finger geometries. Experimental results show that the proposed method has an error rate of 0.13%. PMID:22163741

Efficient method for extracting DNA of parasites causing bovine babesiosis from tick vectors

USDA-ARS?s Scientific Manuscript database

The southern cattle tick, Rhipicephalus (Boophilus) microplus, is an economically important pest costing animal agriculture billions of dollars worldwide. This research focuses on a comparison of three different tick DNA extraction methods: phenol-chloroform extraction (method 1), a modified version...

Extractability and Bioavailability of Pb and As in Historically Contaminated Orchard Soil: Effects of Compost Amendments

PubMed Central

Fleming, Margaret; Yiping, Tai; Ping, Zhuang; McBride, Murray B.

2015-01-01

The availability of Pb and As in an historically contaminated orchard soil, after amendment with compost and aging in the field, was determined by single-step chemical extraction with 1.0 M ammonium acetate at pH 4.8, sequential extraction using the modified BCR test, and a redworm bioassay in the laboratory. The efficiency of soil Pb extraction by ammonium acetate was greater at higher total soil Pb but was reduced by compost amendment. Conversely, the extraction efficiency of total soil As increased with compost amendment, but was not sensitive to total soil As. The redworm bioassay indicated Pb (but not As) bioavailability to be reduced by soil amendment with compost, a result consistent with the ammonium acetate extraction test but not reflected in modified BCR test. Electron microprobe studies of the orchard soil revealed Pb and As to be spatially associated in discrete particles along with phosphorus and iron. PMID:23474982

Effect on in vitro starch digestibility of Mexican blue maize anthocyanins.

PubMed

Camelo-Méndez, Gustavo A; Agama-Acevedo, Edith; Sanchez-Rivera, Mirna M; Bello-Pérez, Luis A

2016-11-15

The purpose of this study was to evaluate the effect of blue maize extracts obtained by acid-methanol treatment on the nutritional in vitro starch fractions such as: rapidly digestive starch (RDS), slowly digestive starch (SDS) and resistant starch (RS) of native and gelatinized commercial maize starch. Chromatographic analysis (HPLC-DAD/ESI-MS) of blue maize extracts showed the presence of seven anthocyanins, where cyanidin-3-(6″-malonylglucoside) was the main. Blue maize extracts modified nutritional in vitro starch fractions (decrease of RDS) while RS content increased (1.17 and 2.02 times for native and gelatinized commercial maize starch, respectively) when anthocyanins extracts were added to starch up to 75% (starch weight). This preliminary observation provides the basis for further suitability evaluation of blue maize extract as natural starch-modifier by the possible anthocyanins-starch interaction. Anthocyanin extracts can be a suitable to produce functional foods with higher RS content with potential human health benefits. Copyright © 2016 Elsevier Ltd. All rights reserved.

Application of wavelet transformation and adaptive neighborhood based modified backpropagation (ANMBP) for classification of brain cancer

NASA Astrophysics Data System (ADS)

Werdiningsih, Indah; Zaman, Badrus; Nuqoba, Barry

2017-08-01

This paper presents classification of brain cancer using wavelet transformation and Adaptive Neighborhood Based Modified Backpropagation (ANMBP). Three stages of the processes, namely features extraction, features reduction, and classification process. Wavelet transformation is used for feature extraction and ANMBP is used for classification process. The result of features extraction is feature vectors. Features reduction used 100 energy values per feature and 10 energy values per feature. Classifications of brain cancer are normal, alzheimer, glioma, and carcinoma. Based on simulation results, 10 energy values per feature can be used to classify brain cancer correctly. The correct classification rate of proposed system is 95 %. This research demonstrated that wavelet transformation can be used for features extraction and ANMBP can be used for classification of brain cancer.

Sulfonated poly(styrene-divinylbenzene) modified with amines and the application for pipette-tip solid-phase extraction of carbendazim in apples.

PubMed

Ma, Yuxin; Liu, Lingling; Tang, Weiyang; Zhu, Tao

2017-10-01

Sulfonated poly(styrene-divinylbenzene) modified with five kinds of amine functional groups was applied to the determination of carbendazim in apple samples with a pipette-tip solid-phase extraction method. The structures of the polymers were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. Five different modifications of the solid-phase extraction sorbent based on sulfonated poly(styrene-divinylbenzene) were tested under static and pipette-tip solid-phase extraction conditions. The polymer modified with p-methoxyaniline showed the best recognition capacity and adsorption amount for carbendazim. Under the optimum conditions, 3.00 mg of the adsorbent, 1.00 mL of ethyl acetate as washing solvent, and 1.00 mL of ammonia/acetonitrile (5:95, v/v) as elution solvent were used in the pretreatment procedure of apple samples. The calibration graphs of carbendazim in methanol were linear over 5.00-200.00 μg/mL, and the limits of detection and quantification were 0.01 and 0.03 μg/mL, respectively. The method recoveries of carbendazim were in the range of 91.31-98.13% with associated intraday relative standard deviations of 0.76-2.13% and interday relative standard deviations of 1.10-1.85%. Sulfonated poly(styrene-divinylbenzene) modified with p-methoxyaniline showed satisfactory results (recovery: 97.96%) and potential for the rapid purification of carbendazim in apple samples combined with the pipette-tip solid-phase extraction. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Allelopathic effect of methanolic extracts of genetically modified and non-genetically modified canola on soybean.

PubMed

Syed, Kashmala; Shinwari, Zabta Khan

2016-03-01

This study on the effect of genetically modified (GM) and non-GM canola on soybean was carried out for physiological and biochemical biosafety assessment of GM canola. Methanolic extracts of GM and non-GM canola were assessed on seed germination and growth of soybean (Glycine max L.) under sterilized conditions. The extracts applied were of 3, 5, and 10% concentrations. The results showed that methanolic extracts of both GM and non-GM canola improved the germination percentage. However, germination rate index was significantly decreased with concomitant increase in mean germination time of soybean. A significant rate of decrease was observed in root fresh weight while increase in shoot length took place; when treatment of GM canola extracts were applied, however, no effect was observed in shoot fresh weight. A significant increase in protein contents, as well as phenolic, carotenoids, proline, and chlorophyll a content, was observed when different GM canola treatments (3, 5, and 10%) were applied to soybean; however, a significant rate of reduction in chlorophyll b content was observed by the application of GM canola treatment. Similar results were observed for superoxide dismutase, peroxidase, and catalase activities. A significant increase in the sugar content levels was observed when GM canola treatments (3, 5, and 10%) were applied to soybean. © The Author(s) 2013.

[Noncollagen bone proteins use in the composition of osteoplactic material Gapkol modified by vacuum].

PubMed

Volozhin, A I; Grigor'ian, A S; Desiatnichenko, K S; Ozhelevskaia, S A; Doktorov, A A; Kurdiumov, S G; Fionova, E V; Gurin, A N; Karakov, K G

2008-01-01

In rat experiments the ability of noncollagen bone proteins (NCBP) in the composition of osteoplactic modified material Gapkol (not tanned in formalin and subjected to vacuum extraction) to increase bone reparation in comparison with traditional Gapkol was studied. Quantitative evaluation was performed on rat parietal bone and qualitative evaluation was performed on rat mandible. It was shown that Gapkol with NCBP (not tanned in formalin and subjected to vacuum extraction) increased reparative osteogenesis.

A magnet built on bronchoscopic suction for extraction of tracheobronchial headscarf pins: a novel technique and review of a tertiary centre experience.

PubMed

Elsayed, Hany H; Mostafa, Ahmed M; Soliman, Saleh; El-Bawab, Hatem Y; Moharram, Adel A; El-Nori, Ahmed A

2016-05-01

Airway metal pins are one of the most commonly inhaled foreign bodies in Eastern societies in young females wearing headscarves. We innovated a modified bronchoscopic technique to extract tracheobronchial headscarf pins by the insertion of a magnet to allow an easy and non-traumatic extraction of the pins. The aim of this study was to assess the feasibility and safety of our new technique and compare it with our large previous experience with the classic bronchoscopic method of extraction of tracheobronchial headscarf pins. We performed a study comparing our retrospective experience of classic bronchoscopic extraction from February 2004 to January 2014 and prospective experience with our modified technique using the magnet from January 2014 to June 2015. An institutional review board and new device approval were obtained. Three hundred and twenty-six procedures on 315 patients were performed during our initial 10-year experience. Of them, 304 patients were females. The median age of our group was 13 (0-62). The median time from inhalation to procedure was 1 day (0-1022). After introducing our modified new technique using the magnet, 20 procedures were performed. Nineteen were females. The median time of the procedure and the need to forcefully bend the pin for extraction were in favour of the new technique in comparison with our classic approach (2 vs 6 min; P < 0.001) (2 patients = 20% vs 192 = 58%; P < 0.001). The conversion rate to surgery was also in favour of the modified technique but did not reach statistical significance (0 = 0% vs 15 = 4.8%; P = 0.32). All patients who underwent the modified technique were discharged home on the same day of the procedure. No procedural complications were recorded. All remain well on a follow-up period of up to 14 months. Bronchoscopic extraction of tracheobronchial inhaled headscarf pins using a novel technique using homemade magnets was safer and simpler in comparison with our large experience with the classic approach. We advise the use of this device (or concept) in selected patients in centres dealing with this problem. © The Author 2016. Published by Oxford University Press on behalf of the European Association for Cardio-Thoracic Surgery. All rights reserved.

The extraction of bitumen from western oil sands. Final report, July 1989--September 1993

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oblad, A.G.; Bunger, J.W.; Dahlstrom, D.A.

1994-03-01

Research and development of surface extraction and upgrading processes of western tar sands are described. Research areas included modified hot water, fluidized bed, and rotary kiln pyrolysis of tar sands for extraction of bitumen. Bitumen upgrading included solvent extraction of bitumen, and catalytic hydrotreating of bitumen. Characterization of Utah tar sand deposits is also included.

Process for the extraction of strontium from acidic solutions

DOEpatents

Horwitz, E.P.; Dietz, M.L.

1994-09-06

The invention is a process for selectively extracting strontium values from aqueous nitric acid waste solutions containing these and other fission product values. The extractant solution is a macrocyclic polyether in an aliphatic hydrocarbon diluent containing a phase modifier. The process will selectively extract strontium values from nitric acid solutions which are up to 6 molar in nitric acid. 4 figs.

Process for the extraction of strontium from acidic solutions

DOEpatents

Horwitz, E. Philip; Dietz, Mark L.

1994-01-01

The invention is a process for selectively extracting strontium values from aqueous nitric acid waste solutions containing these and other fission product values. The extractant solution is a macrocyclic polyether in an aliphatic hydrocarbon diluent containing a phase modifier. The process will selectively extract strontium values from nitric acid solutions which are up to 6 molar in nitric acid.

Process for the extraction of strontium from acidic solutions

DOEpatents

Horwitz, E.P.; Dietz, M.L.

1993-01-01

The invention is a process for selectively extracting strontium values from aqueous nitric acid waste solutions containing these and other fission product values. The extractant solution is a macrocyclic polyether in an aliphatic hydrocarbon diluent containing a phase modifier. The process will selectively extract strontium values from nitric acid solutions which are up to 6 molar in nitric acid.

21 CFR 172.560 - Modified hop extract.

Code of Federal Regulations, 2010 CFR

2010-04-01

... manufactured by one of the following processes: (1) The additive is manufactured from a hexane extract of hops... solids is made up in approximately 0.012 n alkaline methyl alcohol (6 milliliters of 1 n sodium hydroxide... hops by a sequence of extractions and fractionations, using methylene chloride, hexane, and methyl...

21 CFR 172.560 - Modified hop extract.

Code of Federal Regulations, 2013 CFR

2013-04-01

... manufactured by one of the following processes: (1) The additive is manufactured from a hexane extract of hops... solids is made up in approximately 0.012 n alkaline methyl alcohol (6 milliliters of 1 n sodium hydroxide... hops by a sequence of extractions and fractionations, using methylene chloride, hexane, and methyl...

21 CFR 172.560 - Modified hop extract.

Code of Federal Regulations, 2012 CFR

2012-04-01

... manufactured by one of the following processes: (1) The additive is manufactured from a hexane extract of hops... solids is made up in approximately 0.012 n alkaline methyl alcohol (6 milliliters of 1 n sodium hydroxide... hops by a sequence of extractions and fractionations, using methylene chloride, hexane, and methyl...

21 CFR 172.560 - Modified hop extract.

Code of Federal Regulations, 2011 CFR

2011-04-01

... manufactured by one of the following processes: (1) The additive is manufactured from a hexane extract of hops... solids is made up in approximately 0.012 n alkaline methyl alcohol (6 milliliters of 1 n sodium hydroxide... hops by a sequence of extractions and fractionations, using methylene chloride, hexane, and methyl...

Extraction of Carbon Dioxide and Hydrogen from Seawater by an Electrochemical Acidification Cell. Part 4. Electrode Compartments of Cell Modified and Tested in Scaled-Up Mobile Unit

DTIC Science & Technology

2013-09-03

Electrochemical Acidification Cell Part IV: Electrode Compartments of Cell Modified and Tested in Scaled-Up Mobile Unit September 3, 2013 Approved for public...OF ABSTRACT Extraction of Carbon Dioxide and Hydrogen from Seawater by an Electrochemical Acidification Cell Part IV: Electrode Compartments of Cell...Electrochemical acidification cell Carbon dioxide Hydrogen Polarity reversal An electrochemical acidification cell was scaled-up and integrated into a

Identification of Explosives from Porous Materials: Applications Using Reverse Phase High Performance Liquid Chromatography and Gas Chromatography

DOE Office of Scientific and Technical Information (OSTI.GOV)

C.J. Miller; G. Elias; N.C. Schmitt

2010-06-01

High performance liquid chromatography and gas chromatography techniques are well documented and widely used for the detection of trace explosives from organic solvents. These techniques were modified to specifically identify and quantify explosives extracted from various materials taken from people who had recently handled explosives. Documented techniques were modified to specifically detect and quantify RDX, TNT, and PETN from denim, colored flannel, vinyl, and canvas extracted in methanol using no sample cleanup prior to analysis. The methanol extracts were injected directly into several different column types and analyzed by HPLC-UV and/or GC-ECD. This paper describes general screening methods that weremore » used to determine the presence of explosives in unknown samples and techniques that have been optimized for quantification of each explosive from the substrate extracts.« less

Rapid determination of methylmercury in fish and shellfish: method development

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hight, S.C.; Corcoran, M.T.

The AOAC official first action method for methylmercury in fish and shellfish was modified to provide more rapid determination. Methylmercury is isolated from homogenized, acetone-washed tissue by addition of HCl and extraction by toluene of the methylmercuric chloride produced. The extract is analyzed by electron capture gas chromatography (GC) on 5% DEGS-PS treated with mercuric chloride solution. The quantitation limit of the method is 0.25 ..mu..g Hg/g. Swordfish, shark, tuna, shrimp, clams, oysters, and NBS Research Material-50 (tuna) were analyzed for methylmercury by the AOAC official first action method. All products also were analyzed by the modified method and themore » AOAC official method for total Hg. In addition, selected extracts obtained with the modified method were analyzed by GC with Hg-selective, microwave-induced helium plasma detection. There was no significant different between the results for the various methods. Essentially all the Hg present (determined as total Hg) was in the organic form. Coefficients of variation from analyses by the modified method ranged from 1 to 7% for fish and shellfish containing methylmercury at levels of 0.50-2.30 ..mu..g Hg/g. The overall average recovery was 100.5%.« less

[Clinical study of modified Gow-Gates technique of inferior alveolar nerve block in impacted mandibular third molar extraction].

PubMed

Hu, Yi-ping; Jin, Gui-fang

2015-06-01

To introduce a minimally invasive and more effective technique of inferior alveolar nerve block. Two hundred and six patients who needed extraction of the impacted mandibular third molar were divided randomly into 2 groups: the experimental group (105 cases) with modified Gow-Gates technique (modified Gow-Gates group) and the control group (101 cases) with Halstead technique (Halstead group). The anesthetic success rates, effects and complications were recorded and analyzed with SPSS17.0 software package. The anesthetic success rate was 97.15% in modified Gow-Gates group and 89.10% in Halstead group with significant difference between the 2 groups (P=0.038<0.05); In comparing the anesthesia grade, the ration of grade A and B accounted for 90.48% in modified Gow-Gates group and 87.13% in Halstead group (P=0.446>0.05). Modified Gow-Gates group had much fewer of complications than Halstead group (P=0.014<0.05). Modified Gow-Gates technique is a minimally invasive and more effective technique for inferior alveolar nerve block anesthesia. Supported by Science and Technology Planning Project of Yueqing City (2014y027).

[Study on condition for extraction of arctiin from fruits of Arctium lappa using supercritical fluid extraction].

PubMed

Dong, Wen-hong; Liu, Ben

2006-08-01

To study the feasibility of supercritical fluid extraction (SFE) for arctiin from the fruits of Arctium lappa. The extracts were analyzed by HPLC, optimum extraction conditions were studied by orthogonal tests. The optimal extraction conditions were: pressure 40 MPa, temperature 70 degrees C, using methanol as modifier carrier at the rate of 0.55 mL x min(-1), static extraction time 5 min, dynamic extraction 30 min, flow rate of CO2 2 L x min(-1). SFE has the superiority of adjustable polarity, and has the ability of extracting arctiin.

Supercritical fluid extraction of phenolic compounds and antioxidants from grape (Vitis labrusca B.) seeds.

PubMed

Ghafoor, Kashif; Al-Juhaimi, Fahad Y; Choi, Yong Hee

2012-12-01

Supercritical fluid extraction (SFE) technique was applied and optimized for temperature, CO₂ pressure and ethanol (modifier) concentration using orthogonal array design and response surface methodology for the extract yield, total phenols and antioxidants from grape (Vitis labrusca B.) seeds. Effects of extraction temperature and pressure were found to be significant for all these response variables in SFE process. Optimum SFE conditions (44 ~ 46 °C temperature and 153 ~ 161 bar CO₂ pressure) along with ethanol (<7 %) as modifier, for the maximum predicted values of extract yield (12.09 %), total phenols (2.41 mg GAE/ml) and antioxidants (7.08 mg AAE/ml), were used to obtain extracts from grape seeds. The predicted values matched well with the experimental values (12.32 % extract yield, 2.45 mg GAE/ml total phenols and 7.08 mg AAE/ml antioxidants) obtained at optimum SFE conditions. The antiradical assay showed that SFE extracts of grape seeds can scavenge more than 85 % of 1, 1-diphenyl-2-picrylhydrazyl (DPPH) radicals. The grape seeds extracts were also analyzed for hydroxybenzoic acids which included gallic acid (1.21 ~ 3.84 μg/ml), protocatechuic acid (3.57 ~ 11.78 μg/ml) and p-hydroxybenzoic acid (206.72 ~ 688.18 μg/ml).

Trivalent Lanthanide/Actinide Separation Using Aqueous-Modified TALSPEAK Chemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Travis S. Grimes; Richard D. Tillotson; Leigh R. Martin

TALSPEAK is a liquid/liquid extraction process designed to separate trivalent lanthanides (Ln3+) from minor actinides (MAs) Am3+ and Cm3+. Traditional TALSPEAK organic phase is comprised of a monoacidic dialkyl bis(2-ethylhexyl)phosphoric acid extractant (HDEHP) in diisopropyl benzene (DIPB). The aqueous phase contains a soluble aminopolycarboxylate diethylenetriamine-N,N,N’,N”,N”-pentaacetic acid (DTPA) in a concentrated (1.0-2.0 M) lactic acid (HL) buffer with the aqueous acidity typically adjusted to pH 3.0. TALSPEAK balances the selective complexation of the actinides by DTPA against the electrostatic attraction of the lanthanides by the HDEHP extractant to achieve the desired trivalent lanthanide/actinide group separation. Although TALSPEAK is considered a successfulmore » separations scheme, recent fundamental studies have highlighted complex chemical interactions occurring in the aqueous and organic phases during the extraction process. Previous attempts to model the system have shown thermodynamic models do not accurately predict the observed extraction trends in the p[H+] range 2.5-4.8. In this study, the aqueous phase is modified by replacing the lactic acid buffer with a variety of simple and longer-chain amino acid buffers. The results show successful trivalent lanthanide/actinide group separation with the aqueous-modified TALSPEAK process at pH 2. The amino acid buffer concentrations were reduced to 0.5 M (at pH 2) and separations were performed without any effect on phase transfer kinetics. Successful modeling of the aqueous-modified TALSPEAK process (p[H+] 1.6-3.1) using a simplified thermodynamic model and an internally consistent set of thermodynamic data is presented.« less

Thermophilic acetylxylan esterase genes and enzymes from alicyclobacillus acidocaldarius and related organisms and methods

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thompson, Vicki S.; Thompson, David N.; Reed, David W.

A genetically modified organism comprising at least one nucleic acid sequence and/or at least one recombinant nucleic acid isolated from Alicyclobacillus acidocaldarius and encoding a polypeptide involved in at least partially degrading, cleaving, transporting, metabolizing, or removing polysaccharide, lignocellulose, hemicellulose, lignin, chitin, heteroxylan, and/or xylan-decorating group; and at least one nucleic acid sequence and/or at least one recombinant nucleic acid encoding a polypeptide involved in fermenting sugar molecules to a product. Additionally, enzymatic and/or proteinaceous extracts may be isolated from one or more genetically modified organisms. The extracts are utilized to convert biomass into a product. Further provided are methodsmore » of converting biomass into products comprising: placing the genetically modified organism and/or enzymatic extracts thereof in fluid contact with polysaccharides, cellulose, lignocellulose, hemicellulose, lignin, starch, sugars, sugar oligomers, carbohydrates, complex carbohydrates, chitin, heteroxylans, glycosides, and/or xylan-, glucan-, galactan-, or mannan-decorating groups.« less

Highly porous solid-phase microextraction fiber coating based on poly(ethylene glycol)-modified ormosils synthesized by sol-gel technology.

PubMed

da Costa Silva, Raquel Gomes; Augusto, Fabio

2005-04-22

The preparation and characteristics of solid-phase microextraction (SPME) fibers coated with Carbowax 20M ormosil (organically modified silica) are described here. Raw fused silica fibers were coated with Carbowax 20M-modified silica using sol-gel process. Scanning electron micrographs of fibers revealed a highly porous, sponge-like coating with an average thickness of (8 +/- 1) microm. The sol-gel Carbowax fibers were compared to commercial fibers coated with 100 microm polydimethylsiloxane (PDMS) and 65 microm Carbowax-divinylbenzene (DVB). Shorter equilibrium times were possible with the sol-gel Carbowax fiber: for headspace extraction of the test analytes, they ranged from less than 3 min for benzene to 15 min for o-xylene. Extraction efficiencies of the sol-gel Carbowax fiber were superior to those of conventional fibers: for o-xylene, the extracted masses were 230 and 540% of that obtained with 100 microm PDMS and 65 microm Carbowax-DVB fibers, respectively.

Extractant compositions for co-extracting cesium and strontium, a method of separating cesium and strontium from an aqueous feed, and calixarene compounds

DOEpatents

Peterman, Dean R [Idaho Falls, ID; Meikrantz, David H [Idaho Falls, ID; Law, Jack D [Pocatello, ID; Riddle, Catherine L [Idaho Falls, ID; Todd, Terry A [Firth, ID; Greenhalgh, Mitchell R [Iona, ID; Tillotson, Richard D [Moore, ID; Bartsch, Richard A [Lubbock, TX; Moyer, Bruce A [Oak Ridge, TN; Delmau, Laetitia H [Oak Ridge, TN; Bonnesen, Peter V [Knoxville, TN

2012-04-17

A mixed extractant solvent that includes at least one dialkyloxycalix[4]arenebenzocrown-6 compound, 4',4',(5')-di-(t-butyldicyclohexano)-18-crown-6, at least one modifier, and, optionally, a diluent. The dialkyloxycalix[4]arenebenzocrown-6 compound is 1,3-alternate-25,27-di(octyloxy)calix[4]arenebenzocrown-6, 1,3-alternate-25,27-di(decyloxy)calix[4]arenebenzocrown-6, 1,3-alternate-25,27-di(dodecyloxy)calix[4]arenebenzocrown-6, 1,3-alternate-25,27-di(2-ethylhexyl-1-oxy)calix[4]arenebenzocrown-6, 1,3-alternate-25,27-di(3,7-dimethyloctyl-1-oxy)calix[4]arenebenzocrown-6, 1,3-alternate-25,27-di(4-butyloctyl-1-oxy)calix[4]arenebenzocrown-6, or combinations thereof. The modifier is a primary alcohol. A method of separating cesium and strontium from an aqueous feed is also disclosed, as are dialkyloxycalix[4]arenebenzocrown-6 compounds and an alcohol modifier.

Green dyeing process of modified cotton fibres using natural dyes extracted from Tamarix aphylla (L.) Karst. leaves.

PubMed

Baaka, Noureddine; Mahfoudhi, Adel; Haddar, Wafa; Mhenni, Mohamed Farouk; Mighri, Zine

2017-01-01

This research work involves an eco-friendly dyeing process of modified cotton with the aqueous extract of Tamarix aphylla leaves. During this process, the dyeing step was carried out on modified cotton by several cationising agents in order to improve its dyeability. The influence of the main dyeing conditions (dye bath pH, dyeing time, dyeing temperature, salt addition) on the performances of this dyeing process were studied. The dyeing performances of this process were appreciated by measuring the colour yield (K/S) and the fastness properties of the dyed samples. The effect of mordant type with different mordanting methods on dyeing quality was also studied. The results showed that mordanting gave deeper shades and enhanced fastness properties. In addition, environmental indicators (BOD 5 , COD and COD/BOD 5 ) were used to describe potential improvements in the biodegradability of the dyebath wastewater. Further, HPLC was used to identify the major phenolic compounds in the extracted dye.

Methods of combined bioprocessing and related microorganisms, thermophilic and/or acidophilic enzymes, and nucleic acids encoding said enzymes

DOEpatents

Thompson, David N.; Apel, William A.; Thompson, Vicki S.; Ward, Thomas E.

2016-03-22

A genetically modified organism comprising: at least one nucleic acid sequence and/or at least one recombinant nucleic acid isolated from Alicyclobacillus acidocaldarius and encoding a polypeptide involved in at least partially degrading, cleaving, transporting, metabolizing, or removing polysaccharides, cellulose, lignocellulose, hemicellulose, lignin, starch, sugars, sugar oligomers, carbohydrates, complex carbohydrates, chitin, heteroxylans, glycosides, xylan-, glucan-, galactan-, or mannan-decorating groups; and at least one nucleic acid sequence and/or at least one recombinant nucleic acid encoding a polypeptide involved in fermenting sugar molecules to a product. Additionally, enzymatic and/or proteinaceous extracts may be isolated from one or more genetically modified organisms. The extracts are utilized to convert biomass into a product. Further provided are methods of converting biomass into products comprising: placing the genetically modified organism and/or enzymatic extracts thereof in fluid contact with polysaccharides, cellulose, lignocellulose, hemicellulose, lignin, starch, sugars, sugar oligomers, carbohydrates, complex carbohydrates, chitin, heteroxylans, glycosides, and/or xylan-, glucan-, galactan-, or mannan-decorating groups.

Methods of combined bioprocessing and related microorganisms, thermophilic and/or acidophilic enzymes, and nucleic acids encoding said enzymes

DOEpatents

Thompson, David N; Apel, William A; Thompson, Vicki S; Ward, Thomas E

2013-07-23

A genetically modified organism comprising: at least one nucleic acid sequence and/or at least one recombinant nucleic acid isolated from Alicyclobacillus acidocaldarius and encoding a polypeptide involved in at least partially degrading, cleaving, transporting, metabolizing, or removing polysaccharides, cellulose, lignocellulose, hemicellulose, lignin, starch, sugars, sugar oligomers, carbohydrates, complex carbohydrates, chitin, heteroxylans, glycosides, xylan-, glucan-, galactan-, or mannan-decorating groups; and at least one nucleic acid sequence and/or at least one recombinant nucleic acid encoding a polypeptide involved in fermenting sugar molecules to a product. Additionally, enzymatic and/or proteinaceous extracts may be isolated from one or more genetically modified organisms. The extracts are utilized to convert biomass into a product. Further provided are methods of converting biomass into products comprising: placing the genetically modified organism and/or enzymatic extracts thereof in fluid contact with polysaccharides, cellulose, lignocellulose, hemicellulose, lignin, starch, sugars, sugar oligomers, carbohydrates, complex carbohydrates, chitin, heteroxylans, glycosides, and/or xylan-, glucan-, galactan-, or mannan-decorating groups.

Methods of combined bioprocessing and related microorganisms, thermophilic and/or acidophilic enzymes, and nucleic acids encoding said enzymes

DOEpatents

Thompson, David N; Apel, William A; Thompson, Vicki S; Ward, Thomas E

2014-04-08

A genetically modified organism comprising: at least one nucleic acid sequence and/or at least one recombinant nucleic acid isolated from Alicyclobacillus acidocaldarius and encoding a polypeptide involved in at least partially degrading, cleaving, transporting, metabolizing, or removing polysaccharides, cellulose, lignocellulose, hemicellulose, lignin, starch, sugars, sugar oligomers, carbohydrates, complex carbohydrates, chitin, heteroxylans, glycosides, xylan-, glucan-, galactan-, or mannan-decorating groups; and at least one nucleic acid sequence and/or at least one recombinant nucleic acid encoding a polypeptide involved in fermenting sugar molecules to a product. Additionally, enzymatic and/or proteinaceous extracts may be isolated from one or more genetically modified organisms. The extracts are utilized to convert biomass into a product. Further provided are methods of converting biomass into products comprising: placing the genetically modified organism and/or enzymatic extracts thereof in fluid contact with polysaccharides, cellulose, lignocellulose, hemicellulose, lignin, starch, sugars, sugar oligomers, carbohydrates, complex carbohydrates, chitin, heteroxylans, glycosides, and/or xylan-, glucan-, galactan-, or mannan-decorating groups.

Organophosphorus insecticides in honey, pollen and bees (Apis mellifera L.) and their potential hazard to bee colonies in Egypt.

PubMed

Al Naggar, Yahya; Codling, Garry; Vogt, Anja; Naiem, Elsaied; Mona, Mohamed; Seif, Amal; Giesy, John P

2015-04-01

There is no clear single factor to date that explains colony loss in bees, but one factor proposed is the wide-spread application of agrochemicals. Concentrations of 14 organophosphorous insecticides (OPs) in honey bees (Apis mellifera) and hive matrices (honey and pollen) were measured to assess their hazard to honey bees. Samples were collected during spring and summer of 2013, from 5 provinces in the middle delta of Egypt. LC/MS-MS was used to identify and quantify individual OPs by use of a modified Quick Easy Cheap Effective Rugged Safe (QuEChERS) method. Pesticides were detected more frequently in samples collected during summer. Pollen contained the greatest concentrations of OPs. Profenofos, chlorpyrifos, malation and diazinon were the most frequently detected OPs. In contrast, ethoprop, phorate, coumaphos and chlorpyrifos-oxon were not detected. A toxic units approach, with lethality as the endpoint was used in an additive model to assess the cumulative potential for adverse effects posed by OPs. Hazard quotients (HQs) in honey and pollen ranged from 0.01-0.05 during spring and from 0.02-0.08 during summer, respectively. HQs based on lethality due to direct exposure of adult worker bees to OPs during spring and summer ranged from 0.04 to 0.1 for best and worst case respectively. It is concluded that direct exposure and/or dietary exposure to OPs in honey and pollen pose little threat due to lethality of bees in Egypt. Copyright © 2014 Elsevier Inc. All rights reserved.

Validation of a QuEChERS-based gas chromatographic method for analysis of pesticide residues in Cassia angustifolia (senna).

PubMed

Tripathy, Vandana; Saha, Ajoy; Patel, Dilipkumar J; Basak, B B; Shah, Paresh G; Kumar, Jitendra

2016-08-02

A simple multi-residue method based on modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) approach was established for the determination of 17 organochlorine (OC), 15 organophosphorous (OP) and 7 synthetic pyrethroid (SP) pesticides in an economically important medicinal plant of India, Senna (Cassia angustifolia), by gas chromatography coupled to electron capture and flame thermionic detectors (GC/ECD/FTD) and confirmation of residues was done on gas chromatograph coupled with mass spectrometry (GC-MS). The developed method was validated by testing the following parameters: linearity, limit of detection (LOD), limit of quantification (LOQ), matrix effect, accuracy-precision and measurement uncertainty; the validation study clearly demonstrated the suitability of the method for its intended application. All pesticides showed good linearity in the range 0.01-1.0 μg mL(-1) for OCs and OPs and 0.05-2.5 μg mL(-1) for SPs with correlation coefficients higher than 0.98. The method gave good recoveries for most of the pesticides (70-120%) with intra-day and inter-day precision < 20% in most of the cases. The limits of detection varied from 0.003 to 0.03 mg kg(-1), and the LOQs were determined as 0.01-0.049 mg kg(-1). The expanded uncertainties were <30%, which was distinctively less than a maximum default value of ±50%. The proposed method was successfully applied to determine pesticide residues in 12 commercial market samples obtained from different locations in India.

SUBCRITICAL (HOT) WATER/ETHANOL EXTRACTION OF NONYLPHENOL POLYETHOXY CARBOXYLATES IN INDUSTRIAL AND MUNICIPAL SLUDGES. (R821195)

EPA Science Inventory

Subcritical (hot) water with ethanol as modifier was used
to extract nonylphenol polyethoxy carboxylates (NPECs)
with 1-4 ethoxy groups from sludge samples. Quantitative
recovery of native NPECs from sludge was accomplished
by extracting 0.25 g samples for 20 min w...

Supercritical fluid extraction and separation of uranium from other actinides.

PubMed

Quach, Donna L; Mincher, Bruce J; Wai, Chien M

2014-06-15

The feasibility of separating U from nitric acid solutions of mixed actinides using tri-n-butylphosphate (TBP)-modified supercritical fluid carbon dioxide (sc-CO2) was investigated. The actinides U, Np, Pu, and Am were extracted into sc-CO2 modified with TBP from a range of nitric acid concentrations, in the absence of, or in the presence of, a number of traditional reducing and/or complexing agents to demonstrate the separation of these metals from U under sc-CO2 conditions. The separation of U from Pu using sc-CO2 was successful at nitric acid concentrations of less than 3M in the presence of acetohydroxamic acid (AHA) or oxalic acid (OA) to mitigate Pu extraction, and the separation of U from Np was successful at nitric acid concentrations of less than 1M in the presence of AHA, OA, or sodium nitrite to mitigate Np extraction. Americium was not well extracted under any condition studied. Copyright © 2014 Elsevier B.V. All rights reserved.

Method of detecting luminescent target ions with modified magnetic microspheres

DOEpatents

Shkrob, Ilya A; Kaminski, Michael D

2014-05-13

This invention provides methods of using modified magnetic microspheres to extract target ions from a sample in order to detect their presence in a microfluidic environment. In one or more embodiments, the microspheres are modified with molecules on the surface that allow the target ions in the sample to form complexes with specific ligand molecules on the microsphere surface. In one or more embodiments, the microspheres are modified with molecules that sequester the target ions from the sample, but specific ligand molecules in solution subsequently re-extract the target ions from the microspheres into the solution, where the complexes form independent of the microsphere surface. Once the complexes form, they are exposed to an excitation wavelength light source suitable for exciting the target ion to emit a luminescent signal pattern. Detection of the luminescent signal pattern allows for determination of the presence of the target ions in the sample.

Deep Eutectic Solvents Modified Molecular Imprinted Polymers for Optimized Purification of Chlorogenic Acid from Honeysuckle.

PubMed

Li, Guizhen; Wang, Wei; Wang, Qian; Zhu, Tao

2016-02-01

Deep eutectic solvents (DES) were synthesized with choline chloride (ChCl), and DES modified molecular imprinted polymers (DES-MIPs), DES modified non-imprinted polymers (DES-NIPs, without template), MIPs and NIPs were prepared in an identical procedure. Fourier transform infrared spectrometer (FT-IR) and field emission scanning electron microscopy (FE-SEM) were used to characterize the obtained polymers. Rebinding experiment and solid-phase extraction (SPE) were used to prove the high selectivity adsorption properties of the polymers. Box-Behnken design (BBD) with three factors was used to optimize the extraction condition of chlorogenic acid (CA) from honeysuckles. The optimum extraction conditions were found to be ultrasonic time optimized (20 min), the volume fraction of ethanol (60%) and ratio of liquid to material (15 mL g(-1)). Under these conditions, the mean extraction yield of CA was 12.57 mg g(-1), which was in good agreement with the predicted BBD model value. Purification of hawthorn extract was achieved by SPE process, and SPE recoveries of CA were 72.56, 64.79, 69.34 and 60.08% by DES-MIPs, DES-NIPs, MIPs and NIPs, respectively. The results showed DES-MIPs had potential for promising functional adsorption material for the purification of bioactive compounds. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Preparation of an aminopropyl imidazole-modified silica gel as a sorbent for solid-phase extraction of carboxylic acid compounds and polycyclic aromatic hydrocarbons.

PubMed

Wang, Na; Guo, Yong; Wang, Licheng; Liang, Xiaojing; Liu, Shujuan; Jiang, Shengxiang

2014-05-21

In this paper, a kind of aminopropyl imidazole-modified silica sorbent was synthesized and used as a solid-phase extraction (SPE) sorbent for the determination of carboxylic acid compounds and polycyclic aromatic hydrocarbons (PAHs). The resultant aminopropyl imidazole-modified silica sorbent was characterized by Fourier transform infrared spectroscopy (FT-IR) and elemental analysis (EA) to ensure the successful binding of aminopropyl imidazole on the surface of silica gel. Then the aminopropyl imidazole-modified silica sorbent served as a SPE sorbent for the enrichment of carboxylic acid compounds and PAHs. The new sorbent exhibited high extraction efficiency towards the tested compounds and the results show that such a sorbent can offer multiple intermolecular interactions: electrostatic, π-π, and hydrophobic interactions. Several parameters affecting the extraction recovery, such as the pH of sample solution, the pH of eluent, the solubility of eluent, the volume of eluent, and sample loading, were also investigated. Under the optimized conditions, the proposed method was applied to the analysis of four carboxylic acid compounds and four PAHs in environmental water samples. Good linearities were obtained for all the tested compounds with R(2) larger than 0.9903. The limits of detection were found to be in the range of 0.0065-0.5 μg L(-1). The recovery values of spiked river water samples were from 63.2% to 112.3% with relative standard deviations (RSDs) less than 10.1% (n = 4).

Dispersive micro-solid-phase extraction of benzoylurea insecticides in honey samples with a β-cyclodextrin-modified attapulgite composite as sorbent.

PubMed

Zhang, Panjie; Cui, Xiangqian; Yang, Xiaoling; Zhang, Sanbing; Zhou, Wenfeng; Gao, Haixiang; Lu, Runhua

2016-01-01

A β-cyclodextrin-modified attapulgite composite was prepared and used as a dispersive micro-solid-phase extraction sorbent for the determination of benzoylurea insecticides in honey samples. Parameters that may influence the extraction efficiency, such as the type and volume of the eluent, the amount of the sorbent, the extraction time and the ionic strength were investigated and optimized using batch and column procedures. Under optimized conditions, good linearity was obtained for all of the tested compounds, with R(2) values of at least 0.9834. The limits of detection were determined in the range of 0.2-1.0 μg/L. The recoveries of the four benzoylurea insecticides in vitex honey and acacia honey increased from 15.2 to 81.4% and from 14.2 to 82.0%, respectively. Although the β-cyclodextrin-modified attapulgite composite did not show a brilliant adsorption capacity for the selected benzoylurea insecticides, it exhibited a higher adsorption capacity toward relatively hydrophobic compounds, such as chlorfluazuron and hexaflumuron (recoveries in vitex honey samples ranged from 70.0 to 81.4% with a precision of 1.0-3.7%). It seemed that the logPow of the benzoylurea insecticides is related to their recoveries. The results confirmed the possibility of using cyclodextrin-modified palygorskite in the determination of relatively hydrophobic trace pharmaceutical residues. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Takeshita, Kenji

A mathematical model to predict the extraction behavior of metal ion between a polymer gel and an aqueous solution was proposed. It consists of the Flory-Huggins formula for evaluating thermodynamically the physico-chemical properties of polymer gel, the modified Stokes-Einstein equation to evaluate the mass transfer rate of metal ion into polymer gel and the equation to evaluate the extraction equilibrium. The extraction of lanthanide elements, Nd(III), Sm(III) and Gd(III), from an aqueous solution containing nitrate ion was carried out by the use of SDB (styrene-divinylbenzene copolymer) gel swollen with a bidentate organophosphorus compound, CMP (dihexyl-N,N-diethylcarbamoylmethylpohosphonate). The binary extraction and themore » effect of the crosslinking degree of SDB gel on the extraction rate were examined. These experimental results were in agreement with the predictions calculated by the proposed model. It was confirmed that the extraction behavior of lanthanide ions into the SDB gel was predicted accurately, when the physico-chemical properties of SDB gel, such as the affinity between SDB and CMP ({chi}) and the crosslinking degree ({nu}{sub e}), and a coefficient defined in the modified Stokes-Einstein equation (K{sub 0}) were known. This model is available as a tool to design an extraction chromatographic process using polymer gel.« less

Electromembrane extraction combined with cyclodextrin-modified capillary electrophoresis for the quantification of trimipramine enantiomers.

PubMed

Fakhari, Ali R; Tabani, Hadi; Nojavan, Saeed; Abedi, Hamid

2012-02-01

A sensitive, simple and reproducible method was developed for preconcentration and determination of trimipramine (TPM) enantiomers in biological samples using electromembrane extraction combined with cyclodextrin-modified capillary electrophoresis (CE). During the extraction, TPM enantiomers migrated from a 5 mL sample solution through a thin layer of 2-nitrophenyl octyl ether NPOE immobilized in the pores of a hollow fiber, and into a 20 μL acidic aqueous acceptor phase presented inside the lumen of the fiber. A Box-Behnken design and the response surface methodology (RSM) were used for the optimization of different variables on extraction efficiency. Optimized extraction conditions were: NPOE as supported liquid membrane, inter-electrode distance of 5 mm, stirring rate of 1000 rpm, 51 V potential difference, 34 min as the extraction time, acceptor phase pH 1.0 and donor phase pH 4.5. Then, the extract was analyzed using optimized cyclodextrin (CD)-modified CE method for the separation of TPM enantiomers. Best results were achieved using 100 mM phosphate running buffer (pH 2.0) containing 10 mM α-CD as the chiral selector, applied voltage of 18 kV and 20°C. The range of quantitation for both enantiomers was 20-500 ng/mL. The method was very reproducible so that intra- and interday RSDs (n=6) were <6%. The limits of quantitation and detection for both enantiomers were 20 and 7 ng/mL, respectively. Finally, this method was successfully applied to determine the concentration of TPM enantiomers in plasma and urine samples without any pre-treatment. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modified sequential extraction for biochar and petroleum coke: Metal release potential and its environmental implications.

PubMed

von Gunten, Konstantin; Alam, Md Samrat; Hubmann, Magdalena; Ok, Yong Sik; Konhauser, Kurt O; Alessi, Daniel S

2017-07-01

A modified Community Bureau of Reference (CBR) sequential extraction method was tested to assess the composition of untreated pyrogenic carbon (biochar) and oil sands petroleum coke. Wood biochar samples were found to contain lower concentrations of metals, but had higher fractions of easily mobilized alkaline earth and transition metals. Sewage sludge biochar was determined to be less recalcitrant and had higher total metal concentrations, with most of the metals found in the more resilient extraction fractions (oxidizable, residual). Petroleum coke was the most stable material, with a similar metal distribution pattern as the sewage sludge biochar. The applied sequential extraction method represents a suitable technique to recover metals from these materials, and is a valuable tool in understanding the metal retaining and leaching capability of various biochar types and carbonaceous petroleum coke samples. Copyright © 2017 Elsevier Ltd. All rights reserved.

Decomposition Techniques for Icesat/glas Full-Waveform Data

NASA Astrophysics Data System (ADS)

Liu, Z.; Gao, X.; Li, G.; Chen, J.

2018-04-01

The geoscience laser altimeter system (GLAS) on the board Ice, Cloud, and land Elevation Satellite (ICESat), is the first long-duration space borne full-waveform LiDAR for measuring the topography of the ice shelf and temporal variation, cloud and atmospheric characteristics. In order to extract the characteristic parameters of the waveform, the key step is to process the full waveform data. In this paper, the modified waveform decomposition method is proposed to extract the echo components from full-waveform. First, the initial parameter estimation is implemented through data preprocessing and waveform detection. Next, the waveform fitting is demonstrated using the Levenberg-Marquard (LM) optimization method. The results show that the modified waveform decomposition method can effectively extract the overlapped echo components and missing echo components compared with the results from GLA14 product. The echo components can also be extracted from the complex waveforms.

Reactive extraction of lactic acid with trioctylamine/methylene chloride/n-hexane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Han, D.H.; Hong, W.H.

The trioctylamine (TOA)/methylene chloride (MC)/n-hexane system was used as the extraction agent for the extraction of lactic acid. Curves of equilibrium and hydration were obtained at various temperatures and concentrations of TOA. A modified mass action model was proposed to interpret the equilibrium and the hydration curves. The reaction mechanism and the corresponding parameters which best represent the equilibrium data were estimated, and the concentration of water in the organic phase was predicted by inserting the parameters into the simple mathematical equation of the modified model. The concentration of MC and the change of temperature were important factors for themore » extraction and the stripping process. The stripping was performed by a simple distillation which was a combination of temperature-swing regeneration and diluent-swing regeneration. The type of inactive diluent has no influence on the stripping. The stripping efficiencies were about 70%.« less

Fractionation and Purification of Bioactive Compounds Obtained from a Brewery Waste Stream

PubMed Central

Barbosa-Pereira, Letricia; Pocheville, Ainara; Angulo, Inmaculada; Paseiro-Losada, Perfecto; Cruz, Jose M.

2013-01-01

The brewery industry generates waste that could be used to yield a natural extract containing bioactive phenolic compounds. We compared two methods of purifying the crude extract—solid-phase extraction (SPE) and supercritical fluid extraction (SFE)—with the aim of improving the quality of the final extract for potential use as safe food additive, functional food ingredient, or nutraceutical. The predominant fractions yielded by SPE were the most active, and the fraction eluted with 30% (v/v) of methanol displayed the highest antioxidant activity (0.20 g L−1), similar to that of BHA. The most active fraction yielded by SFE (EC50 of 0.23 g L−1) was obtained under the following conditions: temperature 40°C, pressure 140 bar, extraction time 30 minutes, ethanol (6%) as a modifier, and modifier flow 0.2 mL min−1. Finally, we found that SFE is the most suitable procedure for purifying the crude extracts and improves the organoleptic characteristics of the product: the final extract was odourless, did not contain solvent residues, and was not strongly coloured. Therefore, natural extracts obtained from the residual stream and purified by SFE can be used as natural antioxidants with potential applications in the food, cosmetic, and pharmaceutical industries. PMID:23762844

Simulation study on ion extraction from electron cyclotron resonance ion sources

NASA Astrophysics Data System (ADS)

Fu, S.; Kitagawa, A.; Yamada, S.

1994-04-01

In order to study beam optics of NIRS-ECR ion source used in the HIMAC project, the EGUN code has been modified to make it capable of modeling ion extraction from a plasma. Two versions of the modified code are worked out with two different methods in which 1D and 2D sheath theories are used, respectively. Convergence problem of the strong nonlinear self-consistent equations is investigated. Simulations on NIRS-ECR ion source and HYPER-ECR ion source are presented in this paper, exhibiting an agreement with the experiment results.

Hot water extracted wood fiber for production of wood plastic composites (WPCs)

Treesearch

Manuel Raul Pelaez-Samaniego; Vikram Yadama; Eini Lowell; Thomas E. Amidon; Timothy L. Chaffee

2013-01-01

Undebarked ponderosa pine chips were treated by hot water extraction to modify the chemical composition. In the treated pine (TP) , the mass was reduced by approximately 20%, and the extract was composed mainly of degradation products of hemicelluloses. Wood flour produced from TP and unextracted chips (untreated pine, UP) was blended with high-density polyethylene (...

Current lipid extraction methods are significantly enhanced adding a water treatment step in Chlorella protothecoides.

PubMed

Ren, Xiaojie; Zhao, Xinhe; Turcotte, François; Deschênes, Jean-Sébastien; Tremblay, Réjean; Jolicoeur, Mario

2017-02-11

Microalgae have the potential to rapidly accumulate lipids of high interest for the food, cosmetics, pharmaceutical and energy (e.g. biodiesel) industries. However, current lipid extraction methods show efficiency limitation and until now, extraction protocols have not been fully optimized for specific lipid compounds. The present study thus presents a novel lipid extraction method, consisting in the addition of a water treatment of biomass between the two-stage solvent extraction steps of current extraction methods. The resulting modified method not only enhances lipid extraction efficiency, but also yields a higher triacylglycerols (TAG) ratio, which is highly desirable for biodiesel production. Modification of four existing methods using acetone, chloroform/methanol (Chl/Met), chloroform/methanol/H 2 O (Chl/Met/H 2 O) and dichloromethane/methanol (Dic/Met) showed respective lipid extraction yield enhancement of 72.3, 35.8, 60.3 and 60.9%. The modified acetone method resulted in the highest extraction yield, with 68.9 ± 0.2% DW total lipids. Extraction of TAG was particularly improved with the water treatment, especially for the Chl/Met/H 2 O and Dic/Met methods. The acetone method with the water treatment led to the highest extraction level of TAG with 73.7 ± 7.3 µg/mg DW, which is 130.8 ± 10.6% higher than the maximum value obtained for the four classical methods (31.9 ± 4.6 µg/mg DW). Interestingly, the water treatment preferentially improved the extraction of intracellular fractions, i.e. TAG, sterols, and free fatty acids, compared to the lipid fractions of the cell membranes, which are constituted of phospholipids (PL), acetone mobile polar lipids and hydrocarbons. Finally, from the 32 fatty acids analyzed for both neutral lipids (NL) and polar lipids (PL) fractions, it is clear that the water treatment greatly improves NL-to-PL ratio for the four standard methods assessed. Water treatment of biomass after the first solvent extraction step helps the subsequent release of intracellular lipids in the second extraction step, thus improving the global lipids extraction yield. In addition, the water treatment positively modifies the intracellular lipid class ratios of the final extract, in which TAG ratio is significantly increased without changes in the fatty acids composition. The novel method thus provides an efficient way to improve lipid extraction yield of existing methods, as well as selectively favoring TAG, a lipid of the upmost interest for biodiesel production.

Method for extracting lanthanides and actinides from acid solutions by modification of Purex solvent

DOEpatents

Horwitz, E.P.; Kalina, D.G.

1984-05-21

A process has been developed for the extraction of multivalent lanthanide and actinide values from acidic waste solutions, and for the separation of these values from fission product and other values, which utilizes a new series of neutral bi-functional extractants, the alkyl(phenyl)-N, N-dialkylcarbamoylmethylphosphine oxides, in combination with a phase modifier to form an extraction solution. The addition of the extractant to the Purex process extractant, tri-n-butylphosphate in normal paraffin hydrocarbon diluent, will permit the extraction of multivalent lanthanide and actinide values from 0.1 to 12.0 molar acid solutions.

A deconvolution extraction method for 2D multi-object fibre spectroscopy based on the regularized least-squares QR-factorization algorithm

NASA Astrophysics Data System (ADS)

Yu, Jian; Yin, Qian; Guo, Ping; Luo, A.-li

2014-09-01

This paper presents an efficient method for the extraction of astronomical spectra from two-dimensional (2D) multifibre spectrographs based on the regularized least-squares QR-factorization (LSQR) algorithm. We address two issues: we propose a modified Gaussian point spread function (PSF) for modelling the 2D PSF from multi-emission-line gas-discharge lamp images (arc images), and we develop an efficient deconvolution method to extract spectra in real circumstances. The proposed modified 2D Gaussian PSF model can fit various types of 2D PSFs, including different radial distortion angles and ellipticities. We adopt the regularized LSQR algorithm to solve the sparse linear equations constructed from the sparse convolution matrix, which we designate the deconvolution spectrum extraction method. Furthermore, we implement a parallelized LSQR algorithm based on graphics processing unit programming in the Compute Unified Device Architecture to accelerate the computational processing. Experimental results illustrate that the proposed extraction method can greatly reduce the computational cost and memory use of the deconvolution method and, consequently, increase its efficiency and practicability. In addition, the proposed extraction method has a stronger noise tolerance than other methods, such as the boxcar (aperture) extraction and profile extraction methods. Finally, we present an analysis of the sensitivity of the extraction results to the radius and full width at half-maximum of the 2D PSF.

Designed polar cosolvent-modified supercritical CO2 removing caffeine from and retaining catechins in green tea powder using response surface methodology.

PubMed

Huang, Kuo-Jong; Wu, Jia-Jiuan; Chiu, Yung-Ho; Lai, Cheng-Yung; Chang, Chieh-Ming J

2007-10-31

This study examines cosolvent-modified supercritical carbon dioxide (SC-CO2) to remove caffeine from and to retain catechins in green tea powder. The response surface method was adopted to determine the optimal operation conditions in terms of the extraction efficiencies and concentration factors of caffeine and catechins during the extractions. When SC-CO2 was used at 333 K and 300 bar, 91.5% of the caffeine was removed and 80.8% of catechins were retained in the tea: 3600 g of carbon dioxide was used in the extraction of 4 g of tea soaked with 1 g of water. Under the same extraction conditions, 10 g of water was added to <800 g of carbon dioxide in an extraction that completely removed caffeine (that is, the caffeine extraction efficiency was 100%). The optimal result as predicted by three-factor response surface methodology and supported by experimental data was that in 1.5 h of extraction, 640 g of carbon dioxide at 323 K and 275 bar with the addition of 6 g of water extracted 71.9% of the caffeine while leaving 67.8% of the catechins in 8 g of tea. Experimental data indicated that supercritical carbon dioxide decaffeination increased the concentrations of caffeine in the SC-CO2 extracts at 353 K.

Movement of Soil-Applied Imidacloprid and Thiamethoxam into Nectar and Pollen of Squash (Cucurbita pepo)

PubMed Central

Stoner, Kimberly A.; Eitzer, Brian D.

2012-01-01

There has been recent interest in the threat to bees posed by the use of systemic insecticides. One concern is that systemic insecticides may translocate from the soil into pollen and nectar of plants, where they would be ingested by pollinators. This paper reports on the movement of two such systemic neonicotinoid insecticides, imidacloprid and thiamethoxam, into the pollen and nectar of flowers of squash (Cucurbita pepo cultivars “Multipik,” “Sunray” and “Bush Delicata”) when applied to soil by two methods: (1) sprayed into soil before seeding, or (2) applied through drip irrigation in a single treatment after transplant. All insecticide treatments were within labeled rates for these compounds. Pollen and nectar samples were analyzed using a standard extraction method widely used for pesticides (QuEChERS) and liquid chromatography mass spectrometric analysis. The concentrations found in nectar, 10±3 ppb (mean ± s.d) for imidacloprid and 11±6 ppb for thiamethoxam, are higher than concentrations of neonicotinoid insecticides in nectar of canola and sunflower grown from treated seed, and similar to those found in a recent study of neonicotinoids applied to pumpkins at transplant and through drip irrigation. The concentrations in pollen, 14±8 ppb for imidacloprid and 12±9 ppb for thiamethoxam, are higher than those found for seed treatments in most studies, but at the low end of the range found in the pumpkin study. Our concentrations fall into the range being investigated for sublethal effects on honey bees and bumble bees. PMID:22761727

Identification and quantification of fumonisin A1, A2, and A3 in corn by high-resolution liquid chromatography-orbitrap mass spectrometry.

PubMed

Tamura, Masayoshi; Mochizuki, Naoki; Nagatomi, Yasushi; Harayama, Koichi; Toriba, Akira; Hayakawa, Kazuichi

2015-02-16

Three compounds, hypothesized as fumonisin A1 (FA1), fumonisin A2 (FA2), and fumonisin A3 (FA3), were detected in a corn sample contaminated with mycotoxins by high-resolution liquid chromatography-Orbitrap mass spectrometry (LC-Orbitrap MS). One of them has been identified as FA1 synthesized by the acetylation of fumonisin B1 (FB1), and established a method for its quantification. Herein, we identified the two remaining compounds as FA2 and FA3, which were acetylated fumonisin B2 (FB2) and fumonisin B3 (FB3), respectively. Moreover, we examined a method for the simultaneous analysis of FA1, FA2, FA3, FB1, FB2, and FB3. The corn samples were prepared by extraction using a QuEChERS kit and purification using a multifunctional cartridge. The linearity, recovery, repeatability, limit of detection, and limit of quantification of the method were >0.99, 82.9%-104.6%, 3.7%-9.5%, 0.02-0.60 μg/kg, and 0.05-1.98 μg/kg, respectively. The simultaneous analysis of the six fumonisins revealed that FA1, FA2, and FA3 were present in all corn samples contaminated with FB1, FB2, and FB3. The results suggested that corn marketed for consumption can be considered as being contaminated with both the fumonisin B-series and with fumonisin A-series. This report presents the first identification and quantification of FA1, FA2, and FA3 in corn samples.

Analysis of imidacloprid residues in fruits, vegetables, cereals, fruit juices, and baby foods, and daily intake estimation in and around Lucknow, India.

PubMed

Kapoor, Upasana; Srivastava, M K; Srivastava, Ashutosh Kumar; Patel, D K; Garg, Veena; Srivastava, L P

2013-03-01

A total of 250 samples-including fruits, fruit juices, and baby foods (50 samples each), vegetables (70 samples), and cereals (30 samples)-were collected from Lucknow, India, and analyzed for the presence of imidacloprid residues. The QuEChERS (quick, easy, cheap, effective, rugged, and safe) method of extraction coupled with high-performance liquid chromatographic analysis were carried out, and imidacloprid residues were qualitatively confirmed by liquid chromatography-mass spectrometry. Imidacloprid was not detected in samples of fruit juices and baby foods. It was, however, detected in 38 samples of fruits, vegetables, and cereals, which is about 15.20% of the total samples. Of samples of fruits, 22% showed the presence of imidacloprid, and 2% of samples showed residues above the maximal residue limit. Although imidacloprid was detected in 24% of vegetable samples, only 5.71% showed the presence of imidacloprid above the maximal residue limit. However, 33% of cereal samples showed the presence of imidacloprid, and about 3% of samples were above the maximal residue limit. The calculated estimated daily intake ranged between 0.004 and 0.131 µg/kg body weight, and the hazard indices ranged from 0.007 to 0.218 for these food commodities. It is therefore indicated that lifetime consumption of vegetables, fruits, fruit juices, baby foods, wheat, rice, and pulses may not pose a health hazard for the population of Lucknow because the hazard indices for imidacloprid residues were below one. Copyright © 2012 SETAC.

Evaluation of trace analyte identification in complex matrices by low-resolution gas chromatography--Mass spectrometry through signal simulation.

PubMed

Bettencourt da Silva, Ricardo J N

2016-04-01

The identification of trace levels of compounds in complex matrices by conventional low-resolution gas chromatography hyphenated with mass spectrometry is based in the comparison of retention times and abundance ratios of characteristic mass spectrum fragments of analyte peaks from calibrators with sample peaks. Statistically sound criteria for the comparison of these parameters were developed based on the normal distribution of retention times and the simulation of possible non-normal distribution of correlated abundances ratios. The confidence level used to set the statistical maximum and minimum limits of parameters defines the true positive rates of identifications. The false positive rate of identification was estimated from worst-case signal noise models. The estimated true and false positive identifications rate from one retention time and two correlated ratios of three fragments abundances were combined using simple Bayes' statistics to estimate the probability of compound identification being correct designated examination uncertainty. Models of the variation of examination uncertainty with analyte quantity allowed the estimation of the Limit of Examination as the lowest quantity that produced "Extremely strong" evidences of compound presence. User friendly MS-Excel files are made available to allow the easy application of developed approach in routine and research laboratories. The developed approach was successfully applied to the identification of chlorpyrifos-methyl and malathion in QuEChERS method extracts of vegetables with high water content for which the estimated Limit of Examination is 0.14 mg kg(-1) and 0.23 mg kg(-1) respectively. Copyright © 2015 Elsevier B.V. All rights reserved.

Trace analysis of multi-class pesticide residues in Chinese medicinal health wines using gas chromatography with electron capture detection

PubMed Central

Kong, Wei-Jun; Liu, Qiu-Tao; Kong, Dan-Dan; Liu, Qian-Zhen; Ma, Xin-Ping; Yang, Mei-Hua

2016-01-01

A method is described for multi-residue, high-throughput determination of trace levels of 22 organochlorine pesticides (OCPs) and 5 pyrethroid pesticides (PYPs) in Chinese medicinal (CM) health wines using a QuEChERS (quick, easy, cheap, effective, rugged, and safe) based extraction method and gas chromatography-electron capture detection (GC-ECD). Several parameters were optimized to improve preparation and separation time while still maintaining high sensitivity. Validation tests of spiked samples showed good linearities for 27 pesticides (R = 0.9909–0.9996) over wide concentration ranges. Limits of detection (LODs) and quantification (LOQs) were measured at ng/L levels, 0.06–2 ng/L and 0.2–6 ng/L for OCPs and 0.02–3 ng/L and 0.06–7 ng/L for PYPs, respectively. Inter- and intra-day precision tests showed variations of 0.65–9.89% for OCPs and 0.98–13.99% for PYPs, respectively. Average recoveries were in the range of 47.74–120.31%, with relative standard deviations below 20%. The developed method was then applied to analyze 80 CM wine samples. Beta-BHC (Benzene hexachloride) was the most frequently detected pesticide at concentration levels of 5.67–31.55 mg/L, followed by delta-BHC, trans-chlordane, gamma-BHC, and alpha-BHC. The validated method is simple and economical, with adequate sensitivity for trace levels of multi-class pesticides. It could be adopted by laboratories for this and other types of complex matrices analysis. PMID:26883080

Trace analysis of multi-class pesticide residues in Chinese medicinal health wines using gas chromatography with electron capture detection

NASA Astrophysics Data System (ADS)

Kong, Wei-Jun; Liu, Qiu-Tao; Kong, Dan-Dan; Liu, Qian-Zhen; Ma, Xin-Ping; Yang, Mei-Hua

2016-02-01

A method is described for multi-residue, high-throughput determination of trace levels of 22 organochlorine pesticides (OCPs) and 5 pyrethroid pesticides (PYPs) in Chinese medicinal (CM) health wines using a QuEChERS (quick, easy, cheap, effective, rugged, and safe) based extraction method and gas chromatography-electron capture detection (GC-ECD). Several parameters were optimized to improve preparation and separation time while still maintaining high sensitivity. Validation tests of spiked samples showed good linearities for 27 pesticides (R = 0.9909-0.9996) over wide concentration ranges. Limits of detection (LODs) and quantification (LOQs) were measured at ng/L levels, 0.06-2 ng/L and 0.2-6 ng/L for OCPs and 0.02-3 ng/L and 0.06-7 ng/L for PYPs, respectively. Inter- and intra-day precision tests showed variations of 0.65-9.89% for OCPs and 0.98-13.99% for PYPs, respectively. Average recoveries were in the range of 47.74-120.31%, with relative standard deviations below 20%. The developed method was then applied to analyze 80 CM wine samples. Beta-BHC (Benzene hexachloride) was the most frequently detected pesticide at concentration levels of 5.67-31.55 mg/L, followed by delta-BHC, trans-chlordane, gamma-BHC, and alpha-BHC. The validated method is simple and economical, with adequate sensitivity for trace levels of multi-class pesticides. It could be adopted by laboratories for this and other types of complex matrices analysis.

Multiresidue analysis of 22 sulfonamides and their metabolites in animal tissues using quick, easy, cheap, effective, rugged, and safe extraction and high resolution mass spectrometry (hybrid linear ion trap-Orbitrap).

PubMed

Abdallah, H; Arnaudguilhem, C; Jaber, F; Lobinski, R

2014-08-15

A new high performance liquid chromatography-high resolution mass spectrometry (HPLC-HRMS) method was developed for a simultaneous multi-residue analysis of 22 sulfonamides (SAs) and their metabolites in edible animal (pig, beef, sheep and chicken) tissues. Sample preparation was optimized on the basis of the "QuEChERS" protocol. The analytes were identified using their LC retention times and accurate mass; the identification was further confirmed by multi-stage high mass accuracy (<5ppm) mass spectrometry. The performance of the method was evaluated according to the EU guidelines for the validation of screening methods for the analysis of veterinary drugs residues. Acceptable values were obtained for: linearity (R(2)<0.99), limit of detection (LOD, 3-26μg/kg), limit of quantification (LOQ, 11-88μg/kg), accuracy (recovery 88-112%), intra- and inter-day precision 1-14 and 1-17%, respectively, decision limit (CCα) and detection capability (CCβ) around the maximum residue limits (MRL) of SAs (100μg/kg). The method was validated by analysis of a reference material FAPAS-02188 "Pig kidney" with ǀ Z-scoreǀ<0.63. The method was applied to various matrices (kidney, liver, muscle) originated from pig, beef, sheep, and chicken) allowing the simultaneous quantification of target sulfonamides at concentration levels above the MRL/2 and the identification of untargeted compounds such as N(4)-acetyl metabolites using multi-stage high mass accuracy mass spectrometry. Copyright © 2014 Elsevier B.V. All rights reserved.

Solid-phase microfibers based on polyethylene glycol modified single-walled carbon nanotubes for the determination of chlorinated organic carriers in textiles.

PubMed

Zhang, Wei-Ya; Sun, Yin; Wang, Cheng-Ming; Wu, Cai-Ying

2011-09-01

Based on polyethylene glycol modified single-walled carbon nanotubes, a novel sol-gel fiber coating was prepared and applied to the headspace microextraction of chlorinated organic carriers (COCs) in textiles by gas chromatography-electron capture detection. The preparation of polyethylene glycol modified single-walled carbon nanotubes and the sol-gel fiber coating process was stated and confirmed by infrared spectra, Raman spectroscopy, and scanning electron microscopy. Several parameters affecting headspace microextraction, including extraction temperature, extraction time, salting-out effect, and desorption time, were optimized by detecting 11 COCs in simulative sweat samples. Compared with the commercial solid-phase microextraction fibers, the sol-gel polyethylene glycol modified single-walled carbon nanotubes fiber showed higher extraction efficiency, better thermal stability, and longer life span. The method detection limits for COCs were in the range from 0.02 to 7.5 ng L(-1) (S/N = 3). The linearity of the developed method varied from 0.001 to 50 μg L(-1) for all analytes, with coefficients of correlation greater than 0.974. The developed method was successfully applied to the analysis of trace COCs in textiles, the recoveries of the analytes indicated that the developed method was considerably useful for the determination of COCs in ecological textile samples.

Gait recognition based on Gabor wavelets and modified gait energy image for human identification

NASA Astrophysics Data System (ADS)

Huang, Deng-Yuan; Lin, Ta-Wei; Hu, Wu-Chih; Cheng, Chih-Hsiang

2013-10-01

This paper proposes a method for recognizing human identity using gait features based on Gabor wavelets and modified gait energy images (GEIs). Identity recognition by gait generally involves gait representation, extraction, and classification. In this work, a modified GEI convolved with an ensemble of Gabor wavelets is proposed as a gait feature. Principal component analysis is then used to project the Gabor-wavelet-based gait features into a lower-dimension feature space for subsequent classification. Finally, support vector machine classifiers based on a radial basis function kernel are trained and utilized to recognize human identity. The major contributions of this paper are as follows: (1) the consideration of the shadow effect to yield a more complete segmentation of gait silhouettes; (2) the utilization of motion estimation to track people when walkers overlap; and (3) the derivation of modified GEIs to extract more useful gait information. Extensive performance evaluation shows a great improvement of recognition accuracy due to the use of shadow removal, motion estimation, and gait representation using the modified GEIs and Gabor wavelets.

Modified Activated Carbon Prepared from Acorn Shells as a New Solid-Phase Extraction Sorbent for the Preconcentration and Determination of Trace Amounts of Nickel in Food Samples Prior to Flame Atomic Absorption Spectrometry.

PubMed

Ebrahimi, Bahram

2017-03-01

A new solid-phase extraction (SPE) sorbent was introduced based on acidic-modified (AM) activated carbon (AC) prepared from acorn shells of native oak trees in Kurdistan. Hydrochloric acid (15%, w/w) and nitric acid (32.5%, w/w) were used to condition and modify AC. The IR spectra of AC and AM-AC showed that AM lead to the formation of increasing numbers of acidic functional groups on AM-AC. AM-AC was used in the SPE method for the extraction and preconcentration of Ni+2 prior to flame atomic absorption spectrometric determination at ng/mL levels in model and real food samples. Effective parameters of the SPE procedure, such as the pH of the solutions, sorbent dosage, extraction time, sample volume, type of eluent, and matrix ions, were considered and optimized. An enrichment factor of 140 was obtained. The calibration curve was linear with an R2 of 0.997 in the concentration range of 1-220 ng/mL. The RSD was 5.67% (for n = 7), the LOD was 0.352 ng/mL, and relative recoveries in vegetable samples ranged from 96.7 to 103.7%.

OPTIMIZED DETERMINATION OF TRACE JET FUEL VOLATILE ORGANIC COMPOUNDS IN HUMAN BLOOD USING IN-FIELD LIQUID-LIQUID EXTRACTION WITH SUBSEQUENT LABORATORY GAS CHROMATOGRAPHIC-MASS SPECTROMETRIC ANALYSIS AND ON-COLUMN LARGE VOLUME INJECTION

EPA Science Inventory

A practical and sensitive method to assess volatile organic compounds (VOCs) from JP-8 jet fuel in human whole blood was developed by modifying previously established liquid-liquid extraction procedures, optimizing extraction times, solvent volume, specific sample processing te...

A modified method for determining tannin-protein precipitation capacity using accelerated solvent extraction (ASE) and microplate gel filtration.

PubMed

McArt, Scott H; Spalinger, Donald E; Kennish, John M; Collins, William B

2006-06-01

The protein precipitation assay used by Robbins et al., (1987) Ecology 68:98-107 has been shown to predict successfully the reduction in protein availability to some ruminants due to tannins. The procedure, however, is expensive and laborious, which limits its utility, especially for quantitative ecological or nutritional applications where large numbers of assays may be required. We have modified the method to decrease its cost and increase laboratory efficiency by: (1) automating the extraction by using Accelerated Solvent Extraction (ASE); and (2) by scaling and automating the precipitation reaction, chromatography, and spectrometry with microplate gel filtration and an automated UV-VIS microplate spectrometer. ASE extraction is shown to be as effective at extracting tannins as the hot methanol technique. Additionally, the microplate assay is sensitive and precise. We show that the results from the new technique correspond in a nearly 1:1 relationship to the results of the previous technique. Hence, this method could reliably replace the older method with no loss in relevance to herbivore protein digestion. Moreover, the ASE extraction technique should be applicable to other tannin-protein precipitation assays and possibly other phenolic assays.

Modified kernel-based nonlinear feature extraction.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ma, J.; Perkins, S. J.; Theiler, J. P.

2002-01-01

Feature Extraction (FE) techniques are widely used in many applications to pre-process data in order to reduce the complexity of subsequent processes. A group of Kernel-based nonlinear FE ( H E ) algorithms has attracted much attention due to their high performance. However, a serious limitation that is inherent in these algorithms -- the maximal number of features extracted by them is limited by the number of classes involved -- dramatically degrades their flexibility. Here we propose a modified version of those KFE algorithms (MKFE), This algorithm is developed from a special form of scatter-matrix, whose rank is not determinedmore » by the number of classes involved, and thus breaks the inherent limitation in those KFE algorithms. Experimental results suggest that MKFE algorithm is .especially useful when the training set is small.« less

GaN-based LEDs with a high light extraction composite surface structure fabricated by a modified YAG laser lift-off technology and the patterned sapphire substrates

NASA Astrophysics Data System (ADS)

Sun, Yongjian; Trieu, Simeon; Yu, Tongjun; Chen, Zhizhong; Qi, Shengli; Tian, Pengfei; Deng, Junjing; Jin, Xiaoming; Zhang, Guoyi

2011-08-01

Vertical structure LEDs have been fabricated with a novel light extraction composite surface structure composed of a micron grating and nano-structure. The composite surface structure was generated by using a modified YAG laser lift-off technique, separating the wafers from cone-shaped patterned sapphire substrates. LEDs thus fabricated showed the light output power increase about 1.7-2.5 times when compared with conventional vertical structure LEDs grown on plane sapphire substrates. A three-dimensional finite difference time domain method was used to simulate this new kind of LED device. It was determined that nano-structures in composite surface patterns play a key role in the improvement of light extraction efficiency of LEDs.

Integration of carboxyl modified magnetic particles and aqueous two-phase extraction for selective separation of proteins.

PubMed

Gai, Qingqing; Qu, Feng; Zhang, Tao; Zhang, Yukui

2011-07-15

Both of the magnetic particle adsorption and aqueous two-phase extraction (ATPE) were simple, fast and low-cost method for protein separation. Selective proteins adsorption by carboxyl modified magnetic particles was investigated according to protein isoelectric point, solution pH and ionic strength. Aqueous two-phase system of PEG/sulphate exhibited selective separation and extraction for proteins before and after magnetic adsorption. The two combination ways, magnetic adsorption followed by ATPE and ATPE followed by magnetic adsorption, for the separation of proteins mixture of lysozyme, bovine serum albumin, trypsin, cytochrome C and myloglobin were discussed and compared. The way of magnetic adsorption followed by ATPE was also applied to human serum separation. Copyright © 2011 Elsevier B.V. All rights reserved.

Magnetic dispersive solid-phase extraction based on modified magnetic nanoparticles for the detection of cocaine and cocaine metabolites in human urine by high-performance liquid chromatography-mass spectrometry.

PubMed

Yang, Feiyu; Zou, Yun; Ni, Chunfang; Wang, Rong; Wu, Min; Liang, Chen; Zhang, Jiabin; Yuan, Xiaoliang; Liu, Wenbin

2017-11-01

An easy-to-handle magnetic dispersive solid-phase extraction procedure was developed for preconcentration and extraction of cocaine and cocaine metabolites in human urine. Divinyl benzene and vinyl pyrrolidone functionalized silanized Fe 3 O 4 nanoparticles were synthesized and used as adsorbents in this procedure. Scanning electron microscopy, vibrating sample magnetometry, and infrared spectroscopy were employed to characterize the modified adsorbents. A high-performance liquid chromatography with mass spectrometry method for determination of cocaine and its metabolites in human urine sample has been developed with pretreatment of the samples by magnetic dispersive solid-phase extraction. The obtained results demonstrated the higher extraction capacity of the prepared nanoparticles with recoveries between 75.1 to 105.7% and correlation coefficients higher than 0.9971. The limits of detection for the cocaine and cocaine metabolites were 0.09-1.10 ng/mL. The proposed magnetic dispersive solid-phase extraction method provided a rapid, environmentally friendly and magnetic stuff recyclable approach and it was confirmed that the prepared adsorbents material was a kind of highly effective extraction materials for the trace cocaine and cocaine metabolites analyses in human urine. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-throughput and selective solid-phase extraction of urinary catecholamines by crown ether-modified resin composite fiber.

PubMed

Chen, LiQin; Wang, Hui; Xu, Zhen; Zhang, QiuYue; Liu, Jia; Shen, Jun; Zhang, WanQi

2018-08-03

In the present study, we developed a simple and high-throughput solid phase extraction (SPE) procedure for selective extraction of catecholamines (CAs) in urine samples. The SPE adsorbents were electrospun composite fibers functionalized with 4-carboxybenzo-18-crown-6 ether modified XAD resin and polystyrene, which were packed into 96-well columns and used for high-throughput selective extraction of CAs in healthy human urine samples. Moreover, the extraction efficiency of packed-fiber SPE (PFSPE) was examined by high performance liquid chromatography coupled with fluorescence detector. The parameters affecting the extraction efficiency and impurity removal efficiency were optimized, and good linearity ranging from 0.5 to 400 ng/mL was obtained with a low limit of detection (LOD, 0.2-0.5 ng/mL) and a good repeatability (2.7%-3.7%, n = 6). The extraction recoveries of three CAs ranged from 70.5% to 119.5%. Furthermore, stable and reliable results obtained by the fluorescence detector were superior to those obtained by the electrochemical detector. Collectively, PFSPE coupled with 96-well columns was a simple, rapid, selective, high-throughput and cost-efficient method, and the proposed method could be applied in clinical chemistry. Copyright © 2018 Elsevier B.V. All rights reserved.

Direct extraction of genomic DNA from maize with aqueous ionic liquid buffer systems for applications in genetically modified organisms analysis.

PubMed

Gonzalez García, Eric; Ressmann, Anna K; Gaertner, Peter; Zirbs, Ronald; Mach, Robert L; Krska, Rudolf; Bica, Katharina; Brunner, Kurt

2014-12-01

To date, the extraction of genomic DNA is considered a bottleneck in the process of genetically modified organisms (GMOs) detection. Conventional DNA isolation methods are associated with long extraction times and multiple pipetting and centrifugation steps, which makes the entire procedure not only tedious and complicated but also prone to sample cross-contamination. In recent times, ionic liquids have emerged as innovative solvents for biomass processing, due to their outstanding properties for dissolution of biomass and biopolymers. In this study, a novel, easily applicable, and time-efficient method for the direct extraction of genomic DNA from biomass based on aqueous-ionic liquid solutions was developed. The straightforward protocol relies on extraction of maize in a 10 % solution of ionic liquids in aqueous phosphate buffer for 5 min at room temperature, followed by a denaturation step at 95 °C for 10 min and a simple filtration to remove residual biopolymers. A set of 22 ionic liquids was tested in a buffer system and 1-ethyl-3-methylimidazolium dimethylphosphate, as well as the environmentally benign choline formate, were identified as ideal candidates. With this strategy, the quality of the genomic DNA extracted was significantly improved and the extraction protocol was notably simplified compared with a well-established method.

[Improvement of powder flowability and hygroscopicity of traditional Chinese medicine extract by surface coating modification technology].

PubMed

Zeng, Rong-Gui; Jiang, Qie-Ying; Liao, Zheng-Gen; Zhao, Guo-Wei; Luo, Yun; Luo, Juan; Lv, Dan

2016-06-01

To study the improvement of powder flowability and hygroscopicity of traditional Chinese medicine extract by surface coating modification technology. The 1% hydrophobic silica nanoparticles were used as surface modifier, and andrographis extract powder was taken as a model drug. Three different techniques were used for coating model drugs, with angle of repose, compressibility, flat angle and cohesion as the comprehensive evaluation indexes for the powder flowability. The powder particle size and the size distribution were measured by Mastersizer 2000. FEI scanning electron microscope was used to observe the surface morphology and structure of the powder. The percentage of Si element on the powder surface was measured by energy dispersive spectrometer. The hygroscopicity of powder was determined by Chinese pharmacopoeia method. All of the three techniques can improve the flowability of powder extract. In particular, hygroscopicity of extract powder can also be improved by dispersion and then high-speed mixing, which can produce a higher percentage of Si element on the powder surface. The improvement principle may be correlated with a modifier adhered to the powder surface. Copyright© by the Chinese Pharmaceutical Association.

Rapid methods for extraction and concentration of poliovirus from oyster tissues.

PubMed

Richards, G P; Goldmintz, D; Green, D L; Babinchak, J A

1982-12-01

A procedure is discussed for the extraction of poliovirus from oyster meats by modification of several enterovirus extraction techniques. The modified method uses meat extract and Cat-Floc, a polycationic electrolyte, for virus extraction and concentration. Virus recovery from inoculated oyster homogenates is 93-120%. Adsorption of viruses to oyster proteins by acidification of homogenates does not affect virus recovery. Elution of viruses from oyster proteins appears more efficient at pH 9.5 than at pH 8.0. This technique is relatively simple, economical and requires only 2.5 h to complete the combined extraction and concentration procedure.

A novel dianionic amino acid ionic liquid-coated PEG 4000 modified Fe3O4 nanocomposite for the magnetic solid-phase extraction of trypsin.

PubMed

Yang, Qin; Wang, Yuzhi; Zhang, Hongmei; Xu, Kaijia; Wei, Xiaoxiao; Xu, Panli; Zhou, Yigang

2017-11-01

A novel magnetic extractant, PEG 4000 modified Fe 3 O 4 nanomaterial that coated with dianionic amino acid ionic liquid (Fe 3 O 4 @PEG@DAAAIL), was successfully synthesized and characterized. X-ray diffraction (XRD), transmission electron microscope (TEM), vibrating sample magnetometer (VSM), fourier transform infrared spectrometry (FT-IR), thermal gravimetric analysis (TGA) and zeta potentials were used to confirm that the novel nanocomposite was successfully synthesized. Subsequently, the prepared Fe 3 O 4 @PEG@DAAAIL nanocomposite was used as the extractant for trypsin coupled with magnetic solid-phase extraction (MSPE). The concentrations of trypsin in the supernatant were detected by UV-vis spectrophotometer at 278nm. The extraction ability turned out to be better than the other four kinds of extractants prepared in this work. Furthermore, the influence of a series of factors, such as extraction time and temperature, initial trypsin concentration, the value of pH and ionic strength, was systematically investigated. Under the optimal extraction condition, the extraction capacity for trypsin could reach up to 718.73mg/g, absolutely higher than that of other adsorbents reported. This satisfactory extraction capacity could be maintained unchangeable after at least eight days, and kept over 90% of initial extraction capacity after eight recycles. What's more, the activity of trypsin after extraction retained 92.29% of initial activity, verifying the biocompatibility of the prepared extractant. Finally, the developed Fe 3 O 4 @PEG@DAAAIL-MSPE method was successfully applied to the real sample analysis with satisfactory results. All of above proves the potential value of Fe 3 O 4 @PEG@DAAAIL-MSPE in the analysis of biomass. Copyright © 2017 Elsevier B.V. All rights reserved.

Local Charge Injection and Extraction on Surface-Modified Al2O3 Nanoparticles in LDPE.

PubMed

Borgani, Riccardo; Pallon, Love K H; Hedenqvist, Mikael S; Gedde, Ulf W; Haviland, David B

2016-09-14

We use a recently developed scanning probe technique to image with high spatial resolution the injection and extraction of charge around individual surface-modified aluminum oxide nanoparticles embedded in a low-density polyethylene (LDPE) matrix. We find that the experimental results are consistent with a simple band structure model where localized electronic states are available in the band gap (trap states) in the vicinity of the nanoparticles. This work offers experimental support to a previously proposed mechanism for enhanced insulating properties of nanocomposite LDPE and provides a powerful experimental tool to further investigate such properties.

A modified and cost-effective method for hair cortisol analysis.

PubMed

Xiang, Lianbin; Sunesara, Imran; Rehm, Kristina E; Marshall, Gailen D

2016-01-01

Hair cortisol may hold potential as a biomarker for assessment of chronic psychological stress. We report a modified and cost-effective method to prepare hair samples for cortisol assay. Hair samples were ground using an inexpensive ball grinder - ULTRA-TURRAX tube drive. Cortisol was extracted from the powder under various defined conditions. The data showed that the optimal conditions for this method include cortisol extraction at room temperature and evaporation using a stream of room air. These findings should allow more widespread research using economical technology to validate the utility of hair cortisol as a biomarker for assessing chronic stress status.

Uranium extraction: Fuel from seawater

DOE PAGES

Tsouris, Costas; Oak Ridge National Lab.

2017-02-17

Over four billion tonnes of uranium are currently in the oceans that could be harvested for nuclear fuel, but current capture methods have limited performance and reusability. Now, an electrochemical method using modified carbon electrodes is shown to be promising for the extraction of uranium from seawater.

Treatment of psoriatic nails with indigo naturalis oil extract: a non-controlled pilot study.

PubMed

Lin, Yin-Ku; See, Lai-Chu; Chang, Ya-Ching; Huang, Yu-Huei; Chen, Jiun-Liang; Tsou, Teng-Cheng; Leu, Yann-Lii; Shen, Yu-Ming

2011-01-01

In the treatment of nail psoriasis, standardized therapeutic regimens are currently lacking. To evaluate the therapeutic efficacy of indigo naturalis oil extract in patients with nail psoriasis. Patients with nail psoriasis applied indigo naturalis oil extract on affected nails twice daily for 24 weeks. Efficacy was evaluated using the Nail Psoriasis Severity Index (NAPSI) and modified target NAPSI for the single most severely affected nail. Twenty-eight out of 32 patients completed the study. The mean NAPSI was 36.1 ± 14.7 at baseline and decreased to 14.9 ± 11.1 at week 24 while the mean modified target NAPSI was 11.7 ± 3.9 at baseline and decreased to 3.6 ± 3.2 at week 24. Indigo naturalis oil extract appeared to improve nail psoriasis. Although preliminary, these results indicate that it could provide a novel therapeutic option for nail psoriasis, a disease notoriously difficult to treat. Copyright © 2011 S. Karger AG, Basel.

Extraction of rare earth oxides using supercritical carbon dioxide modified with Tri- n-butyl phosphate–nitric acid adducts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baek, Donna L.; Fox, Robert V.; Case, Mary E.

A new tri- n-butylphosphate–nitric acid (TBP–HNO 3) adduct was prepared by combining TBP and fuming (90%) HNO 3. The adduct was characterized, and its phase-equilibrium behavior in supercritical carbon dioxide is reported. Supercritical carbon dioxide (sc-CO 2) was modified with this new adduct [TBP(HNO 3) 5.2(H 2O) 1.7], and the extraction efficacies of selected rare earth oxides (Y, Ce, Eu, Tb, and Dy) at 338 K and 34.5 MPa were compared with those obtained using an adduct formed from concentrated (70%) HNO 3 and TBP [TBP(HNO 3) 1.7(H 2O) 0.6]. All rare earth oxides tested with both adduct species couldmore » be extracted with the exception of cerium oxide. Furthermore, the water and acid concentrations in the different adducts were found to play a significant role in rare earth oxide extraction efficiency.« less

Extraction of rare earth oxides using supercritical carbon dioxide modified with Tri- n-butyl phosphate–nitric acid adducts

DOE PAGES

Baek, Donna L.; Fox, Robert V.; Case, Mary E.; ...

2016-06-14

A new tri- n-butylphosphate–nitric acid (TBP–HNO 3) adduct was prepared by combining TBP and fuming (90%) HNO 3. The adduct was characterized, and its phase-equilibrium behavior in supercritical carbon dioxide is reported. Supercritical carbon dioxide (sc-CO 2) was modified with this new adduct [TBP(HNO 3) 5.2(H 2O) 1.7], and the extraction efficacies of selected rare earth oxides (Y, Ce, Eu, Tb, and Dy) at 338 K and 34.5 MPa were compared with those obtained using an adduct formed from concentrated (70%) HNO 3 and TBP [TBP(HNO 3) 1.7(H 2O) 0.6]. All rare earth oxides tested with both adduct species couldmore » be extracted with the exception of cerium oxide. Furthermore, the water and acid concentrations in the different adducts were found to play a significant role in rare earth oxide extraction efficiency.« less

The "New Oxford English Dictionary" Project.

ERIC Educational Resources Information Center

Fawcett, Heather

1993-01-01

Describes the conversion of the 22,000-page Oxford English Dictionary to an electronic version incorporating a modified Standard Generalized Markup Language (SGML) syntax. Explains that the database designers chose structured markup because it supports users' data searching needs, allows textual components to be extracted or modified, and allows…

Modified natural diatomite and its enhanced immobilization of lead, copper and cadmium in simulated contaminated soils.

PubMed

Ye, Xinxin; Kang, Shenghong; Wang, Huimin; Li, Hongying; Zhang, Yunxia; Wang, Guozhong; Zhao, Huijun

2015-05-30

Natural diatomite was modified through facile acid treatment and ultrasonication, which increased its electronegativity, and the pore volume and surface area achieved to 0.211 cm(3) g(-1) and 76.9 m(2) g(-1), respectively. Modified diatomite was investigated to immobilize the potential toxic elements (PTEs) of Pb, Cu and Cd in simulated contaminated soil comparing to natural diatomite. When incubated with contaminated soils at rates of 2.5% and 5.0% by weight for 90 days, modified diatomite was more effective in immobilizing Pb, Cu and Cd than natural diatomite. After treated with 5.0% modified diatomite for 90 days, the contaminated soils showed 69.7%, 49.7% and 23.7% reductions in Pb, Cu and Cd concentrations after 0.01 M CaCl2 extraction, respectively. The concentrations of Pb, Cu and Cd were reduced by 66.7%, 47.2% and 33.1% in the leaching procedure, respectively. The surface complexation played an important role in the immobilization of PTEs in soils. The decreased extractable metal content of soil was accompanied by improved microbial activity which significantly increased (P<0.05) in 5.0% modified diatomite-amended soils. These results suggested that modified diatomite with micro/nanostructured characteristics increased the immobilization of PTEs in contaminated soil and had great potential as green and low-cost amendments. Copyright © 2015 Elsevier B.V. All rights reserved.

Electrochemical luminescence determination of hyperin using a sol-gel@graphene luminescent composite film modified electrode for solid phase microextraction

NASA Astrophysics Data System (ADS)

Zou, Xiaojun; Shang, Fang; Wang, Sui

2017-02-01

In this paper, a novel electrochemiluminescence (ECL) sensor of sol-gel@graphene luminescent composite film modified electrode for hyperin determination was prepared using graphene (G) as solid-phase microextraction (SPME) material, based on selective preconcentration of target onto an electrode and followed by luminol ECL detection. Hyperin was firstly extracted from aqueous solution through the modified GCE. Hydrogel, electrogenerated chemiluminescence reagents, pH of working solution, extraction time and temperature and scan rate were discussed. Under the optimum conditions, the change of ECL intensity was in proportion to the concentration of hyperin in the range of 0.02-0.24 μg/mL with a detection limit of 0.01 μg/mL. This method showed good performance in stability, reproducibility and precision for the determination of hyperin.

Plant crude extracts could be the solution: extracts showing in vivo antitumorigenic activity.

PubMed

Amara, A A; El-Masry, M H; Bogdady, H H

2008-04-01

Screening active compounds from plants lead to discover new medicinal drugs which have efficient protection and treatment roles against various diseases including cancer. In our study, extracts from different plants represent seeds of: Gossypium barbadense, Ricinus communis, Sesamum indicum, Nigella sativa, Vinca rosea and Melia azedarah; fruits of: Xanthium occidental; flowers of: Atriplex nummularia; barks of: Cinnamomum zeylanicum; latex of: Ficus carica and rhizomes of: Curcuma longa and Zingiber officinale were tested in vivo using three subsequent bioassays: the BST (Brine Shrimp Toxicity bioassay), AWD (Agar well diffusion antimicrobial bioassay) and AtPDT (Agrobacterium tumefaciens Potato Disc Tumor bioassay). AWD technique omitted any extracts have antimicrobial activities while BST omitted any extract did not has physiological activity and determined the various LC(50) of each plant extract. For the first time, using a range of concentrations in the AtPDT modified protocol allowed the detection of tumor promotion caused by extract represented by A. nummularia. Using cluster analysis leads to classifying the different plant extracts activities to six groups regarding to their toxicity, antitumor activities and both of them. The extracts from edible plants represent 50% of the first and the second group which have the highest antitumor activities represented in F. caraica (group 1) and C. longa (group 2) as well as the non-edible plant extracts of Gossypium barbadense and Ricinus communis. A comparison study between the edible and herbaceous plants different extracts for their antitumor activities was performed. We recommended using the modified protocols used in this study for investigating more plants and using crude plant extracts which have antitumor activities in cancer treatment. Edible plants, which show in vivo antitumor activities, are recommended as save sources for antitumor compounds.

Preparation of ionic liquid modified magnetic metal-organic frameworks composites for the solid-phase extraction of α-chymotrypsin.

PubMed

Wei, Xiaoxiao; Wang, Yuzhi; Chen, Jing; Xu, Panli; Zhou, Yigang

2018-05-15

A novel magnetic solid-phase extraction (MSPE) method based on 1-hexyl-3-methyl imidazolium chloride ionic liquid (IL) modified magnetic Fe 3 O 4 nanoparticles, hydroxylated multiwall carbon nanotubes (MWCNTs-OH) and zeolitic imidazolate frameworks (ZIFs) nanocomposites (Fe 3 O 4 -MWCNTs-OH@ZIF-67@IL) were proposed and applied to extract α-chymotrypsin. The magnetic materials were synthesized successfully and characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), thermal gravimetric analysis (TGA), fourier transform infrared spectrometry (FT-IR), vibrating sample magnetometer (VSM) and zeta potentials. Subsequently, the UV-vis spectrophotometer at about 280 nm was utilized to quantitatively analyze the α-chymotrypsin concentration in the supernatant. Furthermore, single factor experiments revealed that the extraction capacity was influenced by initial α-chymotrypsin concentration, ionic strength, extraction time, extraction temperature and pH value. The extraction capacity could reach up to about 635 mg g -1 under the optimized conditions, absolutely higher than that of extraction for Ovalbumin (OVA), Bovine serum albumin (BSA) and Bovine hemoglobin (BHb). In addition, the regeneration studies showed Fe 3 O 4 -MWCNTs-OH@ZIF-67@IL particles could be reused several times and kept a high extraction capacity. Besides, the study of enzymatic activity also indicated that the activity of the extracted α-chymotrypsin was well maintained 93% of initial activity. What's more, the proposed method was successfully applied to extract α-chymotrypsin in porcine pancreas crude extract with satisfactory results. All of above conclusions highlight the great potential of the proposed Fe 3 O 4 -MWCNTs-OH@ZIF-67@IL-MSPE method in the analysis of biomolecules. Copyright © 2018 Elsevier B.V. All rights reserved.

Antifungal sourdough lactic acid bacteria as biopreservation tool in quinoa and rice bread.

PubMed

Axel, Claudia; Brosnan, Brid; Zannini, Emanuele; Furey, Ambrose; Coffey, Aidan; Arendt, Elke K

2016-12-19

The use of sourdough fermented with specific strains of antifungal lactic acid bacteria can reduce chemical preservatives in bakery products. The main objective of this study was to investigate the production of antifungal carboxylic acids after sourdough fermentation of quinoa and rice flour using the antifungal strains Lactobacillus reuteri R29 and Lactobacillus brevis R2Δ as bioprotective cultures and the non-antifungal L. brevis L1105 as a negative control strain. The impact of the fermentation substrate was evaluated in terms of metabolic activity, acidification pattern and quantity of antifungal carboxylic acids. These in situ produced compounds (n=20) were extracted from the sourdough using a QuEChERS method and detected by a new UHPLC-MS/MS chromatography. Furthermore, the sourdough was applied in situ using durability tests against environmental moulds to investigate the biopreservative potential to prolong the shelf life of bread. Organic acid production and TTA values were lowest in rice sourdough. The sourdough fermentation of the different flour substrates generated a complex and significantly different profile of carboxylic acids. Extracted quinoa sourdough detected the greatest number of carboxylic acids (n=11) at a much higher concentration than what was detected from rice sourdough (n=9). Comparing the lactic acid bacteria strains, L. reuteri R29 fermented sourdoughs contained generally higher concentrations of acetic and lactic acid but also the carboxylic acids. Among them, 3-phenyllactic acid and 2-hydroxyisocaproic acid were present at a significant concentration. This was correlated with the superior protein content of quinoa flour and its high protease activity. With the addition of L. reuteri R29 inoculated sourdough, the shelf life was extended by 2 days for quinoa (+100%) and rice bread (+67%) when compared to the non-acidified controls. The L. brevis R2Δ fermented sourdough bread reached a shelf life of 4 days for quinoa (+100%) and rice (+33%). However, the shelf life was similar to the chemically acidified control indicating that the preservation effect of the carboxylic acids seems to have a minor contribution effect on the antifungal activity in gluten-free breads. Copyright © 2016 Elsevier B.V. All rights reserved.

Simultaneous liquid chromatography/mass spectrometry determination of both polar and "multiresidue" pesticides in food using parallel hydrophilic interaction/reversed-phase liquid chromatography and a hybrid sample preparation approach.

PubMed

Robles-Molina, José; Gilbert-López, Bienvenida; García-Reyes, Juan F; Molina-Díaz, Antonio

2017-09-29

Pesticide testing of foodstuffs is usually accomplished with generic wide-scope multi-residue methods based on liquid chromatography tandem mass spectrometry (LC-MS/MS). However, this approach does not cover some special pesticides, the so called "single-residue method" compounds, that are hardly compatible with standard reversed-phase (RP) separations due to their specific properties. In this article, we propose a comprehensive strategy for the integration of single residue method compounds and standard multiresidue pesticides within a single run. It is based on the use of a parallel LC column assembly with two different LC gradients performing orthogonal hydrophilic interaction chromatography (HILIC) and reversed-phase (RPLC) chromatography within one analytical run. Two sample aliquots were simultaneously injected on each column, using different gradients, being the eluents merged post-column prior to mass spectrometry detection. The approach was tested with 41 multiclass pesticides covering a wide range of physicochemical properties across several orders of log K ow (from -4 to +5.5). With this assembly, distinct separation from the void was attained for all the pesticides studied, keeping similar performance in terms of sensitivity, peak area reproducibility (<6 RSD% in most cases) and retention time stability of standard single column approaches (better than±0.1min). The application of the proposed approach using parallel HILIC/RPLC and RPLC/aqueous normal phase (Obelisc) were assessed in leek using LC-MS/MS. For this purpose, a hybrid QuEChERS (Quick, easy, cheap, effective, rugged and safe)/QuPPe (quick method for polar pesticides) method was evaluated based on solvent extraction with MeOH and acetonitrile followed by dispersive solid-phase extraction, delivering appropriate recoveries for most of the pesticides included in the study within the log K ow in the range from -4 to +5.5. The proposed strategy may be extended to other fields such as sport drug testing or environmental analysis, where the same type of variety of analytes featuring poor retention within a single chromatographic separation occurs. Copyright © 2017 Elsevier B.V. All rights reserved.

Comparative Studies on Dyeability with Direct, Acid and Reactive Dyes after Chemical Modification of Jute with Mixed Amino Acids Obtained from Extract of Waste Soya Bean Seeds

NASA Astrophysics Data System (ADS)

Bhaumik, Nilendu Sekhar; Konar, Adwaita; Roy, Alok Nath; Samanta, Ashis Kumar

2017-12-01

Jute fabric was treated with mixed natural amino acids obtained from waste soya bean seed extract for chemical modification of jute for its cataionization and to enhance its dyeability with anionic dyes (like direct, reactive and acid dye) as well enabling soya modified jute for salt free dyeing with anionic reactive dyes maintaining its eco-friendliness. Colour interaction parameters including surface colour strength were assessed and compared for both bleached and soya-modified jute fabric for reactive dyeing and compared with direct and acid dye. Improvement in K/S value (surface colour strength) was observed for soya-modified jute even in absence of salt applied in dye bath for reactive dyes as well as for direct and acid dyes. In addition, reactive dye also shows good dyeability even in acid bath in salt free conditions. Colour fastness to wash was evaluated for bleached and soya-modified jute fabric after dyeing with direct, acid and reactive dyes are reported. Treatment of jute with soya-extracted mixed natural amino acids showed anchoring of some amino/aldemine groups on jute cellulosic polymer evidenced from Fourier Transform Infra-Red (FTIR) Spectroscopy. This amino or aldemine group incorporation in bleached jute causes its cationization and hence when dyed in acid bath for reactive dye (instead of conventional alkali bath) showed dye uptake for reactive dyes. Study of surface morphology by Scanning Electron Microscopy (SEM) of said soya-modified jute as compared to bleached jute was studied and reported.

Phosphatidylinositol 3-Kinase and Protein Kinase C as Molecular Determinants of Chemoresistance in Breast Cancer

DTIC Science & Technology

2004-07-01

medium (Cambrex, San Diego, CA) supplemented with bovine pituitary extract . cancer contained approximately one-half the level of cer- 3-[4,5...rill et al., 1988) as modified by Yoon et al. (1999) was used. Lipid Cytochrome c Release. Cells (4 X 106) were harvested with 0.5% extract aliquots... extracted in chloroform, and the organic phase was dried under a nitrogen z 80- stream. The lipids contained in the organic phase extract were re- 70

High efficiency induction of callus and regeneration of sporophytes of Laminaria japonica (Phaeophyta)

NASA Astrophysics Data System (ADS)

Wang, Xi-Hua; Qin, Song; Li, Xin-Ping; Jiang, Peng; Zeng, Cheng-Kui; Qin, Mei

1998-03-01

Four media (PESI solid, MS liquid, MS solid and ASP-C-I solid medium) were used to induce callus from excised tissues of the kelp Laminaria japonica. Only PESI solid medium and MS solid medium produced calli. Modified MS solid medium supplemented with mannitol (3%,W/V), yeast extract (0.1%, W/V), VB2 (0.5 mg/ml), VB12 (0.5 mg/ml), kinetin (0.108 μg/ml) and NAA (1.860μg/ml) showed much better effect on callus induction than non-modified MS solid medium. After 24 days of induction 75.5% of tissues in PESI solid medium showed callus formation. For modified MS solid medium, after three months of induction 67.3% of tissues dedifferentiated into calli. No callus could be found after five months of induction in either MS liquid or ASP-C-I solid medium. When calli were squashed and cultured in N-P enriched autoclaved seawater, MS liquid medium and ASP12-NTA liquid medium (both modified with kelp extract), differentiation of cells and regeneration of sporophytes were only observed in ASP12-NTA medium supplemented with kelp extract. Gametophyte-like filaments formed first, then eggs were released. It was suggested that sporophyte formation could be a process of parthenogenesis. Sterilization techniques in tissue culture of L. japonica were also tested in this study.

PIASy Mediates SUMO-2/3 Conjugation of Poly(ADP-ribose) Polymerase 1 (PARP1) on Mitotic Chromosomes*

PubMed Central

Ryu, Hyunju; Al-Ani, Gada; Deckert, Katelyn; Kirkpatrick, Donald; Gygi, Steven P.; Dasso, Mary; Azuma, Yoshiaki

2010-01-01

PIASy is a small ubiquitin-related modifier (SUMO) ligase that modifies chromosomal proteins in mitotic Xenopus egg extracts and plays an essential role in mitotic chromosome segregation. We have isolated a novel SUMO-2/3-modified mitotic chromosomal protein and identified it as poly(ADP-ribose) polymerase 1 (PARP1). PARP1 was robustly conjugated to SUMO-2/3 on mitotic chromosomes but not on interphase chromatin. PIASy promotes SUMOylation of PARP1 both in egg extracts and in vitro reconstituted SUMOylation assays. Through tandem mass spectrometry analysis of mitotically SUMOylated PARP1, we identified a residue within the BRCA1 C-terminal domain of PARP1 (lysine 482) as its primary SUMOylation site. Mutation of this residue significantly reduced PARP1 SUMOylation in egg extracts and enhanced the accumulation of species derived from modification of secondary lysine residues in assays using purified components. SUMOylation of PARP1 did not alter in vitro PARP1 enzyme activity, poly-ADP-ribosylation (PARylation), nor did inhibition of SUMOylation of PARP1 alter the accumulation of PARP1 on mitotic chromosomes, suggesting that SUMOylation regulates neither the intrinsic activity of PARP1 nor its localization. However, loss of SUMOylation increased PARP1-dependent PARylation on isolated chromosomes, indicating SUMOylation controls the capacity of PARP1 to modify other chromatin-associated proteins. PMID:20228053

Phenylboronic acid modified solid-phase extraction column: Preparation, characterization, and application to the analysis of amino acids in sepia capsule by removing the maltose.

PubMed

Guo, Mengzhe; Yin, Dengyang; Han, Jie; Zhang, Liyan; Li, Xiao; He, Dandan; Du, Yan; Tang, Daoquan

2016-09-01

Maltose, a common auxiliary material of pharmaceutical preparation, may disturb the analysis of total amino acids in sepia capsule by aldolization. Therefore, it is necessary to remove the maltose through a convenient method. In this work, a phenylboronic acid modified solid-phase extraction column has been synthesized and used to remove the maltose. The materials were synthesized by one step "thiol-ene" reaction and the parameters of the column such as absorption capacity, recovery, and absorption specificity have been investigated. The results showed the column (0.5 cm of length × 0.5 cm of inner diameter) can absorb 4.6 mg maltose with a linear absorption and absorption specificity. Then this technique was applied in the quantification of amino acids in sepia capsule. After the optimization of the method, four kinds of amino acids, which were the most abundant, were quantified by high-performance liquid chromatography with diode array detection. The amounts of the four kinds of amino acids are 1.5∼2 times more than that without the treatment of solid-phase extraction column, which almost overcomes the influence of the maltose. All the results indicate that the phenylboronic acid modified solid-phase extraction column can successfully help to accurately quantify the total amino acids in sepia capsule. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

21 CFR 172.560 - Modified hop extract.

Code of Federal Regulations, 2014 CFR

2014-04-01

... following processes: (1) The additive is manufactured from a hexane extract of hops by simultaneous... approximately 0.012 n alkaline methyl alcohol (6 milliliters of 1 n sodium hydroxide diluted to 500 milliliters... fractionations, using methylene chloride, hexane, and methyl alcohol as solvents, followed by isomerization by...

Dissipation of S-metolachlor in plant and soil and effect on enzymatic activities.

PubMed

Wołejko, Elżbieta; Kaczyński, Piotr; Łozowicka, Bożena; Wydro, Urszula; Borusiewicz, Andrzej; Hrynko, Izabela; Konecki, Rafał; Snarska, Krystyna; Dec, Dorota; Malinowski, Paweł

2017-07-01

The present study aimed at evaluating the dissipation of S-metolachlor (S-MET) at three doses in maize growing on diverse physico-chemical properties of soil. The effect of herbicide on dehydrogenase (DHA) and acid phosphatase (ACP) activity was estimated. A modified QuEChERS method using LC-MS/MS has been developed. The limit of quantification (0.001 mg kg -1 ) and detection (0.0005 mg kg -1 ) were very low for soil and maize samples. The mean recoveries and RSDs for the six spiked levels (0.001-0.5 mg kg -1 ) were 91.3 and 5.8%. The biggest differences in concentration of S-MET in maize were observed between the 28th and 63rd days. The dissipation of S-MET in the alkaline soil was the slowest between the 2nd and 7th days, and in the acidic soil between the 5th and 11th days. DT 50 of S-MET calculated according to the first-order kinetics model was 11.1-14.7 days (soil) and 9.6-13.9 days (maize). The enzymatic activity of soil was higher in the acidic environment. One observed the significant positive correlation of ACP with pH of soil and contents of potassium and magnesium and negative with contents of phosphorus and organic carbon. The results indicated that at harvest time, the residues of S-MET in maize were well below the safety limit for maize. The findings of this study will foster the research on main parameters influencing the dissipation in maize ecosystems.

Rhamnogalacturonan I containing homogalacturonan inhibits colon cancer cell proliferation by decreasing ICAM1 expression

USDA-ARS?s Scientific Manuscript database

Pectin modified with pH, heat or enzymes, has previously been shown to exhibit anti-cancer activity. However, the structural requirements for bioactive modified pectins have rarely been addressed. In this study several pectin extracts representing different structural components of pectin were asses...

Three modified activated carbons by different ligands for the solid phase extraction of copper and lead.

PubMed

Ghaedi, M; Ahmadi, F; Tavakoli, Z; Montazerozohori, M; Khanmohammadi, A; Soylak, M

2008-04-15

In the presented work, 5,5-diphenylimidazolidine-2,4-dione (phenytoin) (DFTD), 5,5-diphenylimidazolidine-2-thione-,4-one (thiophenytoin) (DFID) and 2-(4'-methoxy-benzylidenimine) thiophenole (MBIP) modified activated carbons have been used for the solid phase extraction of copper and lead ions prior to their flame atomic absorption spectrometric determinations. The influences of the various analytical parameters including pH, amounts of reagent, sample volume and eluent type, etc. on the recovery efficiencies of copper and lead ions were investigated. The influences of alkaline, earth alkaline and some transition metals on the adsorption of the analytes were also examined. The detection limits by three sigma for analyte ions were 0.65 and 0.42 microg L(-1) using activated carbon modified with DFID; 0.52 and 0.37 microg L(-1) using activated carbon modified with DFTD and 0.46 and 0.31 microg L(-1) using activated carbon modified with MBIP for Pb(II) and Cu(II), respectively. The procedure was applied to the determination of analytes in natural waters, soil, and blood samples with satisfactory results (recoveries greater than 95%, R.S.D.'s lower than 4%).

Antioxidant activity of Citrus paradisi seeds glyceric extract.

PubMed

Giamperi, Laura; Fraternale, Daniele; Bucchini, Anahi; Ricci, Donata

2004-03-01

The antioxidant activity of Citrus paradisi (grapefruit) seeds glyceric extract dissolved in ethanol and in aqueous media was evaluated using three different methods: evaluation by DPPH assay, by 5-lipoxygenase assay and by luminol/xanthine/xanthine oxidase chemiluminescence assay. The total phenolic content was determined by the Prussian Blue method opportunely modified. The grapefruit seeds glyceric extract utilized as aqueous solutions demonstrated antioxidant properties better than those displayed by alcoholic solutions.

Extractions of High Quality RNA from the Seeds of Jerusalem Artichoke and Other Plant Species with High Levels of Starch and Lipid.

PubMed

Mornkham, Tanupat; Wangsomnuk, Preeya Puangsomlee; Fu, Yong-Bi; Wangsomnuk, Pinich; Jogloy, Sanun; Patanothai, Aran

2013-04-29

Jerusalem artichoke (Helianthus tuberosus L.) is an important tuber crop. However, Jerusalem artichoke seeds contain high levels of starch and lipid, making the extraction of high-quality RNA extremely difficult and the gene expression analysis challenging. This study was aimed to improve existing methods for extracting total RNA from Jerusalem artichoke dry seeds and to assess the applicability of the improved method in other plant species. Five RNA extraction methods were evaluated on Jerusalem artichoke seeds and two were modified. One modified method with the significant improvement was applied to assay seeds of diverse Jerusalem artichoke accessions, sunflower, rice, maize, peanut and marigold. The effectiveness of the improved method to extract total RNA from seeds was assessed using qPCR analysis of four selected genes. The improved method of Ma and Yang (2011) yielded a maximum RNA solubility and removed most interfering substances. The improved protocol generated 29 to 41 µg RNA/30 mg fresh weight. An A260/A280 ratio of 1.79 to 2.22 showed their RNA purity. Extracted RNA was effective for downstream applications such as first-stranded cDNA synthesis, cDNA cloning and qPCR. The improved method was also effective to extract total RNA from seeds of sunflower, rice, maize and peanut that are rich in polyphenols, lipids and polysaccharides.

Effect of Aqueous Extract of the Seaweed Gracilaria domingensis on the Physicochemical, Microbiological, and Textural Features of Fermented Milks.

PubMed

Tavares Estevam, Adriana Carneiro; Alonso Buriti, Flávia Carolina; de Oliveira, Tiago Almeida; Pereira, Elainy Virginia Dos Santos; Florentino, Eliane Rolim; Porto, Ana Lúcia Figueiredo

2016-04-01

The effects of the Gracilaria domingensis seaweed aqueous extract in comparison with gelatin on the physicochemical, microbial, and textural characteristics of fermented milks processed with the mixed culture SAB 440 A, composed of Streptococcus thermophilus, Lactobacillus acidophilus, and Bifidobacterium animalis ssp. lactis, were investigated. The addition of G. domingensis aqueous extract did not affect pH, titratable acidity, and microbial viability of fermented milks when compared with the control (with no texture modifier) and the products with added gelatin. Fermented milk with added the seaweed aqueous extract showed firmness, consistency, cohesiveness, and viscosity index at least 10% higher than those observed for the control product (P < 0.05). At 4 h of fermentation, the fermented milks with only G. domingensis extract showed a texture comparable to that observed for products containing only gelatin. At 5 h of fermentation, firmness and consistency increased significantly (P < 0.05) in products with only seaweed extract added, a behavior not observed in products with the full amount of gelatin, probably due to the differences between the interactions of these ingredients with casein during the development of the gel network throughout the acidification of milk. The G. domingensis aqueous extract appears as a promising gelatin alternative to be used as texture modifier in fermented milks and related dairy products. © 2016 Institute of Food Technologists®

Atomic-absorption determination of mercury in geological materials by flame and carbon-rod atomisation after solvent extraction and using co-extracted silver as a matrix modifier

USGS Publications Warehouse

Sanzolone, R.F.; Chao, T.T.

1983-01-01

Based on modifications and expansion of the original Tindall's solvent extraction flame atomic-absorption procedure, an atomic-absorption spectrophotometric method has been developed for the determination of mercury in geological materials. The sample is digested with nitric and hydrochloric acids in a boiling water-bath. The solution is made ammoniacal and potassium iodide and silver nitrate are added. The mercury is extracted into isobutyl methyl ketone as the tetraiodomercurate(ll). Added silver is co-extracted with mercury and serves as a matrix modifier in the carbon-rod atomiser. The mercury in the isobutyl methyl ketone extract may be determined by either the flame- or the carbon-rod atomisation method, depending on the concentration level. The limits of determination are 0.05-10 p.p.m. of mercury for the carbon-rod atomisation and 1 -200 p.p.m. of mercury for the flame atomisation. Mercury values for reference samples obtained by replicate analyses are in good agreement with those reported by other workers, with relative standard deviations ranging from 2.3 to 0.9%. Recoveries of mercury spiked at two levels were 93-106%. Major and trace elements commonly found in geological materials do not interfere.

Electrically assisted liquid-phase microextraction combined with capillary electrophoresis for quantification of propranolol enantiomers in human body fluids.

PubMed

Tabani, Hadi; Fakhari, Ali Reza; Shahsavani, Abolfath; Gharari Alibabaou, Hossein

2014-05-01

In this study, electromembrane extraction (EME) combined with cyclodextrin (CD)-modified capillary electrophoresis (CE) was applied for the extraction, separation, and quantification of propranolol (PRO) enantiomers from biological samples. The PRO enantiomers were extracted from aqueous donor solutions, through a supported liquid membrane (SLM) consisting of 2-nitrophenyl octyl ether (NPOE) impregnated on the wall of the hollow fiber, and into a 20-μL acidic aqueous acceptor solution into the lumen of hollow fiber. Important parameters affecting EME efficiency such as extraction voltage, extraction time, pH of the donor and acceptor solutions were optimized using a Box-Behnken design (BBD). Then, under these optimized conditions, the acceptor solution was analyzed using an optimized CD-modified CE. Several types of CD were evaluated and best results were obtained using a fused-silica capillary with ammonium acetate (80 mM, pH 2.5) containing 8 mM hydroxypropyl-β-CD as a chiral selector, applied voltage of 18 kV, and temperature of 20°C. The relative recoveries were obtained in the range of 78-95%. Finally, the performance of the present method was evaluated for the extraction and determination of PRO enantiomers in real biological samples. © 2014 Wiley Periodicals, Inc.

Development of a modified cortisol extraction procedure for intermediately sized fish not amenable to whole-body or plasma extraction methods.

PubMed

Guest, Taylor W; Blaylock, Reginald B; Evans, Andrew N

2016-02-01

The corticosteroid hormone cortisol is the central mediator of the teleost stress response. Therefore, the accurate quantification of cortisol in teleost fishes is a vital tool for addressing fundamental questions about an animal's physiological response to environmental stressors. Conventional steroid extraction methods using plasma or whole-body homogenates, however, are inefficient within an intermediate size range of fish that are too small for phlebotomy and too large for whole-body steroid extractions. To assess the potential effects of hatchery-induced stress on survival of fingerling hatchery-reared Spotted Seatrout (Cynoscion nebulosus), we developed a novel extraction procedure for measuring cortisol in intermediately sized fish (50-100 mm in length) that are not amenable to standard cortisol extraction methods. By excising a standardized portion of the caudal peduncle, this tissue extraction procedure allows for a small portion of a larger fish to be sampled for cortisol, while minimizing the potential interference from lipids that may be extracted using whole-body homogenization procedures. Assay precision was comparable to published plasma and whole-body extraction procedures, and cortisol quantification over a wide range of sample dilutions displayed parallelism versus assay standards. Intra-assay %CV was 8.54%, and average recovery of spiked samples was 102%. Also, tissue cortisol levels quantified using this method increase 30 min after handling stress and are significantly correlated with blood values. We conclude that this modified cortisol extraction procedure provides an excellent alternative to plasma and whole-body extraction procedures for intermediately sized fish, and will facilitate the efficient assessment of cortisol in a variety of situations ranging from basic laboratory research to industrial and field-based environmental health applications.

Doppler extraction with a digital VCO

NASA Technical Reports Server (NTRS)

Starner, E. R.; Nossen, E. J.

1977-01-01

Digitally controlled oscillator in phased-locked loop may be useful for data communications systems, or may be modified to serve as information extraction component of microwave or optical system for collision avoidance or automatic braking. Instrument is frequency-synthesizing device with output specified precisely by digital number programmed into frequency register.

Use of fluorinated polybrominated diphenyl ethers and simplified cleanup for the analysis of polybrominated diphenyl ethers in house dust

EPA Science Inventory

A simple, cost-effective method is described for the analysis of polybrominated diphenyl ethers (PBDEs) in house dust using pressurized fluid extraction, cleanup with modified silica solid phase extraction tubes, and fluorinated internal standards. There are 14 PBDE congeners inc...

Kerogen extraction from subterranean oil shale resources

DOEpatents

Looney, Mark Dean; Lestz, Robert Steven; Hollis, Kirk; Taylor, Craig; Kinkead, Scott; Wigand, Marcus

2010-09-07

The present invention is directed to methods for extracting a kerogen-based product from subsurface (oil) shale formations, wherein such methods rely on fracturing and/or rubblizing portions of said formations so as to enhance their fluid permeability, and wherein such methods further rely on chemically modifying the shale-bound kerogen so as to render it mobile. The present invention is also directed at systems for implementing at least some of the foregoing methods. Additionally, the present invention is also directed to methods of fracturing and/or rubblizing subsurface shale formations and to methods of chemically modifying kerogen in situ so as to render it mobile.

Kerogen extraction from subterranean oil shale resources

DOEpatents

Looney, Mark Dean [Houston, TX; Lestz, Robert Steven [Missouri City, TX; Hollis, Kirk [Los Alamos, NM; Taylor, Craig [Los Alamos, NM; Kinkead, Scott [Los Alamos, NM; Wigand, Marcus [Los Alamos, NM

2009-03-10

The present invention is directed to methods for extracting a kerogen-based product from subsurface (oil) shale formations, wherein such methods rely on fracturing and/or rubblizing portions of said formations so as to enhance their fluid permeability, and wherein such methods further rely on chemically modifying the shale-bound kerogen so as to render it mobile. The present invention is also directed at systems for implementing at least some of the foregoing methods. Additionally, the present invention is also directed to methods of fracturing and/or rubblizing subsurface shale formations and to methods of chemically modifying kerogen in situ so as to render it mobile.

Supercritical Fluid Extraction of Bacterial and Archaeal Lipid Biomarkers from Anaerobically Digested Sludge

PubMed Central

Hanif, Muhammad; Atsuta, Yoichi; Fujie, Koichi; Daimon, Hiroyuki

2012-01-01

Supercritical fluid extraction (SFE) was used in the analysis of bacterial respiratory quinone (RQ), bacterial phospholipid fatty acid (PLFA), and archaeal phospholipid ether lipid (PLEL) from anaerobically digested sludge. Bacterial RQ were determined using ultra performance liquid chromatography (UPLC). Determination of bacterial PLFA and archaeal PLEL was simultaneously performed using gas chromatography-mass spectrometry (GC-MS). The effects of pressure, temperature, and modifier concentration on the total amounts of RQ, PLFA, and PLEL were investigated by 23 experiments with five settings chosen for each variable. The optimal extraction conditions that were obtained through a multiple-response optimization included a pressure of 23.6 MPa, temperature of 77.6 °C, and 10.6% (v/v) of methanol as the modifier. Thirty nine components of microbial lipid biomarkers were identified in the anaerobically digested sludge. Overall, the SFE method proved to be more effective, rapid, and quantitative for simultaneously extracting bacterial and archaeal lipid biomarkers, compared to conventional organic solvent extraction. This work shows the potential application of SFE as a routine method for the comprehensive analysis of microbial community structures in environmental assessments using the lipid biomarkers profile. PMID:22489140

A High-Speed Vision-Based Sensor for Dynamic Vibration Analysis Using Fast Motion Extraction Algorithms.

PubMed

Zhang, Dashan; Guo, Jie; Lei, Xiujun; Zhu, Changan

2016-04-22

The development of image sensor and optics enables the application of vision-based techniques to the non-contact dynamic vibration analysis of large-scale structures. As an emerging technology, a vision-based approach allows for remote measuring and does not bring any additional mass to the measuring object compared with traditional contact measurements. In this study, a high-speed vision-based sensor system is developed to extract structure vibration signals in real time. A fast motion extraction algorithm is required for this system because the maximum sampling frequency of the charge-coupled device (CCD) sensor can reach up to 1000 Hz. Two efficient subpixel level motion extraction algorithms, namely the modified Taylor approximation refinement algorithm and the localization refinement algorithm, are integrated into the proposed vision sensor. Quantitative analysis shows that both of the two modified algorithms are at least five times faster than conventional upsampled cross-correlation approaches and achieve satisfactory error performance. The practicability of the developed sensor is evaluated by an experiment in a laboratory environment and a field test. Experimental results indicate that the developed high-speed vision-based sensor system can extract accurate dynamic structure vibration signals by tracking either artificial targets or natural features.

Effervescence-assisted dispersive solid-phase extraction using ionic-liquid-modified magnetic β-cyclodextrin/attapulgite coupled with high-performance liquid chromatography for fungicide detection in honey and juice.

PubMed

Wu, Xiaoling; Yang, Miyi; Zeng, Haozhe; Xi, Xuefei; Zhang, Sanbing; Lu, Runhua; Gao, Haixiang; Zhou, Wenfeng

2016-11-01

In this study, a simple effervescence-assisted dispersive solid-phase extraction method was developed to detect fungicides in honey and juice. Most significantly, an innovative ionic-liquid-modified magnetic β-cyclodextrin/attapulgite sorbent was used because its large specific surface area enhanced the extraction capacity and also led to facile separation. A one-factor-at-a-time approach and orthogonal design were employed to optimize the experimental parameters. Under the optimized conditions, the entire extraction procedure was completed within 3 min. In addition, the calibration curves exhibited good linearity, and high enrichment factors were achieved for pure water and honey samples. For the honey samples, the extraction efficiencies for the target fungicides ranged from 77.0 to 94.3% with relative standard deviations of 2.3-5.44%. The detection and quantitation limits were in the ranges of 0.07-0.38 and 0.23-1.27 μg/L, respectively. Finally, the developed technique was successfully applied to real samples, and satisfactory results were achieved. This analytical technique is cost-effective, environmentally friendly, and time-saving. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evaluating specificity of sequential extraction for chemical forms of lead in artificially-contaminated and field-contaminated soils.

PubMed

Tai, Yiping; McBride, Murray B; Li, Zhian

2013-03-30

In the present study, we evaluated a commonly employed modified Bureau Communautaire de Référence (BCR test) 3-step sequential extraction procedure for its ability to distinguish forms of solid-phase Pb in soils with different sources and histories of contamination. When the modified BCR test was applied to mineral soils spiked with three forms of Pb (pyromorphite, hydrocerussite and nitrate salt), the added Pb was highly susceptible to dissolution in the operationally-defined "reducible" or "oxide" fraction regardless of form. When three different materials (mineral soil, organic soil and goethite) were spiked with soluble Pb nitrate, the BCR sequential extraction profiles revealed that soil organic matter was capable of retaining Pb in more stable and acid-resistant forms than silicate clay minerals or goethite. However, the BCR sequential extraction for field-collected soils with known and different sources of Pb contamination was not sufficiently discriminatory in the dissolution of soil Pb phases to allow soil Pb forms to be "fingerprinted" by this method. It is concluded that standard sequential extraction procedures are probably not very useful in predicting lability and bioavailability of Pb in contaminated soils. Copyright © 2013 Elsevier B.V. All rights reserved.

A comparison of two colorimetric assays, based upon Lowry and Bradford techniques, to estimate total protein in soil extracts.

PubMed

Redmile-Gordon, M A; Armenise, E; White, R P; Hirsch, P R; Goulding, K W T

2013-12-01

Soil extracts usually contain large quantities of dissolved humified organic material, typically reflected by high polyphenolic content. Since polyphenols seriously confound quantification of extracted protein, minimising this interference is important to ensure measurements are representative. Although the Bradford colorimetric assay is used routinely in soil science for rapid quantification protein in soil-extracts, it has several limitations. We therefore investigated an alternative colorimetric technique based on the Lowry assay (frequently used to measure protein and humic substances as distinct pools in microbial biofilms). The accuracies of both the Bradford assay and a modified Lowry microplate method were compared in factorial combination. Protein was quantified in soil-extracts (extracted with citrate), including standard additions of model protein (BSA) and polyphenol (Sigma H1675-2). Using the Lowry microplate assay described, no interfering effects of citrate were detected even with concentrations up to 5 times greater than are typically used to extract soil protein. Moreover, the Bradford assay was found to be highly susceptible to two simultaneous and confounding artefacts: 1) the colour development due to added protein was greatly inhibited by polyphenol concentration, and 2) substantial colour development was caused directly by the polyphenol addition. In contrast, the Lowry method enabled distinction between colour development from protein and non-protein origin, providing a more accurate quantitative analysis. These results suggest that the modified-Lowry method is a more suitable measure of extract protein (defined by standard equivalents) because it is less confounded by the high polyphenolic content which is so typical of soil extracts.

DNA extraction methods for detecting genetically modified foods: A comparative study.

PubMed

Elsanhoty, Rafaat M; Ramadan, Mohamed Fawzy; Jany, Klaus Dieter

2011-06-15

The work presented in this manuscript was achieved to compare six different methods for extracting DNA from raw maize and its derived products. The methods that gave higher yield and quality of DNA were chosen to detect the genetic modification in the samples collected from the Egyptian market. The different methods used were evaluated for extracting DNA from maize kernels (without treatment), maize flour (mechanical treatment), canned maize (sweet corn), frozen maize (sweet corn), maize starch, extruded maize, popcorn, corn flacks, maize snacks, and bread made from corn flour (mechanical and thermal treatments). The quality and quantity of the DNA extracted from the standards, containing known percentages of GMO material and from the different food products were evaluated. For qualitative detection of the GMO varieties in foods, the GMOScreen 35S/NOS test kit was used, to screen the genetic modification in the samples. The positive samples for the 35S promoter and/or the NOS terminator were identified by the standard methods adopted by EU. All of the used methods extracted yielded good DNA quality. However, we noted that the purest DNA extract were obtained using the DNA extraction kit (Roche) and this generally was the best method for extracting DNA from most of the maize-derived foods. We have noted that the yield of DNA extracted from maize-derived foods was generally lower in the processed products. The results indicated that 17 samples were positive for the presence of 35S promoter, while 34% from the samples were positive for the genetically modified maize line Bt-176. Copyright © 2010 Elsevier Ltd. All rights reserved.

Ionic liquid-modified materials for solid-phase extraction and separation: a review.

PubMed

Vidal, Lorena; Riekkola, Marja-Liisa; Canals, Antonio

2012-02-17

In recent years, materials science has propelled to the research forefront. Ionic liquids with unique and fascinating properties have also left their footprints to the developments of materials science during the last years. In this review we highlight some of their recent advances and provide an overview at the current status of ionic liquid-modified materials applied in solid-phase extraction, liquid and gas chromatography and capillary electrochromatography with reference to recent applications. In addition, the potential of ionic liquids in the modification of capillary inner wall in capillary electrophoresis is demonstrated. The main target material modified with ionic liquids is silica, but polymers and monoliths have recently joined the studies. Although imidazolium is still clearly the most commonly used ionic liquid for the covalently modification of materials, the exploitation of pyridinium and phosphonium will most probably increase in the future. Copyright © 2011 Elsevier B.V. All rights reserved.

Surface characterization of weathered wood-plastic composites produced from modified wood flour

Treesearch

James S. Fabiyi; Armando G. McDonald; Nicole M. Stark

2007-01-01

The effects of weathering on the surface properties of wood-plastic composites (WPC) were examined. High-density polyethylene (HDPE) based WPCs made from modified wood flour (untreated, extractives free, and holocellulose (delignified) fibers) were subjected to accelerated (xenon-arc) weathering. Colorimetry and Fourier-transform infrared spectroscopy were employed to...

Effects of modified zeolite on the removal and stabilization of heavy metals in contaminated lake sediment using BCR sequential extraction.

PubMed

Wen, Jia; Yi, Yuanjie; Zeng, Guangming

2016-08-01

Sediment can be applied on land as a soil conditioner. However, toxic substances such as heavy metals within the sediment often lead to soil contamination if no proper management is conducted prior to land application. In order to reduce the bioavailable portion of heavy metals such as Pb, Cu, Zn and Cd, zeolite as a kind of stabilizer was investigated on the effect of metal stabilization in sediment. Zeolite was firstly modified and screened to get the best condition for removal of heavy metals. Results showed that the granulated zeolite with NaCl conditioning had the highest CEC and metal sorption. Using BCR sequential extraction, the selected modified zeolite effectively stabilized Pb, Cu, Zn and Cd in sediment to different extents. It was most suitable for Cd stabilization by reducing its acid exchangeable fraction while increasing the contents of the reducible and residual fractions. Modified zeolite also immobilized Cu, Zn and Pb in sediment by enhancing one stable fraction while decreasing the acid exchangeable fraction. Copyright © 2016 Elsevier Ltd. All rights reserved.

A new separation and preconcentration method for selenium in some foods using modified silica gel with 2,6-diamino-4-phenil-1,3,5-triazine.

PubMed

Mendil, Durali; Demirci, Zafer; Uluozlu, Ozgur Dogan; Tuzen, Mustafa; Soylak, Mustafa

2017-04-15

A novel and simple solid phase extraction method was improved and recommended for selenium. Silica gel was modified with 2,6-diamino-4-phenil-1,3,5-triazine and characterized by FTIR, SEM and elemental analysis and used adsorbent for column solid phase extraction of selenium ions. The experimental parameters (pH, flow rates, amounts of the modified silica gel, concentration and type of eluent, volume of sample, etc.) on the recoveries of selenium were optimized. Standard reference materials were analyzed for validation of method. The present method was successfully applied to the detection of total selenium in water and microwave digested some food samples with quantitative recoveries (> 95%). The relative standard deviations were<8%. Matrix influences were not observed. The adsorption capacity of modified silica gel was 5.90mgg -1 . The LOD was 0.015μgL -1 . Enrichment factor was obtained as 50 for the introduced method. Copyright © 2016 Elsevier Ltd. All rights reserved.

Comparative chromatography-mass spectrometry studies on the antiretroviral drug nevirapine-analytical performance characteristics in human plasma determination.

PubMed

Sichilongo, Kwenga; Chinyama, Mompati; Massele, Amos; Vento, Sandro

2014-01-15

A contrast between the analytical performance characteristics using gas chromatography-mass spectrometry (GC-MS) liquid chromatography-mass spectrometry (LC-MS) and liquid chromatography-ultraviolet (LC-UV) detection for the determination of the antiretroviral drug (ARV) nevirapine (NVP) in fortified human plasma after QuEChERS extraction has been made. Analytical performance characteristics, i.e. linearities, instrument detection limits (IDLs), limits of quantitation (LOQs), method detection limits (MDLs), % mean recoveries and the corresponding relative standard deviations (%RSDs) were estimated using techniques above. Using GC-MS, the correlation coefficients (r(2)) were ≥0.990, which were deemed acceptable linearities. The MDLs ranged between 11.1-29.8μg/L and 13.7-36.0μg/L using helium and hydrogen carrier gases respectively. The LOQs ranged between 16.5-66.7μg/L and 28.4-98.7μg/L using helium and hydrogen carrier gases respectively with a % mean recovery of 83% and %RSD of 4.6%. Using LC-MS and LC-UV, the correlation coefficients (r(2)) were ≥0.990. The MDLs were ranged between 3.14 and 47.1μg/L. The LOQs ranged between 2.85 and 90.0μg/L respectively. The MDLs using GC-MS, LC-MS and LC-UV were below the therapeutic range for NVP in human plasma is considered to be between 2300μg/L (Cmin) and 8000μg/L (Cmax). This study also demonstrated that helium can be substituted with hydrogen which is relatively cheaper and easily obtainable even by use of a generator. Copyright © 2013 Elsevier B.V. All rights reserved.

Scented traces--Dermal exposure of synthetic musk fragrances in personal care products and environmental input assessment.

PubMed

Homem, Vera; Silva, Eduardo; Alves, Arminda; Santos, Lúcia

2015-11-01

Synthetic musks are organic compounds used as fragrance and fixative additives in several personal care products. Until now, little is known about their occurrence and distribution in these household commodities. However, this information is essential to perform a human dermal exposure assessment. Therefore, this study gives an overview on the levels of 12 synthetic musks in 140 personal care products from 7 different categories (body and hair wash, toilet soaps, shaving products, dentifrice products, deodorants/antiperspirants, moisturizers and perfumes). They were analysed by QuEChERS extraction followed by gas chromatography-mass spectrometry. Detection limits were found between 0.01ngg(-1) (galaxolide) and 5.00ngg(-1) (musk xylene). Higher average concentrations of total synthetic musks were detected in perfumes (5245.05μgg(-1)) and shampoos (487.67μgg(-1)) for adults. Galaxolide, exaltolide and cashmeran were the most detected compounds. Combining these results with the daily usage amounts, an average daily dermal exposure of 75.69μgkgbw(-1)day(-1) for adults and 15.54μgkgbw(-1)day(-1) for babies/children was achieved. The main contributors for adult and babies/children dermal exposure were perfumes and lotions, respectively. About 40% of the adult daily dermal exposure is related to exaltolide, 30% galaxolide, and 15% tonalide, while for babies/children 96% occurs due to exaltolide. An estimate of the amount of musks discharged "down-the-drain" into the wastewater treatment systems through the use of toiletries was also performed. An average emission per capita of 6.7mgday(-1) was determined and galaxolide and exaltolide were the predominant musks in the effluents. Copyright © 2015 Elsevier Ltd. All rights reserved.

Dissipation pattern of flubendiamide residues on capsicum fruit (Capsicum annuum L.) under field and controlled environmental conditions.

PubMed

Buddidathi, Radhika; Mohapatra, Soudamini; Siddamallaiah, Lekha; Manikrao, Gourishankar; Hebbar, Shibara Shankara

2016-01-01

This investigation was undertaken to compare the dissipation pattern of flubendiamide in capsicum fruits under poly-house and open field after giving spray applications at the recommended and double doses of 48 g a.i. ha(-1) and 96 g a.i. ha(-1). Extraction and purification of capsicum fruit samples were carried out by the QuEChERS method. Residues of flubendiamide and its metabolite, des-iodo flubendiamide, were analyzed by high-performance liquid chromatography-photodiode array, and confirmed by liquid chromatography-mass spectrometry/mass spectrometry. Limit of quantification of the method was 0.05 mg kg(-1), and recovery of the insecticides was in the range of 89.6-104.3%, with relative standard deviation being 4.5-11.5%. The measurement uncertainty of the analytical method was in the range of 10.7-15.7%. Initial residue deposits of flubendiamide on capsicum fruits grown under poly-house conditions were (0.977 and 1.834 mg kg(-1)) higher than that grown in the field (0.665 and 1.545 mg kg(-1)). Flubendiamide residues persisted for 15 days in field-grown and for 25 days in poly-house-grown capsicum fruits. The residues were degraded with the half-lives of 4.3-4.7 and 5.6-6.6 days in field and poly-house respectively. Des-iodo flubendiamide was not detected in capsicum fruits or soil. The residues of flubendiamide degraded to below the maximum residue limit notified by Codex Alimentarius Commission (FAO/WHO) after 1 and 6 days in open field, and 3 and 10 days in poly-house. The results of the study indicated that flubendiamide applied to capsicum under controlled environmental conditions required longer pre-harvest interval to allow its residues to dissipate to the safe level.

Occurrence, profile and spatial distribution of UV-filters and musk fragrances in mussels from Portuguese coastline.

PubMed

Castro, M; Fernandes, J O; Pena, A; Cunha, S C

2018-07-01

The increasing production and consumption of Personal Care Products (PCPs), containing UV-filters and musk fragrances, has led to its widespread presence in the aquatic environment which can cause harmful effects to the aquatic organisms due to its intrinsic toxicity. This study aims to evaluate the degree of contamination of wild mussels along the entire Portuguese coastline, continually exposed in their habitat to different contaminants. For this purpose, approximately 1000 mussel specimens were sampled during one year in seven different locations, along the Portuguese coastline. Simultaneous quantification of five UV-filters and seven musks in mussels was achieved by a Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) extraction procedure combined with dispersive liquid-liquid microextraction (DLLME) followed by gas chromatography with mass spectrometry (GC-MS) analysis. Ten out of the twelve target analytes were found in the analysed samples, highlighting the presence of AHTN (tonalide), EHS (2-ethylhexylsalicylate) and EHMC (2-ethylhexyl 4-methoxycinnamate) in all positive samples (93%). Overall, the results obtained indicate a widespread contamination of wild mussels along Portuguese coastline, all over the year. UV-filters were more frequently detected (90%) than musk fragrances (70%) and also quantified at higher levels, with average total concentrations reaching 1155.8 ng/g (dw) against 397.7 ng/g (dw) respectively. A high correlation was observed between the most densely populated and industrialized locations and the higher levels of musks and UV-filters found. In other hand, lower levels of PCPs were found in protected areas. As expected, an increase in UV-filters levels was observed after the summer, likely due to the intense period of recreational activities. Copyright © 2018 Elsevier Ltd. All rights reserved.

Identification and Quantification of Fumonisin A1, A2, and A3 in Corn by High-Resolution Liquid Chromatography-Orbitrap Mass Spectrometry

PubMed Central

Tamura, Masayoshi; Mochizuki, Naoki; Nagatomi, Yasushi; Harayama, Koichi; Toriba, Akira; Hayakawa, Kazuichi

2015-01-01

Three compounds, hypothesized as fumonisin A1 (FA1), fumonisin A2 (FA2), and fumonisin A3 (FA3), were detected in a corn sample contaminated with mycotoxins by high-resolution liquid chromatography-Orbitrap mass spectrometry (LC-Orbitrap MS). One of them has been identified as FA1 synthesized by the acetylation of fumonisin B1 (FB1), and established a method for its quantification. Herein, we identified the two remaining compounds as FA2 and FA3, which were acetylated fumonisin B2 (FB2) and fumonisin B3 (FB3), respectively. Moreover, we examined a method for the simultaneous analysis of FA1, FA2, FA3, FB1, FB2, and FB3. The corn samples were prepared by extraction using a QuEChERS kit and purification using a multifunctional cartridge. The linearity, recovery, repeatability, limit of detection, and limit of quantification of the method were >0.99, 82.9%–104.6%, 3.7%–9.5%, 0.02–0.60 μg/kg, and 0.05–1.98 μg/kg, respectively. The simultaneous analysis of the six fumonisins revealed that FA1, FA2, and FA3 were present in all corn samples contaminated with FB1, FB2, and FB3. The results suggested that corn marketed for consumption can be considered as being contaminated with both the fumonisin B-series and with fumonisin A-series. This report presents the first identification and quantification of FA1, FA2, and FA3 in corn samples. PMID:25690692

Ultrahigh-performance liquid chromatography electrospray ionization Q-Orbitrap mass spectrometry for the analysis of 451 pesticide residues in fruits and vegetables: method development and validation.

PubMed

Wang, Jian; Chow, Willis; Chang, James; Wong, Jon W

2014-10-22

This paper presents an application of ultrahigh-performance liquid chromatography electrospray ionization quadrupole Orbitrap high-resolution mass spectrometry (UHPLC/ESI Q-Orbitrap MS) for the determination of 451 pesticide residues in fruits and vegetables. Pesticides were extracted from samples using the QuEChERS (quick, easy, cheap, effective, rugged, and safe) procedure. UHPLC/ESI Q-Orbitrap MS in full MS scan mode acquired full MS data for quantification, and UHPLC/ESI Q-Orbitrap Full MS/dd-MS(2) (i.e., data-dependent scan mode) obtained product ion spectra for identification. UHPLC/ESI Q-Orbitrap MS quantification was achieved using matrix-matched standard calibration curves along with the use of isotopically labeled standards or a chemical analogue as internal standards to achieve optimal method accuracy. The method performance characteristics include overall recovery, intermediate precision, and measurement uncertainty evaluated according to a nested experimental design. For the 10 matrices studied, 94.5% of the pesticides in fruits and 90.7% in vegetables had recoveries between 81 and 110%; 99.3% of the pesticides in fruits and 99.1% of the pesticides in vegetables had an intermediate precision of ≤20%; and 97.8% of the pesticides in fruits and 96.4% of the pesticides in vegetables showed measurement uncertainty of ≤50%. Overall, the UHPLC/ESI Q-Orbitrap MS demonstrated acceptable performance for the quantification of pesticide residues in fruits and vegetables. The UHPLC/ESI Q-Orbitrap Full MS/dd-MS(2) along with library matching showed great potential for identification and is being investigated further for routine practice.

Residue evaluation of imidacloprid, spirotetramat, and spirotetramat-enol in/on grapes (Vitis vinifera L.) and soil.

PubMed

Mohapatra, Soudamini; Kumar, Sampath; Prakash, G S

2015-10-01

A combination of imidacloprid and spirotetramat effectively controls sucking pests on grapevines. Residues of these insecticides on grapes were evaluated after treatment with spirotetramat 12% + imidacloprid 12% (240 SC) three times at 90 and 180 g a.i. ha(-1). The samples were extracted and purified by QuEChERS method and analyzed by high-performance liquid chromatography with a photodiode array detector (imidacloprid) and gas chromatography mass spectrometry (spirotetramat and its metabolite spirotetramat-enol). Satisfactory results were obtained with ranges of 80.6-98.6% for the recovery, 3.1-10% for the relative standard deviation range, and 9.8-15.6% for the uncertainty. The limits of detection and quantification were 0.015 μg mL(-1) and 0.05 mg kg(-1), respectively. Initial residue concentrations of imidacloprid after the 90 and 180 g a.i. ha(-1) treatments were 0.912 (half-life 11 days) and 1.681 mg kg(-1) (half-life 12.4 days), respectively. For spirotetramat + spirotetramat-enol, the residue concentrations were 1.337 (half-life 5.6 days) and 2.0 mg kg(-1) (half-life 7.6 days) for the 90 and 180 g a.i. ha(-1) treatments, respectively. Spirotetramat degraded faster than spirotetramat-enol. After treatment at 90 g a.i. ha(-1), the initial residues of both insecticides were within European Union maximum residue limits and a 1-day pre-harvest interval (PHI) was adequate for safe consumption of grapes. After treatment at 180 g a.i. ha(-1), the required PHI was 7 day. Therefore, a PHI of 7 day should be used after treatment with imidacloprid and spirotetramat.

Risk of DDT residue in maize consumed by infants as complementary diet in southwest Ethiopia.

PubMed

Mekonen, Seblework; Lachat, Carl; Ambelu, Argaw; Steurbaut, Walter; Kolsteren, Patrick; Jacxsens, Liesbeth; Wondafrash, Mekitie; Houbraken, Michael; Spanoghe, Pieter

2015-04-01

Infants in Ethiopia are consuming food items such as maize as a complementary diet. However, this may expose infants to toxic contaminants like DDT. Maize samples were collected from the households visited during a consumption survey and from markets in Jimma zone, southwestern Ethiopia. The residues of total DDT and its metabolites were analyzed using the Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) method combined with dispersive solid phase extraction cleanup (d-SPE). Deterministic and probabilistic methods of analysis were applied to determine the consumer exposure of infants to total DDT. The results from the exposure assessment were compared with the health based guidance value in this case the provisional tolerable daily intake (PTDI). All maize samples (n=127) were contaminated by DDT, with a mean concentration of 1.770 mg/kg, which was far above the maximum residue limit (MRL). The mean and 97.5 percentile (P 97.5) estimated daily intake of total DDT for consumers were respectively 0.011 and 0.309 mg/kg bw/day for deterministic and 0.011 and 0.083 mg/kg bw/day for probabilistic exposure assessment. For total infant population (consumers and non-consumers), the 97.5 percentile estimated daily intake were 0.265 and 0.032 mg/kg bw/day from the deterministic and probabilistic exposure assessments, respectively. Health risk estimation revealed that, the mean and 97.5 percentile for consumers, and 97.5 percentile estimated daily intake of total DDT for total population were above the PTDI. Therefore, in Ethiopia, the use of maize as complementary food for infants may pose a health risk due to DDT residue. Copyright © 2014 Elsevier B.V. All rights reserved.

Optical character recognition with feature extraction and associative memory matrix

NASA Astrophysics Data System (ADS)

Sasaki, Osami; Shibahara, Akihito; Suzuki, Takamasa

1998-06-01

A method is proposed in which handwritten characters are recognized using feature extraction and an associative memory matrix. In feature extraction, simple processes such as shifting and superimposing patterns are executed. A memory matrix is generated with singular value decomposition and by modifying small singular values. The method is optically implemented with two liquid crystal displays. Experimental results for the recognition of 25 handwritten alphabet characters clearly shows the effectiveness of the method.

[The tissue reaction to acrylic plastics modified by supercritical extraction with carbon dioxide].

PubMed

Volozhin, A I; Shekhter, A B; Karakov, K G; Sukhanov, Iu P; Gavril'chak, A V; Popov, V K; Antonov, E N; Karrot, M

1998-01-01

The process of extraction of admixtures from acryl plastic widely used in dentistry by means of supercritical carbon dioxide (sc-CO2) was studied and effects of extraction conditions on biocompatibility and toxicity of resultant materials assessed, sc-CO2 effectively purified the specimens from toxic compounds (monomers and low-molecular oligomers, methylmethacrylate, dichloroethane) and notably improved the biocompatability of polymer implants. Tissue reaction to ethacryl and protacryl depends on the degree of implant polymerization and duration of extraction of toxic substances from polymer.

Modified quadrupole mass analyzer RGA-100 for beam plasma research in forevacuum pressure range

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zolotukhin, D. B.; Tyunkov, A. V.; Yushkov, Yu. G., E-mail: yuyushkov@gmail.com

2015-12-15

The industrial quadrupole RGA-100 residual gas analyzer was modified for the research of electron beam-generated plasma at forevacuum pressure range. The standard ionizer of the RGA-100 was replaced by three electrode extracting unit. We made the optimization of operation parameters in order to provide the maximum values of measured currents of any ion species. The modified analyzer was successfully tested with beam plasma of argon, nitrogen, oxygen, and hydrocarbons.

Rapid preparation of nuclei-depleted detergent-resistant membrane fractions suitable for proteomics analysis.

PubMed

Adam, Rosalyn M; Yang, Wei; Di Vizio, Dolores; Mukhopadhyay, Nishit K; Steen, Hanno

2008-06-05

Cholesterol-rich membrane microdomains known as lipid rafts have been implicated in diverse physiologic processes including lipid transport and signal transduction. Lipid rafts were originally defined as detergent-resistant membranes (DRMs) due to their relative insolubility in cold non-ionic detergents. Recent findings suggest that, although DRMs are not equivalent to lipid rafts, the presence of a given protein within DRMs strongly suggests its potential for raft association in vivo. Therefore, isolation of DRMs represents a useful starting point for biochemical analysis of lipid rafts. The physicochemical properties of DRMs present unique challenges to analysis of their protein composition. Existing methods of isolating DRM-enriched fractions involve flotation of cell extracts in a sucrose density gradient, which, although successful, can be labor intensive, time consuming and results in dilute sucrose-containing fractions with limited utility for direct proteomic analysis. In addition, several studies describing the proteomic characterization of DRMs using this and other approaches have reported the presence of nuclear proteins in such fractions. It is unclear whether these results reflect trafficking of nuclear proteins to DRMs or whether they arise from nuclear contamination during isolation. To address these issues, we have modified a published differential detergent extraction method to enable rapid DRM isolation that minimizes nuclear contamination and yields fractions compatible with mass spectrometry. DRM-enriched fractions isolated using the conventional or modified extraction methods displayed comparable profiles of known DRM-associated proteins, including flotillins, GPI-anchored proteins and heterotrimeric G-protein subunits. Thus, the modified procedure yielded fractions consistent with those isolated by existing methods. However, we observed a marked reduction in the percentage of nuclear proteins identified in DRM fractions isolated with the modified method (15%) compared to DRMs isolated by conventional means (36%). Furthermore, of the 21 nuclear proteins identified exclusively in modified DRM fractions, 16 have been reported to exist in other subcellular sites, with evidence to suggest shuttling of these species between the nucleus and other organelles. We describe a modified DRM isolation procedure that generates DRMs that are largely free of nuclear contamination and that is compatible with downstream proteomic analyses with minimal additional processing. Our findings also imply that identification of nuclear proteins in DRMs is likely to reflect legitimate movement of proteins between compartments, and is not a result of contamination during extraction.

Method for extracting lanthanides and actinides from acid solutions by modification of purex solvent

DOEpatents

Horwitz, E. Philip; Kalina, Dale G.

1986-01-01

A process for the recovery of actinide and lanthanide values from aqueous solutions with an extraction solution containing an organic extractant having the formula: ##STR1## where .phi. is phenyl, R.sup.1 is a straight or branched alkyl or alkoxyalkyl containing from 6 to 12 carbon atoms and R.sup.2 is an alkyl containing from 3 to 6 carbon atoms and phase modifiers in a water-immiscible hydrocarbon diluent. The addition of the extractant to the Purex process extractant, tri-n-butylphosphate in normal paraffin hydrocarbon diluent, will permit the extraction of multivalent lanthanide and actinide values from 0.1 to 12.0 molar acid solutions.

Simple New Screw Insertion Technique without Extraction for Broken Pedicle Screws.

PubMed

Kil, Jin-Sang; Park, Jong-Tae

2018-05-01

Spinal transpedicular screw fixation is widely performed. Broken pedicle screw rates range from 3%-7.1%. Several techniques have been described for extraction of broken pedicle screws. However, most of these techniques require special instruments. We describe a simple, modified technique for management of broken pedicle screws without extraction. No special instruments or drilling in an adjacent pedicle are required. We used a high-speed air drill with a round burr. With C-arm fluoroscopy guidance, the distal fragment of a broken pedicle screw was palpated using free-hand technique through the screw entry hole. A high-speed air drill with a round burr (not a diamond burr) was inserted through the hole. Drilling began slowly and continued until enough space was obtained for new screw insertion. Using this space, we performed new pedicle screw fixation medially alongside the distal fragment of the broken pedicle screw. We performed the insertion with a previously used entry hole and pathway in the pedicle. The same size pedicle screw was used. Three patients were treated with this modified technique. New screw insertion was successful in all cases after partial drilling of the distal broken pedicle screw fragment. There were no complications, such as screw loosening, dural tears, or root injury. We describe a simple, modified technique for management of broken pedicle screws without extraction. This technique is recommended in patients who require insertion of a new screw. Copyright © 2017. Published by Elsevier Inc.

In-vitro evaluation of copper nanoparticles cytotoxicity on prostate cancer cell lines and their antioxidant, sensing and catalytic activity: One-pot green approach.

PubMed

Prasad, P Reddy; Kanchi, S; Naidoo, E B

2016-08-01

In this study, Broccoli green extract was reported as a green and environmental friendly precursor for the one-pot biosynthesis of copper nanoparticles. The synthesized nanoparticles were characterized by UV-vis, FTIR, TEM, DLS, XRD and cyclic voltammetry. The TEM and DLS results showed that the NPs are in spherical and monodispersed with an average particle size of ~4.8nm. The FTIR results confirmed the occurrence of bioactive functional groups that are responsible for reducing cupric sulphate to copper ions. The UV-vis spectrophotometry was used for catalytic reduction of 4-nitrophenol and its dynamic reaction in Britton-Robinson buffer solution. This catalytic activity was further supported with methylene blue and methyl red dyes degradation. The nanocatalyst can be recovered from the reaction mixture and reused many times with none vital loss of catalytic activity. The Broccoli green extract modified copper nanoparticles coated on screen printing electrode laid a new sensing platform and has an excellent electrocatalytic activity. Furthermore, surface modified CuNPs with Broccoli green extract exhibited no cytotoxicity at the concentration ranging from 0.5 to 1.5μM on the prostate cancer (PC-3) cell lines. The maximum scavenging % of Broccoli green extract modified CuNPs was found to be >70.50% at the concentration of 0.25mM against 1,1-diphenyl-2-picrylhydrazyl. Copyright © 2016 Elsevier B.V. All rights reserved.

Determination of residual nonsteroidal anti-inflammatory drugs in aqueous sample using magnetic nanoparticles modified with cetyltrimethylammonium bromide by high performance liquid chromatography.

PubMed

Khoeini Sharifabadi, Malihe; Saber-Tehrani, Mohammad; Waqif Husain, Syed; Mehdinia, Ali; Aberoomand-Azar, Parviz

2014-01-01

A simple and sensitive solid-phase extraction method for separation and preconcentration of trace amount of four nonsteroidal anti-inflammatory drugs (naproxen, indomethacin, diclofenac, and ibuprofen) using Fe3O4 magnetic nanoparticles modified with cetyltrimethylammonium bromide has been developed. For this purpose, the surface of MNPs was modified with cetyltrimethylammonium bromide (CTAB) as a cationic surfactant. Effects of different parameters influencing the extraction efficiency of drugs including the pH, amount of salt, shaking time, eluent type, the volume of solvent, amount of adsorbent, sample volume, and the time of desorption were investigated and optimized. Methanol has been used as desorption solvent and the extracts were analysed on a reversed-phase octadecyl silica column using 0.02 M phosphate-buffer (pH = 6.02) acetonitrile (65 : 35 v/v) as the mobile phase and the effluents were measured at 202 nm with ultraviolet detector. The relative standard deviation (RSD%) of the method was investigated at three concentrations (25, 50, and 200 ng/mL) and was in the range of 3.98-9.83% (n = 6) for 50 ng/mL. The calibration curves obtained for studied drugs show reasonable linearity (R (2) > 0.99) and the limit of detection (LODs) ranged between 2 and 7 ng/mL. Finally, the proposed method has been effectively employed in extraction and determination of the drugs in biological and environmental samples.

Optimization of conditions for supercritical fluid extraction of flavonoids from hops (Humulus lupulus L.)*

PubMed Central

He, Guo-qing; Xiong, Hao-ping; Chen, Qi-he; Ruan, Hui; Wang, Zhao-yue; Traoré, Lonseny

2005-01-01

Waste hops are good sources of flavonoids. Extraction of flavonoids from waste hops (SC-CO2 extracted hops) using supercritical fluids technology was investigated. Various temperatures, pressures and concentrations of ethanol (modifier) and the ratio (w/w) of solvent to material were tested in this study. The results of single factor and orthogonal experiments showed that at 50 °C, 25 MPa, the ratio of solvent to material (50%), ethanol concentration (80%) resulted in maximum extraction yield flavonoids (7.8 mg/g). HPLC-MS analysis of the extracts indicated that flavonoids obtained were xanthohumol, the principal prenylflavonoid in hops. PMID:16187413

Ionic liquids intercalated in montmorillonite as the sorptive phase for the extraction of low-polarity organic compounds from water by rotating-disk sorptive extraction.

PubMed

Fiscal-Ladino, Jhon A; Obando-Ceballos, Mónica; Rosero-Moreano, Milton; Montaño, Diego F; Cardona, Wilson; Giraldo, Luis F; Richter, Pablo

2017-02-08

Montmorillonite (MMT) clays were modified by the intercalation into their galleries of ionic liquids (IL) based on imidazolium quaternary ammonium salts. This new eco-materials exhibited good features for use as a sorptive phase in the extraction of low-polarity analytes from aqueous samples. Spectroscopic analyses of the modified clays were conducted and revealed an increase in the basal spacing and a shifting of the reflection plane towards lower values as a consequence of the effective intercalation of organic cations into the MMT structure. The novel sorbent developed herein was assayed as the sorptive phase in rotating-disk sorptive extraction (RDSE), using polychlorinated biphenyls (PCBs), representative of low-polarity pollutants, as model analytes. The final determination was made by gas chromatography with electron capture detection. Among the synthetized sorptive phases, the selected system for analytical purposes consisted of MMT modified with the 1-hexadecyl-3-methylimidazolium bromide (HDMIM-Br) IL. Satisfactory analytical features were achieved using a sample volume of 5 mL: the relative recoveries from a wastewater sample were higher than 80%, the detection limits were between 3 ng L -1 and 43 ng L -1 , the precision (within-run precision) expressed as the relative standard deviation ranged from 2% to 24%, and the enrichment factors ranged between 18 and 28. Using RDSE, the extraction efficiency achieved for the selected MMT-HDMIM-Br phase was compared with other commercial solid phases/supports, such as polypropylene, polypropylene with 1-octanol (as a supported liquid membrane), octadecyl (C18) and octyl (C8), and showed the highest response for all the studied analytes. Under the optimized extraction conditions, this new device was applied in the analysis of the influent of a wastewater treatment plant in Santiago (Chile), demonstrating its applicability through the good recoveries and precision achieved with real samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Modified biopolymers as sorbents for the removal of naphthenic acids from oil sands process affected water (OSPW).

PubMed

Arshad, Muhammad; Khosa, M A; Siddique, Tariq; Ullah, Aman

2016-11-01

Oil sands operations consume large volumes of water in bitumen extraction process and produce tailings that express pore water to the surface of tailings ponds known as oil sands process-affected water (OSPW). The OSPW is toxic and cannot be released into the environment without treatment. In addition to metals, dissolved solids, dissolved gases, hydrocarbons and polyaromatic compounds etc., OSPW also contains a complex mixture of dissolved organic acids, referred to as naphthenic acids (NAs). The NAs are highly toxic and react with metals to develop highly corrosive functionalities which cause corrosion in the oil sands processing and refining processes. We have chemically modified keratin biopolymer using polyhedral oligomeric silsesquioxanes (POSS) nanocages and goethite dopant to unfold keratinous structure for improving functionality. The untreated neat keratin and two modified sorbents were characterized to investigate structural, morphological, dimensional and thermal properties. These sorbents were then tested for the removal of NAs from OSPW. The NAs were selectively extracted and quantified before and after sorption process. The biosorption capacity (Q), rejection percentage (R%) and isotherm models were studied to investigate NAs removal efficiency of POSS modified keratin biopolymer (PMKB) and goethite modified keratin biopolymer (GMKB) from aliquots of OSPW. Copyright © 2016 Elsevier Ltd. All rights reserved.

The influence of volatile semiochemicals from stink bug eggs and oviposition-damaged plants on the foraging behaviour of the egg parasitoid Telenomus podisi.

PubMed

Michereff, M F F; Borges, M; Aquino, M F S; Laumann, R A; Mendes Gomes, A C M; Blassioli-Moraes, M C

2016-10-01

During host selection, physical and chemical stimuli provide important cues that modify search behaviours of natural enemies. We evaluated the influence of volatiles released by eggs and egg extracts of the stink bug Euschistus heros and by soybean plants treated with the eggs and egg extracts on Telenomus podisi foraging behaviour. Responses to volatiles were evaluated in Y-tube olfactometers after exposure to (1) one egg cluster for 24 h; (2) plants with eggs laid by the stink bug, tested at 24, 48, and 72 h after treatment; (3) plants with eggs laid artificially, tested at 24, 48, and 72 h after treatment; and (4) plants treated with acetone or hexane extracts of eggs. Telenomus podisi was attracted to volatiles emitted by one egg cluster and to acetone extracts of one egg cluster, but not to air or acetone controls. There were no responses to odours of plants treated with eggs or egg extracts. Analysis of acetone extracts of egg clusters by gas chromatography revealed the major components were saturated and unsaturated fatty acids, including hexadecanoic acid, linoleic acid, and (Z)-9-octadecenoic acid. Our results suggest that one egg cluster and the acetone extract of one egg cluster contain volatile compounds that can modify T. podisi foraging behaviour, and that the amounts of these compounds, probably together with some minor compounds, are important for host recognition by T. podisi. Also, the oviposition damage or egg extracts on the plant did not elicit indirect defences that attracted Telenomus podisi.

Simultaneous extraction and HPLC determination of 3-indole butyric acid and 3-indole acetic acid in pea plant by using ionic liquid-modified silica as sorbent.

PubMed

Sheikhian, Leila; Bina, Sedigheh

2016-01-15

In this study, ionic liquid-modified silica was used as sorbent for simultaneous extraction and preconcentration of 3-indole butyric acid and 3-indole acetic acid in pea plants. The effect of some parameters such as pH and ionic strength of sample solution, amount of sorbent, flow rate of aqueous sample solution and eluent solution, concentration of eluent solution, and temperature were studied for each hormone solution. Percent extraction of 3-indole butyric acid and 3-indole acetic acid was strongly affected by pH of aqueous sample solution. Ionic strength of aqueous phase and temperature showed no serious effects on extraction efficiency of studied plant hormones. Obtained breakthrough volume was 200mL for each of studied hormones. Preconcentration factor for spectroscopic and chromatographic determination of studied hormones was 100 and 4.0×10(3) respectively. Each solid sorbent phase was reusable for almost 10 times of extraction/stripping procedure. Relative standard deviations of extraction/stripping processes of 3-indole butyric acid and 3-indole acetic acid were 2.79% and 3.66% respectively. The calculated limit of detections for IBA and IAA were 9.1×10(-2)mgL(-1) and 1.6×10(-1)mgL(-1) respectively. Copyright © 2015 Elsevier B.V. All rights reserved.

Cocos nucifera Linn. (Palmae) husk fiber ethanolic extract: antioxidant capacity and electrochemical investigation.

PubMed

Oliveira, Monika Bezerra dos Santos; Valentim, Iara Barros; de Vasconcelos, Camila Calado; Omena, Cristhiane Maria Bazílio; Bechara, Etelvino José Henriques; da Costa, João Gomes; Freitas, Mikael de Lima; Sant'Ana, Antônio Euzébio Goulart; Goulart, Marília Oliveira Fonseca

2013-02-01

The present study aims to determine the antioxidant capacity of the ethanolic extracts of husk fiber of four coconut (Cocos nucifera L.) varieties (yellow dwarf, green dwarf, giant and hybrid) and to evaluate the electrochemical behavior of these extracts on a glassy carbon electrode and on a modified glassy carbon electrode. The highest values of total phenolic content were obtained for the hybrid (531 ± 24 mg GAE g(-1) dry extract) and yellow dwarf (501 ± 29 mg GAE g(-1) dry extract) varieties and the lowest was for the green dwarf variety with 58 ± 9 mg GAE g(-1) dry extract. The ability of the extracts to scavenge DPPH˙ radicals was in the order of giant > yellow dwarf > hybrid > green dwarf and the IC50 values varied from 8.6 to 55.9 μg mL(-1). All varieties showed reducing potential by the use of FRAP and CUPRAC methods, with the lowest performance obtained for the green dwarf variety. Additionally, through the use of mimetic biomembranes, ethanolic extracts of coconut husk were shown to protect lipids against oxidative damage independent of the variety. The main antioxidants identified in the extract of yellow dwarf variety by UPLC-MS were quercetin and catechin. Cyclic voltammetric studies of the ethanolic extracts on glassy carbon electrode confirmed the presence of easily oxidized compounds, and the high antioxidant capacity of the varieties. This capacity was expressed as mg quercetin equivalents g(-1) dry extract and ranged from 25.9 up to 53.5 mg QE g(-1). A poly-xanthurenic acid (poly-Xa)/multi-walled carbon nanotube (MWCNT) / glassy carbon modified electrode (poly-Xa/MWCNT/GCE) was used for this purpose. Our findings suggest that these extracts are potentially important antioxidant supplements for the everyday human diet, pharmaceutical and cosmetic industries, thereby aggregating value to the enormous amount of waste from the coconut industry, mostly used for burning purposes.

Interlaboratory study of DNA extraction from multiple ground samples, multiplex real-time PCR, and multiplex qualitative PCR for individual kernel detection system of genetically modified maize.

PubMed

Akiyama, Hiroshi; Sakata, Kozue; Makiyma, Daiki; Nakamura, Kosuke; Teshima, Reiko; Nakashima, Akie; Ogawa, Asako; Yamagishi, Toru; Futo, Satoshi; Oguchi, Taichi; Mano, Junichi; Kitta, Kazumi

2011-01-01

In many countries, the labeling of grains, feed, and foodstuff is mandatory if the genetically modified (GM) organism content exceeds a certain level of approved GM varieties. We previously developed an individual kernel detection system consisting of grinding individual kernels, DNA extraction from the individually ground kernels, GM detection using multiplex real-time PCR, and GM event detection using multiplex qualitative PCR to analyze the precise commingling level and varieties of GM maize in real sample grains. We performed the interlaboratory study of the DNA extraction with multiple ground samples, multiplex real-time PCR detection, and multiplex qualitative PCR detection to evaluate its applicability, practicality, and ruggedness for the individual kernel detection system of GM maize. DNA extraction with multiple ground samples, multiplex real-time PCR, and multiplex qualitative PCR were evaluated by five laboratories in Japan, and all results from these laboratories were consistent with the expected results in terms of the commingling level and event analysis. Thus, the DNA extraction with multiple ground samples, multiplex real-time PCR, and multiplex qualitative PCR for the individual kernel detection system is applicable and practicable in a laboratory to regulate the commingling level of GM maize grain for GM samples, including stacked GM maize.

Large-Scale Membrane- and Lignin-Modified Adsorbent-Assisted Extraction and Preconcentration of Triazine Analogs and Aflatoxins

PubMed Central

Hu, Shun-Wei; Chen, Shushi

2017-01-01

The large-scale simultaneous extraction and concentration of aqueous solutions of triazine analogs, and aflatoxins, through a hydrocarbon-based membrane (e.g., polyethylene, polyethylene/polypropylene copolymer) under ambient temperature and atmospheric pressure is reported. The subsequent adsorption of analyte in the extraction chamber over the lignin-modified silica gel facilitates the process by reducing the operating time. The maximum adsorption capacity values for triazine analogs and aflatoxins are mainly adsorption mechanism-dependent and were calculated to be 0.432 and 0.297 mg/10 mg, respectively. The permeation, and therefore the percentage of analyte extracted, ranges from 1% to almost 100%, and varies among the solvents examined. It is considered to be vapor pressure- and chemical polarity-dependent, and is thus highly affected by the nature and thickness of the membrane, the discrepancy in the solubility values of the analyte between the two liquid phases, and the amount of adsorbent used in the process. A dependence on the size of the analyte was observed in the adsorption capacity measurement, but not in the extraction process. The theoretical interaction simulation and FTIR data show that the planar aflatoxin molecule releases much more energy when facing toward the membrane molecule when approaching it, and the mechanism leading to the adsorption. PMID:28398252

Application of RT-PCR in formalin-fixed and paraffin-embedded lung cancer tissues.

PubMed

Zhang, Fan; Wang, Zhuo-min; Liu, Hong-yu; Bai, Yun; Wei, Sen; Li, Ying; Wang, Min; Chen, Jun; Zhou, Qing-hua

2010-01-01

To analyze gene expression in formalin-fixed, paraffin-embedded lung cancer tissues using modified method. Total RNA from frozen tissues was extracted using TRIZOL reagent. RNA was extracted from formalin-fixed, paraffin-embedded tissues by digestion with proteinase K before the acid-phenol:chloroform extraction and carrier precipitation. We modified this method by using a higher concentration of proteinase K and a longer digestion time, optimized to 16 hours. RT-PCR and real-time RT-PCR were used to check reproducibility and the concordance between frozen and paraffin-embedded samples. The results showed that the RNA extracted from the paraffin-embedded lung tissues had high quality with the most fragment length between 28S and 18S bands (about 1000 to 2000 bases). The housekeeping gene GUSB exhibited low variation of expression in frozen and paraffin-embedded lung tissues, whereas PGK1 had the lowest variation in lymphoma tissues. Furthermore, real-time PCR analysis of the expression of known prognostic genes in non-small cell lung carcinoma (NSCLC) demonstrated an extremely high correlation (r>0.880) between the paired frozen and formalin-fixed, paraffin-embedded specimens. This improved method of RNA extraction is suitable for real-time quantitative RT-PCR, and may be used for global gene expression profiling of paraffin-embedded tissues.

Large-Scale Membrane- and Lignin-Modified Adsorbent-Assisted Extraction and Preconcentration of Triazine Analogs and Aflatoxins.

PubMed

Hu, Shun-Wei; Chen, Shushi

2017-04-11

The large-scale simultaneous extraction and concentration of aqueous solutions of triazine analogs, and aflatoxins, through a hydrocarbon-based membrane (e.g., polyethylene, polyethylene/polypropylene copolymer) under ambient temperature and atmospheric pressure is reported. The subsequent adsorption of analyte in the extraction chamber over the lignin-modified silica gel facilitates the process by reducing the operating time. The maximum adsorption capacity values for triazine analogs and aflatoxins are mainly adsorption mechanism-dependent and were calculated to be 0.432 and 0.297 mg/10 mg, respectively. The permeation, and therefore the percentage of analyte extracted, ranges from 1% to almost 100%, and varies among the solvents examined. It is considered to be vapor pressure- and chemical polarity-dependent, and is thus highly affected by the nature and thickness of the membrane, the discrepancy in the solubility values of the analyte between the two liquid phases, and the amount of adsorbent used in the process. A dependence on the size of the analyte was observed in the adsorption capacity measurement, but not in the extraction process. The theoretical interaction simulation and FTIR data show that the planar aflatoxin molecule releases much more energy when facing toward the membrane molecule when approaching it, and the mechanism leading to the adsorption.

Improving the recovery of qPCR-grade DNA from sludge and sediment.

PubMed

Bonot, Sébastien; Courtois, Sophie; Block, Jean-Claude; Merlin, Christophe

2010-08-01

DNA extraction is often considered as the limiting step of most molecular approaches in ecology and environmental microbiology. Ten existing DNA extraction protocols were compared for recovery of DNA from sludge and a modified version of the protocol described by Porteous et al. (Mol Ecol 6:787-791, 1997) was determined to be the best method for recovery of DNA suitable for PCR. In this respect, it appeared that the commonly used guanidine isothiocyanate could impair the quality of the extracted DNA unless its concentration is lowered. Second, conditioning the samples as liquors as opposed to pellets critically impacts the outcome of the extraction. The suitability of the modified Porteous protocol for quantitative PCR applications is demonstrated in a series of experiments showing the absence of interfering coextracted inhibitors and the linear correspondence between the concentrations of input target DNA and PCR product. Interestingly, it is also shown that the nature of the environmental matrices affects the recovery yield of both circular plasmids and chromosomal DNA, resulting in an apparent fluctuation of the plasmid copy number per cell. This means that quantitative data obtained by PCR remain comparable as long as they apply to an identical target sequence extracted from a similar environment and amplified under the same conditions.

Discovering body site and severity modifiers in clinical texts

PubMed Central

Dligach, Dmitriy; Bethard, Steven; Becker, Lee; Miller, Timothy; Savova, Guergana K

2014-01-01

Objective To research computational methods for discovering body site and severity modifiers in clinical texts. Methods We cast the task of discovering body site and severity modifiers as a relation extraction problem in the context of a supervised machine learning framework. We utilize rich linguistic features to represent the pairs of relation arguments and delegate the decision about the nature of the relationship between them to a support vector machine model. We evaluate our models using two corpora that annotate body site and severity modifiers. We also compare the model performance to a number of rule-based baselines. We conduct cross-domain portability experiments. In addition, we carry out feature ablation experiments to determine the contribution of various feature groups. Finally, we perform error analysis and report the sources of errors. Results The performance of our method for discovering body site modifiers achieves F1 of 0.740–0.908 and our method for discovering severity modifiers achieves F1 of 0.905–0.929. Discussion Results indicate that both methods perform well on both in-domain and out-domain data, approaching the performance of human annotators. The most salient features are token and named entity features, although syntactic dependency features also contribute to the overall performance. The dominant sources of errors are infrequent patterns in the data and inability of the system to discern deeper semantic structures. Conclusions We investigated computational methods for discovering body site and severity modifiers in clinical texts. Our best system is released open source as part of the clinical Text Analysis and Knowledge Extraction System (cTAKES). PMID:24091648

Discovering body site and severity modifiers in clinical texts.

PubMed

Dligach, Dmitriy; Bethard, Steven; Becker, Lee; Miller, Timothy; Savova, Guergana K

2014-01-01

To research computational methods for discovering body site and severity modifiers in clinical texts. We cast the task of discovering body site and severity modifiers as a relation extraction problem in the context of a supervised machine learning framework. We utilize rich linguistic features to represent the pairs of relation arguments and delegate the decision about the nature of the relationship between them to a support vector machine model. We evaluate our models using two corpora that annotate body site and severity modifiers. We also compare the model performance to a number of rule-based baselines. We conduct cross-domain portability experiments. In addition, we carry out feature ablation experiments to determine the contribution of various feature groups. Finally, we perform error analysis and report the sources of errors. The performance of our method for discovering body site modifiers achieves F1 of 0.740-0.908 and our method for discovering severity modifiers achieves F1 of 0.905-0.929. Results indicate that both methods perform well on both in-domain and out-domain data, approaching the performance of human annotators. The most salient features are token and named entity features, although syntactic dependency features also contribute to the overall performance. The dominant sources of errors are infrequent patterns in the data and inability of the system to discern deeper semantic structures. We investigated computational methods for discovering body site and severity modifiers in clinical texts. Our best system is released open source as part of the clinical Text Analysis and Knowledge Extraction System (cTAKES).

Method for extracting lanthanides and actinides from acid solutions by modification of Purex solvent

DOEpatents

Horwitz, E.P.; Kalina, D.G.

1986-03-04

A process is described for the recovery of actinide and lanthanide values from aqueous solutions with an extraction solution containing an organic extractant having the formula as shown in a diagram where [phi] is phenyl, R[sup 1] is a straight or branched alkyl or alkoxyalkyl containing from 6 to 12 carbon atoms and R[sup 2] is an alkyl containing from 3 to 6 carbon atoms and phase modifiers in a water-immiscible hydrocarbon diluent. The addition of the extractant to the Purex process extractant, tri-n-butylphosphate in normal paraffin hydrocarbon diluent, will permit the extraction of multivalent lanthanide and actinide values from 0.1 to 12.0 molar acid solutions. 6 figs.

A method suitable for DNA extraction from humus-rich soil.

PubMed

Miao, Tianjin; Gao, Song; Jiang, Shengwei; Kan, Guoshi; Liu, Pengju; Wu, Xianming; An, Yingfeng; Yao, Shuo

2014-11-01

A rapid and convenient method for extracting DNA from soil is presented. Soil DNA is extracted by direct cell lysis in the presence of EDTA, SDS, phenol, chloroform and isoamyl alcohol (3-methyl-1-butanol) followed by precipitation with 2-propanol. The extracted DNA is purified by modified DNA purification kit and DNA gel extraction kit. With this method, DNA extracted from humus-rich dark brown forest soil was free from humic substances and, therefore, could be used for efficient PCR amplification and restriction digestion. In contrast, DNA sample extracted with the traditional CTAB-based method had lower yield and purity, and no DNA could be extracted from the same soil sample with a commonly-used commercial soil DNA isolation kit. In addition, this method is time-saving and convenient, providing an efficient choice especially for DNA extraction from humus-rich soils.

21 CFR 177.1050 - Acrylonitrile/styrene copoly-mer modified with butadiene/styrene elastomer.

Code of Federal Regulations, 2014 CFR

2014-04-01

... for use E, F, or G described in table 2 of § 176.170(c) of this chapter. (a) Identity. For the purpose... with 250 milliliters spectral grade n-heptane at reflux temperature for 2 hours. (e) Accelerated extraction end test. The modified copolymer shall yield acrylonitrile monomer not in excess of 0.4 ppm when...

Anti-corrosion and Anti-bacteria Property of Modified Pomegranate Peel Extract

NASA Astrophysics Data System (ADS)

Gu, Xue-Fan; Chang, Xiao-Feng; Cheng, Chao; Zhang, Li; Zhang, Yong-Ming; Zhang, Jie; Chen, Gang

2018-03-01

Using weight loss method, the pomegranate peel extract (PPE), that is a green corrosion inhibitors, have been studied in the corrosion inhibition of Q235A steel in 1M hydrochloric acid solution at 30°C, 45°C, 60°C, respectively. The inhibition rate of extract varies with the extraction concentration in the range of 10 ∼ 1000mg / L, up to 92.7%. Extract inhibits corrosion through adsorption mechanisms. Besides polyphenols hydroxyl and ether groups can slow down corrosion by capturing H+. Polyphenols can remove the dissolved O2, and curb oxygen reducing corrosion. PPE is antifungal active against TGB and FB, but not so active against SRB.

Methods of combined bioprocessing and related microorganisms, thermophilic and/or acidophilic enzymes, and nucleic acids encoding said enzymes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thompson, David N.; Apel, William A.; Thompson, Vicki S.

A genetically modified organism comprising: at least one nucleic acid sequence and/or at least one recombinant nucleic acid isolated from Alicyclobacillus acidocaldarius and encoding a polypeptide involved in at least partially degrading, cleaving, transporting, metabolizing, or removing polysaccharides, cellulose, lignocellulose, hemicellulose, lignin, starch, sugars, sugar oligomers, carbohydrates, complex carbohydrates, chitin, heteroxylans, glycosides, xylan-, glucan-, galactan-, or mannan-decorating groups; and at least one nucleic acid sequence and/or at least one recombinant nucleic acid encoding a polypeptide involved in fermenting sugar molecules to a product. Additionally, enzymatic and/or proteinaceous extracts may be isolated from one or more genetically modified organisms. The extractsmore » are utilized to convert biomass into a product. Further provided are methods of converting biomass into products comprising: placing the genetically modified organism and/or enzymatic extracts thereof in fluid contact with polysaccharides, cellulose, lignocellulose, hemicellulose, lignin, starch, sugars, sugar oligomers, carbohydrates, complex carbohydrates, chitin, heteroxylans, glycosides, and/or xylan-, glucan-, galactan-, or mannan-decorating groups.« less

Modified Denavit-Hartenberg parameters for better location of joint axis systems in robot arms

NASA Technical Reports Server (NTRS)

Barker, L. K.

1986-01-01

The Denavit-Hartenberg parameters define the relative location of successive joint axis systems in a robot arm. A recent justifiable criticism is that one of these parameters becomes extremely large when two successive joints have near-parallel rotational axes. Geometrically, this parameter then locates a joint axis system at an excessive distance from the robot arm and, computationally, leads to an ill-conditioned transformation matrix. In this paper, a simple modification (which results from constraining a transverse vector between successive joint rotational axes to be normal to one of the rotational axes, instead of both) overcomes this criticism and favorably locates the joint axis system. An example is given for near-parallel rotational axes of the elbow and shoulder joints in a robot arm. The regular and modified parameters are extracted by an algebraic method with simulated measurement data. Unlike the modified parameters, extracted values of the regular parameters are very sensitive to measurement accuracy.

Sensitivity enhancement for nitrophenols using cationic surfactant-modified activated carbon for solid-phase extraction surface-assisted laser desorption/ionization mass spectrometry.

PubMed

Chen, Y C; Tsai, M F

2000-01-01

Previous work has demonstrated that a combination of solid-phase extraction with surface-assisted laser desorption/ionization (SPE-SALDI) mass spectrometry can be applied to the determination of trace nitrophenols in water. An improved method to lower the detection limit of this hyphenated technique is described in this present study. Activated carbon powder is used as both the SPE adsorbent and the SALDI solid in the analysis by SPE-SALDI. The surface of the activated carbon is modified by passing an aqueous solution of a cationic surfactant through the SPE cartridge. The results demonstrate that the sensitivity for nitrophenols in the analysis by SPE-SALDI can be improved by using cationic surfactants to modify the surface of the activated carbon. The detection limit for nitrophenols is about 25 ppt based on a signal-to-noise ratio of 3 by sampling from 100 mL of solution. Copyright 2000 John Wiley & Sons, Ltd.

Solvent-modified solid-phase microextraction for the determination of diazepam in human plasma samples by capillary gas chromatography.

PubMed

Krogh, M; Grefslie, H; Rasmussen, K E

1997-02-21

This paper describes microextraction and gas chromatographic analysis of diazepam from human plasma. The method was based on immobilisation of 1.5 microliters of 1-octanol on a polyacrylate-coated fiber designed for solid-phase microextraction. The solvent-modified fibre was used to extract diazepam from the samples. The plasma sample was pre-treated to release diazepam from the protein binding. The fibre was inserted into the modified plasma sample, adjusted to pH 5.5 an internal standard was added and the mixture was carefully stirred for 4 min. The fibre with the immobilised solvent and the enriched analytes was injected into the capillary gas chromatograph. The solvent and the extracted analytes were evaporated at 300 degrees C in the split-splitless injection port of the gas chromatograph, separated on a methylsilicon capillary column and detected with a nitrogen-phosphorus detector. The method was shown to be reproducible with a detection limit of 0.10 nmol/ml in human plasma.

Amorphous titania modified with boric acid for selective capture of glycoproteins.

PubMed

Jin, Shanxia; Liu, Liping; Zhou, Ping

2018-05-22

Amorphous titania was modified with boric acid, and the resulting material was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray powder diffraction and X-ray photoelectron spectrometry. The new material, in contrast to conventional boronate affinity materials containing boronic acid ligands, bears boric acid groups. It is shown to exhibit high specificity for glycoproteins, and this was applied to design a method for solid phase extraction of glycoproteins as shown for ribonuclease B, horse radish peroxidase and ovalbumin. Glycoproteins were captured under slightly alkaline environment and released in acidic solutions. The glycoproteins extracted were detected by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. The binding capacities for ribonuclease B, horse radish peroxidase and ovalbumin typically are 9.3, 26.0 and 53.0 mg ∙ g -1 , respectively. The method was successfully applied to the selective enrichment of ovalbumin from egg white. Graphical abstract Schematic presentation of the capture of glycoproteins by amorphous titania modified with boric acid.