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.

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.

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.

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.

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.

Simultaneous determination of five plant growth regulators in fruits by modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction and liquid chromatography-tandem mass spectrometry.

PubMed

Shi, Xiaomei; Jin, Fen; Huang, Yuting; Du, Xinwei; Li, Chunmei; Wang, Miao; Shao, Hua; Jin, Maojun; Wang, Jing

2012-01-11

An effective method using liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed and optimized to obtain a complete separation of five representative plant growth regulators (PGRs) [gibberellic acid, 2,4-dichlorophenoxyacetic acid (2,4-D), thidiazuron, forchlorfenuron, and paclobutrazol] in fruits. Extraction was performed with acetonitrile containing 0.1% (v/v) acetic acid, applying modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) methodology. LC-MS/MS conditions including composition of mobile phases and mass spectrometry (MS) conditions were evaluated to achieve the highest sensitivity in MS detection. All of the data acquisition was employed in the segmented multiple-reaction monitoring mode for the selected negative and positive transition ions. The octadecylsilyl (C18) dispersive solid-phase extraction (SPE) sorbent was found to provide the more satisfied recoveries than primary secondary amine (PSA) and graphitized carbon black (GCB) for five target PGRs. The optimized method allowed for recoveries of 76-112% for the five PGRs from fruit samples with relative standard deviation (RSD) values less than 10%. Limits of quantification (0.5-16.5 μg/kg) were lower than the maximum limit of residues established for PGRs. The results demonstrated that the developed LC-MS/MS and QuEChERS extraction method is highly effective for analyzing trace amounts of target PGRs in fruit samples. Finally, the method was successfully used to detect residual PGRs in Beijing, China, in 2010. The concentrations of 2,4-D (5.1-1503 μg/kg) and paclobutrazol (1-1381 μg/kg) found in orange and peach, respectively, suggesting that the use of these PGRs in these fruits should be regulated in China in the future.

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...

Determination of sulfonamides in animal tissues by modified QuEChERS and liquid chromatography tandem mass spectrometry.

PubMed

Wen, Ching-Hsuan; Lin, Shu-Ling; Fuh, Ming-Ren

2017-03-01

In this study, the salting-out solvent extraction and dispersive solid-phase extraction (dSPE) clean-up steps in QuEChERS (quick, easy, cheap, effective, rugged, and safe) method were optimized to reduce matrix effect and efficiently extract target sulfonamides from a variety of edible animal tissues. The extracted sulfonamides were then analyzed using liquid chromatography tandem mass spectrometry (LC-MS/MS). Good extraction recoveries (74.0-100.3% in five different sources of animal tissues; n=3) with acceptable matrix effect (<10%, except for liver samples) were obtained using the proposed method. For the first time, a commercial ND-lipids cartridge was used to remove hydrophobic matrix components from fat-rich animal tissues in the clean-up step of QuEChERS. In addition, good linearity (0.125-12.5ngg -1 ) was observed using matrix-matched calibration (in beef). Limits of detection (LODs) were estimated at 0.01-0.03ngg -1 in beef, pork, and chicken samples. For beef tripe and pig liver samples, the LODs were in the range of 0.02-0.04ngg -1 . Good intra-day/inter-day precision (1.0-10.5%/0.4-8.0%) and accuracy (95.2-107.2%/97.8-102.1%) were also achieved using the modified QuEChERS for sample pretreatment. The applicability of the modified QuEChERS-LC-MS/MS method was demonstrated by determining the occurrence of target sulfonamides in various edible animal tissues for potential food safety analysis. Copyright © 2016 Elsevier B.V. All rights reserved.

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 ...

A modified QuEChERS method for the determination of some herbicides in yogurt and milk by high performance liquid chromatography.

PubMed

Li, Na; Lei, Lei; Nian, Li; Zhang, Rui; Wu, Shuting; Ren, Ruibing; Wang, Yeqiang; Zhang, Hanqi; Yu, Aimin

2013-02-15

A modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) method was applied to the extraction of triazines and phenylureas from milk and yogurt. The herbicides was extracted by the mixture of ethyl acetate and n-hexane and cleaned by primary secondary amine (10mg/mL). The frozen-out centrifugation was applied to further remove fatty. The proposed method can achieve efficient extraction and cleanup. Some experimental parameters, such as extraction method, extraction solvent and adsorbent, pH of sample solution, extraction time and amount of primary secondary amine and sodium chloride were investigated and optimized. The precision and absolute recoveries of eight herbicides vary from 0.07 to 5.86% and from 78.9 to 99.9%, respectively. The detection limits for simeton, monuron, chlorotoluron, simetryne, atrazine, karmex, ametryne and propazine range from 0.15 to 0.35 ng/mL. Copyright © 2012 Elsevier B.V. All rights reserved.

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 ...

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.

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.

Fast determination of pyrethroid pesticides in tobacco by GC-MS-SIM coupled with modified QuEChERS sample preparation procedure.

PubMed

Gao, Yan; Sun, Ying; Jiang, Chunzhu; Yu, Xi; Wang, Yuanpeng; Zhang, Hanqi; Song, Daqian

2013-01-01

An analytical method was developed for the extraction and determination of pyrethroid pesticide residues in tobacco. The modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method was applied for preparing samples. In this study, methyl cyanide (MeCN)-saturated salt aqueous was used as the two-phase extraction solvent for the first time, and a vortex shaker was used for the simultaneous shaking and concentration of the analytes. The effects of experimental parameters on extraction and clean-up efficiency were investigated and optimized. The analytes were determined by gas chromatography-mass spectrometry-selected ion monitoring (GC-MS-SIM). The obtained recoveries of the analytes at three different fortification levels were 76.85-114.1% and relative standard deviations (RSDs) were lower than 15.7%. The limits of quantification (LOQs) were from 1.28 to 26.6 μg kg(-1). This method was also applied to the analysis of actual commercial tobacco products and the analytical results were satisfactory.

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

Evaluation of a modified QuEChERS extraction of multiple classes of pesticides from a rice paddy soil by LC-APCI-MS/MS.

PubMed

Caldas, Sergiane S; Bolzan, Cátia M; Cerqueira, Maristela B; Tomasini, Débora; Furlong, Eliana B; Fagundes, Carlos; Primel, Ednei G

2011-11-23

A new method for the determination of clomazone, fipronil, tebuconazole, propiconazole, and azoxystrobin in samples of rice paddy soil is presented. The extraction of the pesticides from soil samples was performed by using a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) method. Some extraction conditions such as salt addition, sample acidification, use of buffer, and cleanup step were evaluated. The optimized method dealt with a single extraction of the compounds under study with acidified acetonitrile, followed by the addition of MgSO(4) and NaCl prior to the final determination by liquid chromatography-atmospheric chemical pressure ionization-tandem mass spectrometry. Validation studies were carried out in soil samples. Recoveries of the spiked samples ranged between 70.3 and 120% with relative standard deviation lower than 18.2%. The limits of quantification were between 10 and 50 μg kg(-1). The method was applied to the analysis of real samples of soils where rice is cultivated.

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.

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.

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

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.

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.

Simultaneous determination of atropine and scopolamine in buckwheat and related products using modified QuEChERS and liquid chromatography tandem mass spectrometry.

PubMed

Chen, Hongping; Marín-Sáez, Jesús; Romero-González, Roberto; Garrido Frenich, Antonia

2017-03-01

A method was developed for the determination of atropine and scopolamine in buckwheat and related products. A modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) extraction procedure was evaluated. Dispersive solid phase extraction (d-SPE) was studied as clean-up step, using graphitized black carbon (GBC) and primary secondary amine (PSA). The extract was diluted with water (50:50, v/v) prior to chromatographic analysis. The method was validated and recoveries (except chia samples spiked at 10μg/kg) ranged from 75% to 92%. Intra and inter-day precision was lower than or equal to 17%. The limit of quantification of atropine and scopolamine was 0.4 and 2μg/kg, respectively. Eight types of samples (buckwheat, wheat, soy, buckwheat flour, buckwheat noodle, amaranth grain, chia seeds and peeled millet) were analyzed. Target compounds were not found above the detection limits of the method, but three transformation products of scopolamine (norscopine, hydroscopolamine and dihydroxyscopolamine) were putative identified in the tested samples using high resolution mass spectrometry (Exactive-Orbitrap). Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

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.

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.

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.

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.

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.

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.

Multi-residue analysis of pharmaceuticals in aqueous environmental samples by online solid-phase extraction-ultra-high-performance liquid chromatography-tandem mass spectrometry: optimisation and matrix effects reduction by quick, easy, cheap, effective, rugged and safe extraction.

PubMed

Bourdat-Deschamps, Marjolaine; Leang, Sokha; Bernet, Nathalie; Daudin, Jean-Jacques; Nélieu, Sylvie

2014-07-04

The aim of this study was to develop and optimise an analytical method for the quantification of a bactericide and 13 pharmaceutical products, including 8 antibiotics (fluoroquinolones, tetracyclines, sulfonamides, macrolide), in various aqueous environmental samples: soil water and aqueous fractions of pig slurry, digested pig slurry and sewage sludge. The analysis was performed by online solid-phase extraction coupled to ultra-high performance liquid chromatography with tandem mass spectrometry (online SPE-UHPLC-MS-MS). The main challenge was to minimize the matrix effects observed in mass spectrometry, mostly due to ion suppression. They depended on the dissolved organic carbon (DOC) content and its origin, and ranged between -22% and +20% and between -38% and -93% of the signal obtained without matrix, in soil water and slurry supernatant, respectively. The very variable levels of these matrix effects suggested DOC content cut-offs above which sample purification was required. These cut-offs depended on compounds, with concentrations ranging from 30 to 290mgC/L for antibiotics (except tylosine) up to 600-6400mgC/L for the most apolar compounds. A modified Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) extraction procedure was therefore optimised using an experimental design methodology, in order to purify samples with high DOC contents. Its performance led to a compromise, allowing fluoroquinolone and tetracycline analysis. The QuEChERS extraction salts consisted therefore of sodium acetate, sodium sulfate instead of magnesium sulfate, and sodium ethylenediaminetetraacetate (EDTA) as a ligand of divalent cations. The modified QuEChERS procedure employed for the extraction of pharmaceuticals in slurry and digested slurry liquid phases reduced the matrix effects for almost all the compounds, with extraction recoveries generally above 75%. The performance characteristics of the method were evaluated in terms of linearity, intra-day and inter-day precision, accuracy and limits of quantification, which reached concentration ranges of 5-270ng/L in soil water and sludge supernatant, and 31-2400ng/L in slurry and digested slurry supernatants, depending on the compounds. The new method was then successfully applied for the determination of the target compounds in environmental samples. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

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.

Multi-residue methods for the determination of over four hundred pesticides in solid and liquid high sucrose content matrices by tandem mass spectrometry coupled with gas and liquid chromatograph.

PubMed

Lozowicka, Bozena; Ilyasova, Gulzhakhan; Kaczynski, Piotr; Jankowska, Magdalena; Rutkowska, Ewa; Hrynko, Izabela; Mojsak, Patrycja; Szabunko, Julia

2016-05-01

For the first time three methods: matrix solid phase dispersion (MSPD), original and modified QuEChERS, with and without clean up step were studied in order to evaluate the extraction efficiency of various classes of pesticides from solid and liquid high sucrose content matrices. Determinations over four hundred pesticides were performed by gas and liquid chromatography with triple quadrupole mass spectrometry (GC/LC/MS/MS) using multiple reaction monitoring. The proposed methods were validated on sugar beets and their technological product beet molasses. In general, the recoveries obtained for the original QuEChERS and MSPD method were lower (<70%) than for the modified QuEChERS without clean up in sugar beet and with clean up in beet molasses. Among these methods, high extraction yields were achieved as recommended in SANCO/12571/2013, with repeatability of 4.4-19.2% and within-laboratory reproducibility of 7.1-18.4% for citrate QuEChERS, whereas greater ruggedness were observed for MSPD. The limit of quantification (LOQ) at (the lowest MRL=0.01mgkg(-1)e.g. for oxamyl()) or below (0.005mgkg(-1)) the regulatory maximum residue level for the pesticides were achieved. The expanded measurement uncertainty was not higher than 30% for all target analytes. Matrix effects were compared and observed for both matrices at both gas and liquid chromatography. The most compounds showed signal enhancement and it was compensated by using matrix-matched calibration and modified QuEChERS characterized lower matrix effects. The confirmation of suitability citrate QuEChERS optimized method was to use for routine testing of several dozen samples determination and residue of epoxiconazole and tebuconazole (both at 0.01mgkg(-1)) in the samples of beet molasses and cyfluthrin (0.06mgkg(-1)) in sugar beet were found. Copyright © 2016 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.

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

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.

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.

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.

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.

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 (

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.

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.

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.

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.

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...

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.

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.

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...

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.

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.

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.

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.

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).

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.

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.

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...

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.

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.

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.

A sensitive and efficient method for routine pesticide multiresidue analysis in bee pollen samples using gas and liquid chromatography coupled to tandem mass spectrometry.

PubMed

Vázquez, P Parrilla; Lozano, A; Uclés, S; Ramos, M M Gómez; Fernández-Alba, A R

2015-12-24

Several clean-up methods were evaluated for 253 pesticides in pollen samples concentrating on efficient clean-up and the highest number of pesticides satisfying the recovery and precision criteria. These were: (a) modified QuEChERS using dSPE with PSA+C18; (b) freeze-out prior to QuEChERS using dSPE with PSA+C18; (c) freeze-out prior to QuEChERS using dSPE with PSA+C18+Z-Sep; and (d) freeze-out followed by QuEChERS using dSPE with PSA+C18 and SPE with Z-Sep. Determinations were made using LC-MS/MS and GC-MS/MS. The modified QuEChERS protocol applying a freeze-out followed by dSPE with PSA+C18 and SPE clean-up with Z-Sep was selected because it provided the highest number of pesticides with mean recoveries in the 70-120% range, as well as relative standard deviations (RSDs) typically below 20% (12.2% on average) and ensured much better removal of co-extracted matrix compounds of paramount importance in routine analysis. Limits of quantification at levels as low as 5μgkg(-1) were obtained for the majority of the pesticides. The proposed methodology was applied to the analysis of 41 pollen bee samples from different areas in Spain. Pesticides considered potentially toxic to bees (DL50<2μg/bee) were detected in some samples with concentrations up to 72.7μgkg(-1), which could negatively affect honeybee health. Copyright © 2015 Elsevier B.V. All rights reserved.

Evaluation of the QuEChERS method for the extraction of pharmaceuticals and personal care products from drinking-water treatment sludge with determination by UPLC-ESI-MS/MS.

PubMed

Cerqueira, Maristela B R; Guilherme, Juliana R; Caldas, Sergiane S; Martins, Manoel L; Zanella, Renato; Primel, Ednei G

2014-07-01

A modified version of the QuEChERS method has been evaluated for the determination of 21 pharmaceuticals and 6 personal care products (PPCPs) in drinking-water sludge samples by employing ultra high liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The performance of the method was evaluated through linearity, recovery, precision (intra-day), method detection and quantification limits (MDL and MQL) and matrix effect. The calibration curves prepared in acetonitrile and in the matrix extract showed a correlation coefficient ranging from 0.98 to 0.99. MQLs values were on the ng g(-1) order of magnitude for most compounds. Recoveries between 50% and 93% were reached with RSDs lower than 10% for most compounds. Matrix effect was almost absent with values lower than 16% for 93% of the compounds. By coupling a quick and simple extraction called QuEChERS with the UPLC-MS/MS analysis, a method that is both selective and sensitive was obtained. This methodology was successfully applied to real samples and caffeine and benzophenone-3 were detected in ng g(-1) levels. Copyright © 2014 Elsevier Ltd. All rights reserved.

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.

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.

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.

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.

Residues and dissipation of kresoxim methyl in apple under field condition.

PubMed

Malhat, Farag; Kamel, Essam; Saber, Ayman; Hassan, Ehab; Youssef, Ahmed; Almaz, Monir; Hassan, Ayman; Fayz, Abd El-Salam

2013-09-01

The dissipation and residual levels of kresoxim methyl in apple under field condition were determined by using HPLC-DAD with QuEChERS method. At fortification levels of 0.05, 0.1, 0.5 and 1.0 mg kg(-1) in apple, it was shown that recoveries were ranged from 91.1% to 96.9% with coefficient variation of the method (CV%) for repeatability ranged from 1.27% to 4.77%. The limit of quantification (LOQ) of the method was 0.05 mg kg(-1). The dissipation rates of kresoxim methyl were described by using first-order kinetics and its half-life, as they are ranged from 4.58 to 4.77 days in apple. The terminal residues of kresoxim methyl were below the FAO/WHO maximum residue limit (MRL, 0.2 mg kg(-1)) in apple when measured 14 days after the final application, which suggested that the use of this fungicide was safe for humans. This study would help in providing the basic information for developing regulation to guard a safe use of kresoxim methyl in apple orchard and to prevent health problem from consumers. Copyright © 2013 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.

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.

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.

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.

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

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.

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.

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.

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.

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.

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.

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.

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.

Development of a simple one-pot extraction method for various drugs and metabolites of forensic interest in blood by modifying the QuEChERS method.

PubMed

Matsuta, Shuntaro; Nakanishi, Keiko; Miki, Akihiro; Zaitsu, Kei; Shima, Noriaki; Kamata, Tooru; Nishioka, Hiroshi; Katagi, Munehiro; Tatsuno, Michiaki; Tsuboi, Kento; Tsuchihashi, Hitoshi; Suzuki, Koichi

2013-10-10

A rapid and convenient extraction method has been developed for the determination of various drugs and metabolites of forensic interest in blood by modifying the dispersive solid-phase extraction method "QuEChERS". The following 13 analytes with various chemical properties were used for the method development and its validation: amphetamine, methamphetamine, zolpidem, the carboxylate-form major metabolite of zolpidem M-1, flunitrazepam, 7-aminoflunitrazepam, phenobarbital, triazolam, α-hydroxytriazolam, brotizolam, α-hydroxybrotizolam, chlorpromazine, and promethazine. The modification of the QuEChERS method includes the use of relatively large amounts of inorganic salts in order to coagulate blood, which allows easy isolation of the organic extract phase. A combination of 100 mg anhydrous magnesium sulfate as a dehydrating agent, 50mg sodium chloride as a salting-out agent, and 500 μL acetonitrile containing 0.2% acetic acid as the organic solvent provided the optimum conditions for processing a 100 μL whole blood sample. The recoveries of the analytes spiked into whole blood at 0.5 μg/mL ranged between 59% and 93%. Although the addition of the graphitized carbon Envi-carb for cleanup decreased the recoveries of zolpidem and its carboxylate-form metabolite M-1, it was very effective in avoiding interferences by cholesterol. The present method can provide a rapid, effective, user-friendly, and relatively hygienic method for the simultaneous extraction of a wide range of drugs and metabolites in whole blood specimens. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

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.

Liquid chromatography-electrospray ionization tandem mass spectrometry and dynamic multiple reaction monitoring method for determining multiple pesticide residues in tomato.

PubMed

Andrade, G C R M; Monteiro, S H; Francisco, J G; Figueiredo, L A; Botelho, R G; Tornisielo, V L

2015-05-15

A quick and sensitive liquid chromatography-electrospray ionization tandem mass spectrometry method, using dynamic multiple reaction monitoring and a 1.8-μm particle size analytical column, was developed to determine 57 pesticides in tomato in a 13-min run. QuEChERS (quick, easy, cheap, effective, rugged, and safe) method for samples preparations and validations was carried out in compliance with EU SANCO guidelines. The method was applied to 58 tomato samples. More than 84% of the compounds investigated showed limits of detection equal to or lower than 5 mg kg(-1). A mild (<20%), medium (20-50%), and strong (>50%) matrix effect was observed for 72%, 25%, and 3% of the pesticides studied, respectively. Eighty-one percent of the pesticides showed recoveries ranging between 70% and 120%. Twelve pesticides were detected in 35 samples, all below the maximum residue levels permitted in the Brazilian legislation; 15 samples exceeded the maximum residue levels established by the EU legislation for methamidophos; and 10 exceeded limits for acephate and four for bromuconazole. Copyright © 2014 Elsevier Ltd. 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

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.

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.

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.

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.

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).

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.

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.

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.

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...

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.

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

Determination of residues of fipronil and its metabolites in cauliflower by using gas chromatography-tandem mass spectrometry.

PubMed

Duhan, Anil; Kumari, Beena; Duhan, Saroj

2015-02-01

Fipronil is a widely used insecticide with a well-described toxicological pathway. Recently it has been widely used in India to control vegetable pests. The present study has been carried out to observe the persistence pattern of fipronil and its metabolites-fipronil sulfone, fipronil sulfide, fipronil desulfinyl in cauliflower and soil so as to know the potential risk if any to consumers and environment. Fipronil was applied @ 56 g a.i. ha(-1). Samples of cauliflower and soil were collected periodically; processed using QuEChERS method and analyzed by GCMS/MS. In cauliflower, residues of fipronil and its metabolites reached below detectable level before 30 days of application whereas in soil about 95% of total fipronil residues got degraded within same time period. Washing and washing followed by cooking or boiling was found effective in reducing residues. A safe waiting period of 15 days is therefore suggested before consuming cauliflower.

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.

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.

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.

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.

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.

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.

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.

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...

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.

Determination of pesticide and phthalate residues in tea by QuEChERS method and their fate in processing.

PubMed

Yadav, Sapna; Rai, Satyajeet; Srivastava, Ashutosh K; Panchal, Smita; Patel, D K; Sharma, V P; Jain, Sudha; Srivastava, L P

2017-01-01

In this study, the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method was applied for the analysis of the multiclass pesticide residues of 12 organochlorines (OCs), 9 organophosphates (OPs), 11 synthetic pyrethroids (SPs), 4 herbicides, 6 phthalates in raw tea (loose tea, branded tea and herbal tea), and tea infusion in 4 different containers (glass cup, earthen cup, plastic bag and disposal cup). In loose tea and branded tea residues, malathion (0.257 and 0.118 mg kg -1 ), cypermethrin (0.065 and 0.030 mg kg -1 ), and fenvalerate (0.032 and 0.030 mg kg -1 ) were detected, respectively. In herbal tea, residues of only cypermethrin (0.053 mg kg -1 ) and fenvalerate (0.045 mg kg -1 ) were detected. Tea infusion samples contained in a plastic bag were found to be contaminated with only dibutyl phthalate (DBP) (0.038 mg kg -1 ). Disposable cup was found to be contaminated with DBP (0.026 mg kg -1 ) and diethyl phthalate (DEP) (0.004 mg kg -1 ). Further, to know the processing behavior of pesticides, the spiked raw tea was subjected to tea infusion at different brewing times (2, 5, 10 min). The analysis demonstrated that dimethoate, dichlorvos, and malathion had shown more than 10 % of translocation at 5 min of brewing time. Further brewing for 10 min revealed the reduction in concentration of pesticides. Leaching of phthalate residues from different plastic containers was also studied at 10, 30, and 60 min. DBP, benzyl butyl phthalate (BzBP), and di-2-(ethylhexyl) phthalate (DEHP) were leached in the tea infusion samples packed in plastic bags. On the other hand, in disposable cups, leaching of DBP, DEP, and dimethyl phthalate were found. The concentration of phthalate residues increased with retention time. Pesticide and phthalate contaminants were recorded at low quantities in few samples only.

Analysis of pesticide residues in strawberries and soils by GC-MS/MS, LC-MS/MS and two-dimensional GC-time-of-flight MS comparing organic and integrated pest management farming.

PubMed

Fernandes, Virgínia C; Lehotay, Steven J; Geis-Asteggiante, Lucía; Kwon, Hyeyoung; Mol, Hans G J; van der Kamp, Henk; Mateus, Nuno; Domingues, Valentina F; Delerue-Matos, Cristina

2014-01-01

This study analysed 22 strawberry and soil samples after their collection over the course of 2 years to compare the residue profiles from organic farming with integrated pest management practices in Portugal. For sample preparation, we used the citrate-buffered version of the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method. We applied three different methods for analysis: (1) 27 pesticides were targeted using LC-MS/MS; (2) 143 were targeted using low pressure GC-tandem mass spectrometry (LP-GC-MS/MS); and (3) more than 600 pesticides were screened in a targeted and untargeted approach using comprehensive, two-dimensional gas chromatography time-of-flight mass spectrometry (GC × GC-TOF-MS). Comparison was made of the analyses using the different methods for the shared samples. The results were similar, thereby providing satisfactory confirmation of both similarly positive and negative findings. No pesticides were found in the organic-farmed samples. In samples from integrated pest management practices, nine pesticides were determined and confirmed to be present, ranging from 2 µg kg(-1) for fluazifop-p-butyl to 50 µg kg(-1) for fenpropathrin. Concentrations of residues in strawberries were less than European maximum residue limits.

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.

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.

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

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.

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.

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.

Benzimidazole Carbamate Residues in Milk: Detection by SPR Biosensor; using a Modified QuEChERS Method for Extraction

USDA-ARS?s Scientific Manuscript database

A surface plasmon resonance (SPR) biosensor screening assay was developed and validated to detect 11 benzimidazole carbamate (BZT) veterinary drug residues in milk. The polyclonal antibody used was raised in sheep against a methyl 5 (6)-[(carboxypentyl)-thio]-2-benzimidazole carbamate protein conjug...

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.

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 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.

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.

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 (

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.

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.

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.

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.

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.

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.

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.

Reduction of carcinogenic polycyclic aromatic hydrocarbons in meat by sugar-smoking and dietary exposure assessment in taiwan.

PubMed

Chen, Shaun; Kao, Tsai Hua; Chen, Chia Ju; Huang, Chung Wei; Chen, Bing Huei

2013-08-07

Polycyclic aromatic hydrocarbons (PAHs) represent an important pollutant in foods and/or the environment. This study aimed to determine the PAH contents in sugar-smoked meat by employing a quick, easy, cheap, effective, rugged, safe (QuEChERS) method combined with a GC-MS technique and assess the dietary exposure of PAHs in Taiwan. Results showed that the longer the sugar-smoking duration, the more the total PAH formation. By sugar-smoking for 6 min, the total PAH contents generated in red meat (33.9 ± 3.1-125.5 ± 9.2 ppb) were higher than in poultry meat (19.1 ± 2.0-28.2 ± 1.2 ppb) and seafood (9.1 ± 1.4-31.8 ± 1.8 ppb), with lamb steak containing the largest amount of total PAHs. Most importantly, the highly carcinogenic benzo[a]pyrene remained undetected in all of the sugar-smoked meat samples. In addition, the cancer risk due to dietary PAH exposure based on total intake of meat in Taiwan was <2 × 10(-7). This outcome demonstrates that sugar-smoking can be adopted to replace the traditional smoking process with wood as smoke source.

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.

[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.

Determination of Acid Herbicides Using Modified QuEChERS with Fast Switching ESI(+)/ESI(-) LC-MS/MS.

PubMed

Sack, Chris; Vonderbrink, John; Smoker, Michael; Smith, Robert E

2015-11-04

A method for the determination of 35 acid herbicides in food matrices was developed, validated, and implemented. It utilizes a modified QuEChERS extraction procedure coupled with quantitation by liquid chromatography tandem mass spectrometry (LC-MS/MS). The acid herbicides analyzed are all organic carboxylic acids, including the older chlorophenoxy acid herbicides such as 2,4-dichlorophenoxyacetic acid (2,4-D), dicamba, 4-chlorophenoxyacetic acid (4-CPA), quinclorac, and many of the newer imidazolinone herbicides such as imazethapyr and imazaquin. In the procedure, 10 mL of water is added to 5 g of sample and then extracted with 1% formic acid in acetonitrile for 1 min. The acetonitrile phase is salted out of the extract by adding sodium chloride and magnesium sulfate, followed by centrifugation. The acetonitrile is diluted 1:1 with water to enable quantitation by LC-MS/MS using fast switching between positive and negative electrospray ionization modes. The average recoveries for all the compounds except aminocyclopyrachlor were 95% with a precision of 8%. The method detection limits for all residues were less than 10 ng/g, and the correlation coefficients for the calibration curves was greater than 0.99 for all but two compounds tested. The method was used successfully for the quantitation of acid herbicides in the FDA's total diet study. The procedure proved to be accurate, precise, linear, sensitive, and rugged.

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.

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.

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.

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.

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.

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.

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.

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.

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

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.

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.

Dissipation kinetics of organophosphorus pesticides in milled toasted maize and wheat flour (gofio) during storage.

PubMed

González-Curbelo, Miguel Ángel; Socas-Rodríguez, Bárbara; Herrero, Miguel; Herrera-Herrera, Antonio V; Hernández-Borges, Javier

2017-08-15

The dissipation/degradation of the pesticides dimethoate, terbufos, disulfoton, and pirimiphos-methyl were evaluated in milled toasted maize and wheat flour (gofio) during three months of storage. Their dissipation kinetics and residual levels were determined, as well as their possible decomposition into some of their main transformation products (disulfoton sulfoxide, terbufos sulfone and disulfoton sulfone). For this purpose, pesticide-free milled toasted maize and wheat samples were spiked with the pesticides, and they were then stored in the darkness at ambient temperature in a closed container to simulate current storage conditions of such packed food. A multiresidue analysis based on the QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method was performed for the simultaneous determination of these pesticides and their metabolites. After three months of storage, the dissipation of residues ranged between 34% (pirimiphos-methyl) and 86% (disulfoton) for maize gofio and between 69% (terbufos) and 92% (disulfoton and pirimiphos-methyl) for wheat gofio. The results demonstrated that the degradation was slower in gofio than in wheat gofio and that none of the selected metabolites were detected in any of the samples. Dissipation curves of all studied pesticides fitted to a first-order decay curve in both types of cereals. Copyright © 2017 Elsevier Ltd. All rights reserved.

Residue level and dissipation of carbendazim in/on pomegranate fruits and soil.

PubMed

Mohapatra, Soudamini; S, Lekha

2016-07-01

Carbendazim is widely used on pomegranate for control of a large number of fungal diseases. Its residue levels in/on pomegranate fruits and soil were evaluated under field conditions. The quick, easy, cheap, effective, rugged, and safe (QuEChERS) method in conjunction with liquid-chromatography mass spectrometry was used for analysis of carbendazim. Recovery of carbendazim was within 78.92-96.28 % and relative standard deviation within 3.8-10.9 % (n = 6). Carbendazim residues on pomegranate fruits dissipated at the half lives of 17.3 and 22.8 days from treatments at 500 and 1000 g active ingredient (a.i.) ha(-1), respectively. Its residues in pomegranate aril were highest on the tenth day and reduced thereafter. The residue level of carbendazim on pomegranate whole fruits from standard dose treatment was less than the EU maximum residue limit (MRL) of 0.1 mg kg(-1) at harvest. The carbendazim residues were

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.

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.

Risk assessment and monitoring of dinotefuran and its metabolites for Chinese consumption of apples.

PubMed

Yu, Weiwei; Huang, Min; Chen, Jiaojiao; Wu, Sizhuo; Zheng, Kunming; Zeng, Song; Zhang, Kankan; Hu, Deyu

2017-09-26

Residues of dinotefuran and its metabolites, 1-methyl-3-(tetrahydro-3-furylmethyl)urea (UF) and 1-methyl-3-(tetrahydro-3-furylmethyl)guanidine (DN), in apple were investigated using a "QuEChERS" (quick, easy, cheap, effective, rugged, safe) pretreatment and liquid chromatography-tandem mass spectrometry. Limits of detection (LODs) and quantification (LOQs) of dinotefuran, UF, and DN in apples were 0.011-0.960 and 0.037-3.200 μg/kg, respectively. The average recoveries of dinotefuran, UF, and DN in apple ranged from 70.0 to 83.6% with relative standard deviations less than 13%. A formulation of 20% water-dispersible dinotefuran granules was sprayed at 1-1.5-fold the recommended dose 3-4 times on apple trees. Total terminal residues of dinotefuran in apple were less than 2 mg/kg, which is the maximum residue limit (MRL) set by Japan. When following the recommended application guidelines, dinotefuran is unlikely to present significant health concerns to the Chinese population because the risk quotient (RQ) is less than 100%. This work could provide guidance for the safe use of dinotefuran and serve as a reference for the establishment of a maximum residue limit of dinotefuran in apple in China.

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.

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.

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.

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.

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.

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

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.

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.

[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 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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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

[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.

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.

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.

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.

Residue behavior and risk assessment of imidacloprid applied on greenhouse-cultivated strawberries under different application conditions.

PubMed

Cang, Tao; Sun, Caixia; Zhao, Hua; Tang, Tao; Zhang, Changpeng; Yu, Ruixian; Wang, Xinquan; Wang, Qiang; Dai, Fen; Zhao, Xueping

2018-02-01

A risk assessment for imidacloprid applied on strawberries under different conditions was performed after residue determination using the quick, cheap, effective, rugged, and safe (QuEChERS) method. The application conditions were varied according to the applied dosage, addition of a plant oil or organosilicon surfactant, water volume, and sprayer type. The degradation dynamics of imidacloprid on strawberries followed first-order kinetics. At applied doses of 30-60 g a.i. ha -1 , the half-lives of imidacloprid were 2.89-3.46, 1.98-3.65, and 2.57-2.77 days after application without a surfactant or with a plant oil or organosilicon surfactant, respectively. For water volumes of 112.5, 225, 450, 675, and 900 L ha -1 , the half-lives of imidacloprid applied in the presence of the plant oil surfactant were 3.30, 7.70, 5.33, 7.70, and 6.30 days, respectively. The half-lives after application with a knapsack mist duster, electric sprayer, and manual sprayer were 2.16, 5.77, and 7.70 days, respectively. The health risk assessment revealed risk quotients less than 1 in all cases, indicating that the application of imidacloprid poses a low health risk to humans after a pre-harvest interval of 10 days under our application conditions. The risk assessment results can provide reference data for setting a reasonable maximum residue limit for imidacloprid on strawberries in China.

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.

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.

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.

Development and in-house validation of a rapid and simple to use ELISA for the detection and measurement of the mycotoxin sterigmatocystin.

PubMed

Oplatowska-Stachowiak, Michalina; Reiring, Claudine; Sajic, Nermin; Haasnoot, Willem; Brabet, Catherine; Campbell, Katrina; Elliott, Christopher T; Salden, Martin

2018-05-01

Sterigmatocystin (STG) is a highly toxic secondary fungal metabolite structurally closely related to the well-known carcinogenic aflatoxins. Its presence has been reported in grains and grain-based products as well as in other foodstuffs like nuts, green coffee beans, spices, beer and cheese. Due to the lack of suitable data on the occurrence of STG, in 2013, the European Food Safety Authority (EFSA) could not characterise its risk for human health and recommended that more data on STG in food and feed needed to be collected. In order to provide a new tool for the specific detection of STG, a competitive enzyme-linked immunosorbent assay (ELISA) was developed, optimised and validated in this study based on a sensitive monoclonal antibody specific to STG with no cross-reactivity with aflatoxins. The sample preparation method for rice, wheat and maize was based on a modified QuEChERS (quick, easy, cheap, effective, rugged and safe) approach. The assay was validated for the detection of STG in rice, wheat and maize in accordance with the guidelines for validation of semi-quantitative screening methods included in Commission Regulation (EU) 519/2014. The screening target concentration (STC) was set at 1.5 μg/kg. The cutoffs for rice, wheat and maize were 1.2, 1.2 and 1.3 μg/kg and the false suspected rates were 0.34, 1.15 and 0.78%, respectively. Good correlation was found between the results obtained by the STG ELISA and LC-MS/MS method for naturally contaminated rice samples. This validated method can be applied as a sensitive and high-throughput screening for the presence of STG in a range of agricultural commodities. Graphical abstract A new enzyme-linked immunosorbent assay based on an antibody specific to sterigmatocystin for the detection of this mycotoxin in corn, wheat and rice.

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.

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.

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.

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.

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.

Atmospheric pressure gas chromatography quadrupole-time-of-flight mass spectrometry for simultaneous determination of fifteen organochlorine pesticides in soil and water.

PubMed

Cheng, Zhipeng; Dong, Fengshou; Xu, Jun; Liu, Xingang; Wu, Xiaohu; Chen, Zenglong; Pan, Xinglu; Zheng, Yongquan

2016-02-26

In this study, the application of atmospheric pressure gas chromatography quadrupole-time-of-flight mass spectrometry (APGC-QTOF-MS) has been investigated for simultaneous determination of fifteen organochlorine pesticides in soil and water. Soft ionization of atmospheric pressure gas chromatography was evaluated by comparing with traditional more energetic electron impact ionization (EI). APGC-QTOF-MS showed a sensitivity enhancement by approximately 7-305 times. The QuEChERs (Quick, Easy, Cheap, Effective, Rugged, and Safe) method was used to pretreat the soil samples and solid phase extraction (SPE) cleanup was used for water samples. Precision, accuracy and stability experiments were undertaken to evaluate the feasibility of the method. The results showed that the mean recoveries for all the pesticides from the soil samples were 70.3-118.9% with 0.4-18.3% intra-day relative standard deviations (RSD) and 1.0-15.6% inter-day RSD at 10, 50 and 500 μg/L levels, while the mean recoveries of water samples were 70.0-118.0% with 1.1-17.8% intra-day RSD and 0.5-12.2% inter-day RSD at 0.1, 0.5 and 1.0 μg/L levels. Excellent linearity (0.9931 ≦ r(2)≤ 0.9999) was obtained for each pesticides in the soil and water matrix calibration curves within the range of 0.01-1.0mg/L. The limits of detection (LOD) for each of the 15 pesticides was less than 3.00 μg/L, while the limit of quantification (LOQ) was less than 9.99 μg/L in soil and water. Furthermore, the developed method was successfully applied to monitor the targeted pesticides in real soil and water samples. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

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.

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.

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.

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.

Depletion study, withdrawal period calculation and bioaccumulation of sulfamethazine in tilapia (Oreochromis niloticus) treated with medicated feed.

PubMed

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

2018-04-01

The residue depletion of sulfamethazine (SMZ) was evaluated in tilapia (Oreochromis niloticus) after 11 days of administration of medicated feed containing SMZ, at the dose of 422 mg/kg body weight (bw). The determination of SMZ in feed and tilapia fillet was carried out using the QuEChERS approach for sample preparation, and high performance liquid chromatography with diode array detector (HPLC-DAD) and ultra-high performance liquid chromatography-quadrupole time-of-flight mass spectrometry (UPLC-QToF-MS) for quantitation, respectively. Both methods were validated based on international and Brazilian guidelines and shown to be suitable for the intended purposes. The withdrawal period to reach the maximum residue level (MRL) of 100 μg/kg, according to the European Union (EU) legislative framework to all substances belonging to the sulfonamide (SA) group (EU, 2010), was 10 days (260 °C-day). After treatment, the maximum level of SMZ accumulation in the tilapia muscle was 1.6 mg/kg. SMZ was shown to be quickly excreted by tilapia. Thus, considering the acceptable daily intake of SMZ established by the Codex Commission (0-0.05 mg/kg bw), and a factor of 5 times the upper amount of fish consumption in Brazil (38 kg/year), this study showed that there is a low risk of adverse effects to consumers. This study offers subsidies not only for the establishment of public policies with regard to the use of veterinary drugs currently not allowed in a country by their legal legislative framework for fish farming, but also to fish producers for the proper handling to ensure safe fish fillets. Copyright © 2018 Elsevier Ltd. All rights reserved.

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.

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.

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.

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.

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.

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. ...

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...

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.

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.

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...

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

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.

Decontamination of chlorantraniliprole residues on cabbage and cauliflower through household processing methods.

PubMed

Kar, Abhijit; Mandal, Kousik; Singh, Balwinder

2012-04-01

A supervised field trial was conducted to study the residues of chlorantraniliprole on cabbage and cauliflower. Three applications of chlorantraniliprole at 10 days interval were made @ 9.25 and 18.50 g a.i. ha(-1). The samples of marketable size heads and curds of cabbage and cauliflower were collected at 0 and 1 day after the last application. QuEChERS sample preparation was used for the determination of chlorantraniliprole residues on cabbage heads and cauliflower curds. The residues of chlorantraniliprole were quantified by high performance liquid chromatography (HPLC) with photo diode array (PDA) detector and confirmed by high performance thin layer chromatography (HPTLC). Washing of cabbage and cauliflower with tap water removed about 17%-40% of chlorantraniliprole residues. However, boiling removed 100% of chlorantraniliprole residues on cabbage and cauliflower in both the cases.

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.

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.

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.

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 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.

Development of an Analytical Procedure for the Determination of Multiclass Compounds for Forensic Veterinary Toxicology.

PubMed

Sell, Bartosz; Sniegocki, Tomasz; Zmudzki, Jan; Posyniak, Andrzej

2018-04-01

Reported here is a new analytical multiclass method based on QuEChERS technique, which has proven to be effective in diagnosing fatal poisoning cases in animals. This method has been developed for the determination of analytes in liver samples comprising rodenticides, carbamate and organophosphorus pesticides, coccidiostats and mycotoxins. The procedure entails addition of acetonitrile and sodium acetate to 2 g of homogenized liver sample. The mixture was shaken intensively and centrifuged for phase separation, which was followed by an organic phase transfer into a tube containing sorbents (PSA and C18) and magnesium sulfate, then it was centrifuged, the supernatant was filtered and analyzed by liquid chromatography tandem mass spectrometry. A validation of the procedure was performed. Repeatability variation coefficients <15% have been achieved for most of the analyzed substances. Analytical conditions allowed for a successful separation of variety of poisons with the typical screening detection limit at ≤10 μg/kg levels. The method was used to investigate more than 100 animals poisoning incidents and proved that is useful to be used in animal forensic toxicology cases.

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.

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.

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.

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.

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.

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.

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.

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.

Effect of paste processing on residue levels of imidacloprid, pyraclostrobin, azoxystrobin and fipronil in winter jujube.

PubMed

Peng, Wei; Zhao, Liuwei; Liu, Fengmao; Xue, Jiaying; Li, Huichen; Shi, Kaiwei

2014-01-01

The changes of imidacloprid, pyraclostrobin, azoxystrobin and fipronil residues were studied to investigate the carryover of pesticide residues in winter jujube during paste processing. A multi-residue analytical method for winter jujube was developed based on the QuEChERS approach. The recoveries for the pesticides were between 87.5% and 116.2%. LODs ranged from 0.002 to 0.1 mg kg(-1). The processing factor (Pf) is defined as the ratio of pesticide residue concentration in the paste to that in winter jujube. Pf was higher than 1 for the removal of extra water, and other steps were generally less than 1, indicating that the whole process resulted in lower pesticide residue levels in paste. Peeling would be the critical step for pesticide removal. Processing factors varied among different pesticides studied. The results are useful to address optimisation of the processing techniques in a manner that leads to considerable pesticide residue reduction.

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.

21 CFR 530.22 - Safe levels and analytical methods for food-producing animals.

Code of Federal Regulations, 2011 CFR

2011-04-01

... analytical method; or (3) Establish a safe level based on other appropriate scientific, technical, or... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Safe levels and analytical methods for food... § 530.22 Safe levels and analytical methods for food-producing animals. (a) FDA may establish a safe...

21 CFR 530.22 - Safe levels and analytical methods for food-producing animals.

Code of Federal Regulations, 2014 CFR

2014-04-01

... analytical method; or (3) Establish a safe level based on other appropriate scientific, technical, or... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Safe levels and analytical methods for food... § 530.22 Safe levels and analytical methods for food-producing animals. (a) FDA may establish a safe...

21 CFR 530.22 - Safe levels and analytical methods for food-producing animals.

Code of Federal Regulations, 2012 CFR

2012-04-01

... analytical method; or (3) Establish a safe level based on other appropriate scientific, technical, or... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Safe levels and analytical methods for food... § 530.22 Safe levels and analytical methods for food-producing animals. (a) FDA may establish a safe...

21 CFR 530.22 - Safe levels and analytical methods for food-producing animals.

Code of Federal Regulations, 2013 CFR

2013-04-01

... analytical method; or (3) Establish a safe level based on other appropriate scientific, technical, or... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Safe levels and analytical methods for food... § 530.22 Safe levels and analytical methods for food-producing animals. (a) FDA may establish a safe...

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.

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

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.

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.

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.

Bioefficacy evaluation and dissipation pattern of nanoformulation versus commercial formulation of pyridalyl in tomato (Solanum lycopersicum).

PubMed

Saini, Priya; Gopal, Madhuban; Kumar, Rajesh; Gogoi, Robin; Srivastava, Chitra

2015-08-01

A study was undertaken to evaluate the decline of the residues of pyridalyl in tomatoes grown in two different cultivation systems: open field (conventional cultivation) and net house (pot experiment). Field experiment was conducted with commercial (10 EC) and nanoformulation of pyridalyl on tomato crop. Tomato plants were subjected to pesticide spray, when fruits were close to ripeness. Fruit samples were taken periodically and cleaned up using QuEChERS methodology, and the residue of pyridalyl was analyzed by ultrahigh-performance liquid chromatography (UHPLC). It dissipated in tomato fruit following the first-order kinetics. In field, average initial deposit of pyridalyl in tomato was observed to be 0.222 and 0.371 μg g(-1) at recommended and double the recommended application rate, respectively, using nanoformulation while it was 0.223 and 0.393 μg g(-1) on using commercial formulation, respectively. The half-life (t1/2) value of nanopyridalyl in tomato fruit was 2.8 and 3.2 days while for commercial formulation, it was 2.5 and 2.6 days for recommended and double the recommended dose, respectively. In India, maximum residue limit (MRL) on tomato has not been fixed for pyridalyl but its residues were always below European MRLs (5 μg g(-1)) on tomato at both application rates. The results of terminal residue showed that pyridalyl residues were below the available MRL. Low residues in tomatoes suggested that this pesticide is safe to use under the recommended dosage. No statistical differences were observed between the cultivation systems in relation to the residue levels of pyridalyl.

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.

Dissipation and residue behavior of emamectin benzoate on apple and cabbage field application.

PubMed

Wang, Lei; Zhao, Pengyue; Zhang, Fengzu; Li, Yanjie; Du, Fengpei; Pan, Canping

2012-04-01

A LC-ESI-MS/MS method with QuEChERS for analysis of emamectin benzoate in cabbage, apple and soil was established. At fortification levels of 0.001, 0.01 and 0.1 mg/kg in cabbage, apple and soil, it was shown that recoveries ranged from 75.9 to 97.0 percent with relative standard deviation (RSD) of 4.4-19.0 percent. The limit of quantification (LOQ) was 0.001 mg/kg for cabbage, apple and soil. The dissipation half-lives of emamectin benzoate in cabbage, apple and soil were 1.34-1.72 day, 2.75-3.09 day and 1.89-4.89 day, respectively. The final residues of emamectin benzoate ranged from 0.001 to 0.052 mg/kg in cabbages, 0.003 to 0.090 mg/kg in apples and 0.001 to 0.089 mg/kg in soils, respectively. Therefore, it would be unlikely to cause health problems if emamectin benzoate was applied according to the use pattern suggested by the manufactures on the label. Crown Copyright © 2011. Published by Elsevier Inc. 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.

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

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.

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.

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.

Simultaneous determination of seventeen mycotoxins residues in Puerariae lobatae radix by liquid chromatography-tandem mass spectrometry.

PubMed

Wang, Shufang; Cheng, Ling; Ji, Shen; Wang, Ke

2014-09-01

This work reported an efficient and accurate liquid chromatography tandem mass spectrometry (LC-MS/MS) method for simultaneous determination of seventeen mycotoxins in Puerariae lobatae radix, a frequently used traditional Chinese medicine (TCM). The effects of four different clean-up methods, including TC-M160, TC-T220, Mycosep 227, and QuEChERS method, on the recoveries of mycotoxins were investigated and compared. Finally, TC-M160 was chosen for better recovery and repeatability for mycotoxins analysis. The analytes were separated on an Agilent ZORBAX SB C18 column (4.6mm×250mm, 5μm particle size), and eluted with a mobile phase consisting of (A) water containing 0.1% formic acid and (B) acetonitrile containing 0.1% formic acid at a flow rate of 0.6mL/min. The separated compounds were detected by a triple quadrupole mass spectrometer operating in positive electrospray ionization with multiple reaction monitoring (MRM) mode. The results of method validation accorded with the requirement of analytical method for mycotoxins in COMMISSION REGULATION (EC) No 401/2006. The developed method was successfully applied for determination of mycotoxins in seventeen batches of Puerariae lobatae radix collected from different provinces of China. Three batches of them were found with contamination of mycotoxins AFB1 at (0.751±0.176)μg/kg, T-2 at (1.10±0.01)μg/kg, and T-2 at (0.853±0.044)μg/kg, respectively. The results demonstrated that the proposed method was suitable for monitoring mycotoxins residues in Puerariae lobatae radix. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

Fail-safe reactivity compensation method for a nuclear reactor

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

Nygaard, Erik T.; Angelo, Peter L.; Aase, Scott B.

The present invention relates generally to the field of compensation methods for nuclear reactors and, in particular to a method for fail-safe reactivity compensation in solution-type nuclear reactors. In one embodiment, the fail-safe reactivity compensation method of the present invention augments other control methods for a nuclear reactor. In still another embodiment, the fail-safe reactivity compensation method of the present invention permits one to control a nuclear reaction in a nuclear reactor through a method that does not rely on moving components into or out of a reactor core, nor does the method of the present invention rely on themore » constant repositioning of control rods within a nuclear reactor in order to maintain a critical state.« less

Risk Assessment of Florists Exposed to Pesticide Residues through Handling of Flowers and Preparing Bouquets.

PubMed

Toumi, Khaoula; Joly, Laure; Vleminckx, Christiane; Schiffers, Bruno

2017-05-13

Flowers are frequently treated with pesticides and, as a result, florists handling daily a large number of flowers can be exposed to pesticide residues. A study was conducted among twenty volunteer florists located in Namur Province and in the Brussels Capital Region of Belgium in order to assess their potential dermal exposure to dislodgeable pesticide residues transferred from flowers to hands. Two pairs of cotton gloves were worn during two consecutive half days while handling flowers and preparing bouquets (from min 2 h to max 3 h/day). The residual pesticide deposits on the glove samples were extracted with a multi-residue Quick Easy Cheap Effective Rugged Safe (QuEChERS) method and analyzed by a combination of gas and liquid chromatography tandem mass spectrometry (GC-MS/MS and LC-MS/MS) by an accredited laboratory. A total of 111 active substances (mainly insecticides and fungicides) were detected, with an average of 37 active substances per sample and a total concentration per glove sample of 22.22 mg/kg. Several predictive levels of contamination were considered to assess the risk. The potential dermal exposures (PDE) of florists were estimated at the average, for different percentiles, and at the maximum concentration of residues in samples. At the PDE P90 and at the PDE MAX (or worst case) values, three and five active substances respectively exceed the Acceptable Operator Exposure Level (AOEL), indicating risk situations. For the systemic exposure (SE), one active substance (clofentezine) exceeds the AOEL at the P90 predictive level. In the worst case, SE MAX (at the maximum concentrations), four active substances (clofentezine, famoxadone, methiocarb, and pyridaben) exceed their respective AOEL values. Among the 14 most frequently detected active substances, two have SE MAX values exceeding the AOEL. Exposure could be particularly critical for clofentezine with an SE MAX value four times higher than the AOEL (393%). The exposure of florists appeared to be an example of a unique professional situation in which workers are exposed regularly to both a very high number of toxic chemicals and rather high concentration levels. Therefore the priority should be to raise the level of awareness among the florists who must change their habits and practices if they want to minimize their exposure.

Risk Assessment of Florists Exposed to Pesticide Residues through Handling of Flowers and Preparing Bouquets

PubMed Central

Toumi, Khaoula; Joly, Laure; Vleminckx, Christiane; Schiffers, Bruno

2017-01-01

Flowers are frequently treated with pesticides and, as a result, florists handling daily a large number of flowers can be exposed to pesticide residues. A study was conducted among twenty volunteer florists located in Namur Province and in the Brussels Capital Region of Belgium in order to assess their potential dermal exposure to dislodgeable pesticide residues transferred from flowers to hands. Two pairs of cotton gloves were worn during two consecutive half days while handling flowers and preparing bouquets (from min 2 h to max 3 h/day). The residual pesticide deposits on the glove samples were extracted with a multi-residue Quick Easy Cheap Effective Rugged Safe (QuEChERS) method and analyzed by a combination of gas and liquid chromatography tandem mass spectrometry (GC-MS/MS and LC-MS/MS) by an accredited laboratory. A total of 111 active substances (mainly insecticides and fungicides) were detected, with an average of 37 active substances per sample and a total concentration per glove sample of 22.22 mg/kg. Several predictive levels of contamination were considered to assess the risk. The potential dermal exposures (PDE) of florists were estimated at the average, for different percentiles, and at the maximum concentration of residues in samples. At the PDE P90 and at the PDEMAX (or worst case) values, three and five active substances respectively exceed the Acceptable Operator Exposure Level (AOEL), indicating risk situations. For the systemic exposure (SE), one active substance (clofentezine) exceeds the AOEL at the P90 predictive level. In the worst case, SEMAX (at the maximum concentrations), four active substances (clofentezine, famoxadone, methiocarb, and pyridaben) exceed their respective AOEL values. Among the 14 most frequently detected active substances, two have SEMAX values exceeding the AOEL. Exposure could be particularly critical for clofentezine with an SEMAX value four times higher than the AOEL (393%). The exposure of florists appeared to be an example of a unique professional situation in which workers are exposed regularly to both a very high number of toxic chemicals and rather high concentration levels. Therefore the priority should be to raise the level of awareness among the florists who must change their habits and practices if they want to minimize their exposure. PMID:28505067

Pesticides in Ichkeul Lake-Bizerta Lagoon Watershed in Tunisia: use, occurrence, and effects on bacteria and free-living marine nematodes.

PubMed

Salem, Fida Ben; Said, Olfa Ben; Aissa, Patricia; Mahmoudi, Ezzeddine; Monperrus, Mathilde; Grunberger, Olivier; Duran, Robert

2016-01-01

This study aimed to identify the most commonly used agricultural pesticides around Ichkeul Lake-Bizerta Lagoon watershed. First survey of pesticide use on agricultural watershed was performed with farmers, Regional Commissioner for Agricultural Development, and pesticide dealers. Then, sediment contamination by pesticides and response of benthic communities (bacteria and free-living marine nematode) were investigated. The analysis of 22 active organochlorine pesticides in sediments was performed according to quick, easy, cheap, effective, rugged, and safe (QuEChERS) method, biodiversity of indigenous bacterial community sediment was determined by terminal restriction fragment length polymorphism (T-RFLP), and free-living marine nematodes were counted. The results of the field survey showed that iodosulfuron, mesosulfuron, 2,4-dichlorophenoxyacetic acid (2,4 D), glyphosate, and fenoxaprops were the most used herbicides, tebuconazole and epoxiconazole the most used fungicides, and deltamethrin the most used insecticide. Sixteen organochlorine pesticide compounds among the 22 examined were detected in sediments up to 2 ppm in Ichkeul Lake, endrin, dieldrin, and hexachlorocyclohexane being the most detected molecules. The most pesticide-contaminated site in the lake presented the higher density of nematode, but when considering all sites, no clear correlation with organochlorine pesticide (OCP) content could be established. The bacterial community structure in the most contaminated site in the lake was characterized by the terminal restriction fragments (T-RFs) 97, 146, 258, 285, and 335 while the most contaminated site in the lagoon was characterized by the T-RFs 54, 263, 315, 403, and 428. Interestingly, T-RFs 38 and 143 were found in the most contaminated sites of both lake and lagoon ecosystems, indicating that they were resistant to OCPs and able to cope with environmental fluctuation of salinity. In contrast, the T-RFs 63, 100, 118, and 381 in the lake and the T-RFs 40, 60, 80, 158, 300, 321, and 357 in the lagoon were sensitive to OCPs. This study highlighted that the intensive use of pesticides in agriculture, through transfer to aquatic ecosystem, may disturb the benthic ecosystem functioning of the protected area. The free-living marine nematodes and bacterial communities represent useful proxy to follow the ecosystem health and its capacity of resilience.

Pesticide Residues on Three Cut Flower Species and Potential Exposure of Florists in Belgium.

PubMed

Toumi, Khaoula; Vleminckx, Christiane; van Loco, Joris; Schiffers, Bruno

2016-09-23

In order to assess the prevalence of pesticide contamination and the risk of florists' exposure when handling cut flowers, sampling and analysis of 90 bouquets of the most commonly sold cut flowers in Belgium (50 bouquets of roses; 20 of gerberas, and 20 of chrysanthemums) were carried out. The bouquets were collected from 50 florists located in the seven largest cities of Belgium (Antwerp, Brussels, Charleroi, Ghent, Leuven, Liege, and Namur) and from five supermarkets located in the different regions. To have a better understanding of the route of exposure and professional practices a questionnaire was also addressed to a group of 25 florists who volunteered to take part in the survey. All florists were interviewed individually when collecting the questionnaire. The residual pesticide deposit values on cut flowers were determined in an accredited laboratory using a multi-residue (QuEChERS Quick Easy Cheap Effective Rugged Safe) method and a combination of gas chromatography (GC) and liquid chormatograhphy (LC) analysis. A total of 107 active substances were detected from all samples; i.e., an average of about 10 active substances per bouquet. The most severely contaminated bouquet accumulated a total concentration of residues up to 97 mg/kg. Results show that roses are the most contaminated cut flowers; with an average of 14 substances detected per sample and a total concentration per rose sample of 26 mg/kg. Some active substances present an acute toxicity (acephate, methiocarb, monocrotophos, methomyl, deltamethrin, etc.) and exposure can generate a direct effect on the nervous system of florists. Nevertheless, fungicides (dodemorph, propamocarb, and procymidone) were the most frequently detected in samples and had the highest maximum concentrations out of all the active substances analysed. Dodemorph was the most frequently detected substance with the highest maximum concentration (41.9 mg/kg) measured in the rose samples. It appears from the survey that, despite being exposed to high deposits of residues, florists usually do not protect themselves from contact with residues even if they spend several hours handling cut flowers and preparing bouquets (from 2 to 6 h/day, depending on the time of year and/or selling periods) daily. Bad habits (eating, drinking, or smoking at work) and absence of personal protective equipment of most florists also increase the risk of contact with pesticide residues.

Pesticide Residues on Three Cut Flower Species and Potential Exposure of Florists in Belgium

PubMed Central

Toumi, Khaoula; Vleminckx, Christiane; van Loco, Joris; Schiffers, Bruno

2016-01-01

In order to assess the prevalence of pesticide contamination and the risk of florists’ exposure when handling cut flowers, sampling and analysis of 90 bouquets of the most commonly sold cut flowers in Belgium (50 bouquets of roses; 20 of gerberas, and 20 of chrysanthemums) were carried out. The bouquets were collected from 50 florists located in the seven largest cities of Belgium (Antwerp, Brussels, Charleroi, Ghent, Leuven, Liege, and Namur) and from five supermarkets located in the different regions. To have a better understanding of the route of exposure and professional practices a questionnaire was also addressed to a group of 25 florists who volunteered to take part in the survey. All florists were interviewed individually when collecting the questionnaire. The residual pesticide deposit values on cut flowers were determined in an accredited laboratory using a multi-residue (QuEChERS Quick Easy Cheap Effective Rugged Safe) method and a combination of gas chromatography (GC) and liquid chormatograhphy (LC) analysis. A total of 107 active substances were detected from all samples; i.e., an average of about 10 active substances per bouquet. The most severely contaminated bouquet accumulated a total concentration of residues up to 97 mg/kg. Results show that roses are the most contaminated cut flowers; with an average of 14 substances detected per sample and a total concentration per rose sample of 26 mg/kg. Some active substances present an acute toxicity (acephate, methiocarb, monocrotophos, methomyl, deltamethrin, etc.) and exposure can generate a direct effect on the nervous system of florists. Nevertheless, fungicides (dodemorph, propamocarb, and procymidone) were the most frequently detected in samples and had the highest maximum concentrations out of all the active substances analysed. Dodemorph was the most frequently detected substance with the highest maximum concentration (41.9 mg/kg) measured in the rose samples. It appears from the survey that, despite being exposed to high deposits of residues, florists usually do not protect themselves from contact with residues even if they spend several hours handling cut flowers and preparing bouquets (from 2 to 6 h/day, depending on the time of year and/or selling periods) daily. Bad habits (eating, drinking, or smoking at work) and absence of personal protective equipment of most florists also increase the risk of contact with pesticide residues. PMID:27669276

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.

Residue analysis and persistence evaluation of fipronil and its metabolites in cotton using high-performance liquid chromatography-tandem mass spectrometry.

PubMed

Wu, Xiaohu; Yu, Yang; Xu, Jun; Dong, Fengshou; Liu, Xingang; Du, Pengqiang; Wei, Dongmei; Zheng, Yongquan

2017-01-01

A simple residue analytical method based on the QuEChERS approach and high-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) detection was developed for the analysis of fipronil and its three metabolites in cottonseed, cotton plant and soil. The average recoveries of four test compounds from all three matrices were 78.6-108.9% at the level of 0.005 to 0.5 mg/kg, with an RSD in the range of 0.6 to 13.7%. The limit of quantification (LOQ) of the four test compounds ranged from 0.005 to 0.01 mg/kg. The results of the residual dynamics experiments showed that fipronil dissipated rapidly in cotton plants and soil and that oxidation and photolysis were the main degradation pathways. Moreover, the bi-exponential models demonstrated a good fit of the measured data for fipronil in cotton plants and soil, with R2 in the range of 0.8989 to 0.9989. Furthermore, a total of 40 samples of cottonseed from Shandong Province were analyzed, and all of the samples were free from the four test compound residues.

Simultaneous determination of organophosphorus pesticides in fruits and vegetables using atmospheric pressure gas chromatography quadrupole-time-of-flight mass spectrometry.

PubMed

Cheng, Zhipeng; Dong, Fengshou; Xu, Jun; Liu, Xingang; Wu, Xiaohu; Chen, Zenglong; Pan, Xinglu; Gan, Jay; Zheng, Yongquan

2017-09-15

This paper describes the application of atmospheric pressure gas chromatography quadrupole-time-of-flight mass spectrometry for the simultaneous determination of organophosphorus pesticides in apple, pear, tomato, cucumber and cabbage. Soft ionization with atmospheric pressure ionization source was compared with traditional electron impact ionization (EI). The sensitivity of GC coupled to atmospheric pressure ionization (APGC) for all the analytes was enhanced by 1.0-8.2 times. The ionization modes with atmospheric pressure ionization source was studied by comparing the charge-transfer and proton-transfer conditions. The optimized QuEChERs method was used to pretreat the samples. The calibration curves were found linear from 10 to 1000μg/L, obtaining correlation coefficients higher than 0.9845. Satisfactory mean recovery values, in the range of 70.0-115.9%, and satisfactory precision, with all RSD r <19.7% and all RSD R values <19.5% at the three fortified concentration levels for all the fifteen OPPs. The results demonstrate the potential of APGC-QTOF-MS for routine quantitative analysis of organophosphorus pesticide in fruits and vegetables. Copyright © 2017 Elsevier Ltd. All rights reserved.

Residue analysis and persistence evaluation of fipronil and its metabolites in cotton using high-performance liquid chromatography-tandem mass spectrometry

PubMed Central

Wu, Xiaohu; Yu, Yang; Xu, Jun; Dong, Fengshou; Liu, Xingang; Du, Pengqiang; Wei, Dongmei; Zheng, Yongquan

2017-01-01

A simple residue analytical method based on the QuEChERS approach and high-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) detection was developed for the analysis of fipronil and its three metabolites in cottonseed, cotton plant and soil. The average recoveries of four test compounds from all three matrices were 78.6–108.9% at the level of 0.005 to 0.5 mg/kg, with an RSD in the range of 0.6 to 13.7%. The limit of quantification (LOQ) of the four test compounds ranged from 0.005 to 0.01 mg/kg. The results of the residual dynamics experiments showed that fipronil dissipated rapidly in cotton plants and soil and that oxidation and photolysis were the main degradation pathways. Moreover, the bi-exponential models demonstrated a good fit of the measured data for fipronil in cotton plants and soil, with R2 in the range of 0.8989 to 0.9989. Furthermore, a total of 40 samples of cottonseed from Shandong Province were analyzed, and all of the samples were free from the four test compound residues. PMID:28291815

[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 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.

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.

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.

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.

Direct detection of Mycobacterium tuberculosis rifampin resistance in bio-safe stained sputum smears.

PubMed

Lavania, Surabhi; Anthwal, Divya; Bhalla, Manpreet; Singh, Nagendra; Haldar, Sagarika; Tyagi, Jaya Sivaswami

2017-01-01

Direct smear microscopy of sputum forms the mainstay of TB diagnosis in resource-limited settings. Stained sputum smear slides can serve as a ready-made resource to transport sputum for molecular drug susceptibility testing. However, bio-safety is a major concern during transport of sputum/stained slides and for laboratory workers engaged in processing Mycobacterium tuberculosis infected sputum specimens. In this study, a bio-safe USP (Universal Sample Processing) concentration-based sputum processing method (Bio-safe method) was assessed on 87 M. tuberculosis culture positive sputum samples. Samples were processed for Ziehl-Neelsen (ZN) smear, liquid culture and DNA isolation. DNA isolated directly from sputum was subjected to an IS6110 PCR assay. Both sputum DNA and DNA extracted from bio-safe ZN concentrated smear slides were subjected to rpoB PCR and simultaneously assessed by DNA sequencing for determining rifampin (RIF) resistance. All sputum samples were rendered sterile by Bio-safe method. Bio-safe smears exhibited a 5% increment in positivity over direct smear with a 14% increment in smear grade status. All samples were positive for IS6110 and rpoB PCR. Thirty four percent samples were RIF resistant by rpoB PCR product sequencing. A 100% concordance (κ value = 1) was obtained between sequencing results derived from bio-safe smear slides and bio-safe sputum. This study demonstrates that Bio-safe method can address safety issues associated with sputum processing, provide an efficient alternative to sample transport in the form of bio-safe stained concentrated smear slides and can also provide information on drug (RIF) resistance by direct DNA sequencing.

Direct detection of Mycobacterium tuberculosis rifampin resistance in bio-safe stained sputum smears

PubMed Central

Lavania, Surabhi; Anthwal, Divya; Bhalla, Manpreet; Singh, Nagendra; Haldar, Sagarika; Tyagi, Jaya Sivaswami

2017-01-01

Direct smear microscopy of sputum forms the mainstay of TB diagnosis in resource-limited settings. Stained sputum smear slides can serve as a ready-made resource to transport sputum for molecular drug susceptibility testing. However, bio-safety is a major concern during transport of sputum/stained slides and for laboratory workers engaged in processing Mycobacterium tuberculosis infected sputum specimens. In this study, a bio-safe USP (Universal Sample Processing) concentration-based sputum processing method (Bio-safe method) was assessed on 87 M. tuberculosis culture positive sputum samples. Samples were processed for Ziehl-Neelsen (ZN) smear, liquid culture and DNA isolation. DNA isolated directly from sputum was subjected to an IS6110 PCR assay. Both sputum DNA and DNA extracted from bio-safe ZN concentrated smear slides were subjected to rpoB PCR and simultaneously assessed by DNA sequencing for determining rifampin (RIF) resistance. All sputum samples were rendered sterile by Bio-safe method. Bio-safe smears exhibited a 5% increment in positivity over direct smear with a 14% increment in smear grade status. All samples were positive for IS6110 and rpoB PCR. Thirty four percent samples were RIF resistant by rpoB PCR product sequencing. A 100% concordance (κ value = 1) was obtained between sequencing results derived from bio-safe smear slides and bio-safe sputum. This study demonstrates that Bio-safe method can address safety issues associated with sputum processing, provide an efficient alternative to sample transport in the form of bio-safe stained concentrated smear slides and can also provide information on drug (RIF) resistance by direct DNA sequencing. PMID:29216262

Quantitative determination of carcinogenic mycotoxins in human and animal biological matrices and animal-derived foods using multi-mycotoxin and analyte-specific high performance liquid chromatography-tandem mass spectrometric methods.

PubMed

Cao, Xiaoqin; Li, Xiaofei; Li, Jian; Niu, Yunhui; Shi, Lu; Fang, Zhenfeng; Zhang, Tao; Ding, Hong

2018-01-15

A sensitive and reliable multi-mycotoxin-based method was developed to identify and quantify several carcinogenic mycotoxins in human blood and urine, as well as edible animal tissues, including muscle and liver tissue from swine and chickens, using liquid chromatography-tandem mass spectrometry (LC-MS/MS). For the toxicokinetic studies with individual mycotoxins, highly sensitive analyte-specific LC-MS/MS methods were developed for rat plasma and urine. Sample purification consisted of a rapid 'dilute and shoot' approach in urine samples, a simple 'dilute, evaporate and shoot' approach in plasma samples and a 'QuEChERS' procedure in edible animal tissues. The multi-mycotoxin and analyte-specific methods were validated in-house: The limits of detection (LOD) for the multi-mycotoxin and analyte-specific methods ranged from 0.02 to 0.41 μg/kg (μg/L) and 0.01 to 0.19 μg/L, respectively, and limits of quantification (LOQ) between 0.10 to 1.02 μg/kg (μg/L) and 0.09 to 0.47 μg/L, respectively. Apparent recoveries of the samples spiked with 0.25 to 4 μg/kg (μg/L) ranged from 60.1% to 109.8% with relative standard deviations below 15%. The methods were successfully applied to real samples. To the best of our knowledge, this is the first study carried out using a small group of patients from the Chinese population with hepatocellular carcinoma to assess their exposure to carcinogenic mycotoxins using biomarkers. Finally, the multi-mycotoxin method is a useful analytical method for assessing exposure to mycotoxins edible in animal tissues. The analyte-specific methods could be useful during toxicokinetic and toxicological studies. Copyright © 2017. Published by Elsevier B.V.

Comparison of Two Educational Methods on Nurses' Adoption of Safe Patient Handling Techniques

ERIC Educational Resources Information Center

Folami, Florence

2010-01-01

Musculoskeletal injuries caused by patient lifting and transfers are a concern to health care workers. The Safe Patient Handling Act calls for all health care organizations to move to mechanical assistance from previous manual methods of transfers. This research analyzed two different educational programs that addressed safe patient handling for…

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.

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.

[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.

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)).

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.

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.

SOME PROBLEMS OF "SAFE DOSE" ESTIMATION

EPA Science Inventory

In environmental carcinogenic risk assessment, the usually defined "safe doses" appear subjective in some sense. n this paper a method of standardizing "safe doses" based on some objective parameters is introduced and a procedure of estimating safe doses under the competing risks...

Dissipation behaviour, residue distribution and dietary risk assessment of tetraconazole and kresoxim-methyl in greenhouse strawberry via RRLC-QqQ-MS/MS technique.

PubMed

Chen, Xiaoxin; Fan, Xueqi; Ma, Yecheng; Hu, Jiye

2018-02-01

20% commercial suspension emulsion (SE) of (8% tetraconazole + 12% kresoxim-methyl), as a pre-registered product in China, was firstly investigated under Chinese greenhouse-field conditions. A MWCNTs-based QuEChERS method for simultaneous determination of tetraconazole and kresoxim-methyl in strawberry was developed and validated via RRLC-QqQ-MS/MS. On basis of this method, the dissipation behaviours, residue distributions and dietary risk probability of these fungicides in strawberry were further investigated for food safety. The dissipations of tetraconazole and kresoxim-methyl followed first-order kinetics with the half-lives of 8.0-18.2 days. The highest residues (HRs) of these fungicides in the supervised trials at the pre-harvest interval (PHI, 3 days) were below 0.8970mgkg -1 . The total national estimated daily intake (NEDI) of tetraconazole and kresoxim-methy in strawberry at the PHI 3day was 0.2784mg and 0.4031mg, respectively, based on Chinese dietary pattern and terminal residue distributions under good agricultural practices (GAP) conditions. The risk quotients (RQs) of tetraconazole and kresoxim-methy at PHI 3 days were below 82.7% and 1.6%, respectively, showing that the evaluated strawberry exhibited an acceptably low dietary risk to consumers. The current study could not only guide reasonable usage of the formulation, but also facilitate the setting of maximum residue limits (MRLs) of tetraconazole in strawberry. Copyright © 2017 Elsevier Inc. All rights reserved.

Patterns of presence and concentration of pesticides in fish and waters of the Júcar River (Eastern Spain).

PubMed

Belenguer, Vicent; Martinez-Capel, Francisco; Masiá, Ana; Picó, Yolanda

2014-01-30

The Júcar River, in a typical Mediterranean Basin, is expected to suffer a decline in water quality and quantity as a consequence of the climate change. This study is focused on the presence and distribution of pesticides in water and fish, using the first extensive optimization and application of the QuEChERS method to determine pesticides in freshwater fish. Majority pesticides in water - in terms of presence and concentration - were dichlofenthion, chlorfenvinphos, imazalil, pyriproxyfen and prochloraz (associated with a frequent use in farming activities), as well as buprofezin, chlorpyriphos and hexythiazox. In fish, the main compounds were azinphos-ethyl, chlorpyriphos, diazinon, dimethoate and ethion. The analysis of bio-concentration in fish indicated differences by species. The maximum average concentration was detected in European eel (a critically endangered fish species). The wide presence of pesticides in water and fish suggests potential severe effects on fish populations and other biota in future scenarios of climate change, in a river basin with several endemic and endangered fish species. The potential effects of pesticides in combination with multiple stressors require further research to prioritize the management of specific chemicals and suggest effective restoration actions at the basin scale. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

26 CFR 1.401(a)(4)-0 - Table of contents.

Code of Federal Regulations, 2010 CFR

2010-04-01

...) Composition-of-work-force method. (3) Minimum-benefit method. (4) Grandfather rules for plans in existence on... allocation rates. (3) Safe harbor testing method for cash balance plans. (d) Safe-harbor testing method for...-crediting period. (e) Family aggregation rules. [Reserved] (f) Governmental plans. [Reserved] (g) Corrective...

Monitoring Moving Queries inside a Safe Region

PubMed Central

Al-Khalidi, Haidar; Taniar, David; Alamri, Sultan

2014-01-01

With mobile moving range queries, there is a need to recalculate the relevant surrounding objects of interest whenever the query moves. Therefore, monitoring the moving query is very costly. The safe region is one method that has been proposed to minimise the communication and computation cost of continuously monitoring a moving range query. Inside the safe region the set of objects of interest to the query do not change; thus there is no need to update the query while it is inside its safe region. However, when the query leaves its safe region the mobile device has to reevaluate the query, necessitating communication with the server. Knowing when and where the mobile device will leave a safe region is widely known as a difficult problem. To solve this problem, we propose a novel method to monitor the position of the query over time using a linear function based on the direction of the query obtained by periodic monitoring of its position. Periodic monitoring ensures that the query is aware of its location all the time. This method reduces the costs associated with communications in client-server architecture. Computational results show that our method is successful in handling moving query patterns. PMID:24696652

Removing Hair Safely

MedlinePlus

... For Consumers Home For Consumers Consumer Updates Removing Hair Safely Share Tweet Linkedin Pin it More sharing ... related to common methods of hair removal. Laser Hair Removal In this method, a laser destroys hair ...

Safe semi-supervised learning based on weighted likelihood.

PubMed

Kawakita, Masanori; Takeuchi, Jun'ichi

2014-05-01

We are interested in developing a safe semi-supervised learning that works in any situation. Semi-supervised learning postulates that n(') unlabeled data are available in addition to n labeled data. However, almost all of the previous semi-supervised methods require additional assumptions (not only unlabeled data) to make improvements on supervised learning. If such assumptions are not met, then the methods possibly perform worse than supervised learning. Sokolovska, Cappé, and Yvon (2008) proposed a semi-supervised method based on a weighted likelihood approach. They proved that this method asymptotically never performs worse than supervised learning (i.e., it is safe) without any assumption. Their method is attractive because it is easy to implement and is potentially general. Moreover, it is deeply related to a certain statistical paradox. However, the method of Sokolovska et al. (2008) assumes a very limited situation, i.e., classification, discrete covariates, n(')→∞ and a maximum likelihood estimator. In this paper, we extend their method by modifying the weight. We prove that our proposal is safe in a significantly wide range of situations as long as n≤n('). Further, we give a geometrical interpretation of the proof of safety through the relationship with the above-mentioned statistical paradox. Finally, we show that the above proposal is asymptotically safe even when n(')

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.

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.

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.

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

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.

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.

Weak form implementation of the semi-analytical finite element (SAFE) method for a variety of elastodynamic waveguides

NASA Astrophysics Data System (ADS)

Hakoda, Christopher; Lissenden, Clifford; Rose, Joseph L.

2018-04-01

Dispersion curves are essential to any guided wave NDE project. The Semi-Analytical Finite Element (SAFE) method has significantly increased the ease by which these curves can be calculated. However, due to misconceptions regarding theory and fragmentation based on different finite-element software, the theory has stagnated, and adoption by researchers who are new to the field has been slow. This paper focuses on the relationship between the SAFE formulation and finite element theory, and the implementation of the SAFE method in a weak form for plates, pipes, layered waveguides/composites, curved waveguides, and arbitrary cross-sections is shown. The benefits of the weak form are briefly described, as is implementation in open-source and commercial finite element software.

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.

Validation and application of a multiresidue method based on liquid chromatography-tandem mass spectrometry for evaluating the plant uptake of 74 microcontaminants in crops irrigated with treated municipal wastewater.

PubMed

Martínez-Piernas, A B; Polo-López, M I; Fernández-Ibáñez, P; Agüera, A

2018-01-26

Reuse of treated wastewater for agricultural purposes can mitigate water stress in some regions where the lack of water is an extended problem. However, the environmental long-term consequences of this practice are still unknown. It is demonstrated that using reclaimed water for irrigation lead to accumulation and translocation of some microcontaminants (MCs) in soil and crops. However, so far, only a small group of contaminants has been investigated. This study aims to develop and validate a simple and efficient multiresidue method based on QuEChERs (Quick, Easy, Cheap, Effective and Rugged) extraction coupled to liquid chromatography tandem mass spectrometry (LC-MS/MS). The novelty of the study relays in the large number of MCs analyzed (74), some of them not previously investigated, in three commodities (lettuce, radish and strawberry). Optimized conditions yielded good results for the three commodities under study. Up to 84% of the compounds were recovered within a 70-120% range, with good repeatability (relative standard deviations below 20% in most cases). Method detection (MDLs) and quantification limits (MQLs) ranged from 0.01 to 2 ng/g. The proposed method was successfully applied to assess the potential uptake of MCs by lettuce and radish crops irrigated with wastewater under controlled conditions for 3 and 1.5 months, respectively. 12 compounds were detected in the crops with concentrations ranging from 0.03 to 57.6 ng/g. N-Formyl-4-aminoantipyrine (4FAA) was the most concentrated compound. The application of this method demonstrated for the first time the accumulation of 5 contaminants of emerging concern (CECs) not previously reported: 4FAA, N-Acetyl-4-aminoantipyrine (4AAA), hydrochlorothiazide, mepivacaine and venlafaxine. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

Digital computer operation of a nuclear reactor

DOEpatents

Colley, R.W.

1982-06-29

A method is described for the safe operation of a complex system such as a nuclear reactor using a digital computer. The computer is supplied with a data base containing a list of the safe state of the reactor and a list of operating instructions for achieving a safe state when the actual state of the reactor does not correspond to a listed safe state, the computer selects operating instructions to return the reactor to a safe state.

Digital computer operation of a nuclear reactor

DOEpatents

Colley, Robert W.

1984-01-01

A method is described for the safe operation of a complex system such as a nuclear reactor using a digital computer. The computer is supplied with a data base containing a list of the safe state of the reactor and a list of operating instructions for achieving a safe state when the actual state of the reactor does not correspond to a listed safe state, the computer selects operating instructions to return the reactor to a safe state.

Fracture control methods for space vehicles. Volume 1: Fracture control design methods. [for space shuttle configuration planning

NASA Technical Reports Server (NTRS)

Liu, A. F.

1974-01-01

A systematic approach for applying methods for fracture control in the structural components of space vehicles consists of four major steps. The first step is to define the primary load-carrying structural elements and the type of load, environment, and design stress levels acting upon them. The second step is to identify the potential fracture-critical parts by means of a selection logic flow diagram. The third step is to evaluate the safe-life and fail-safe capabilities of the specified part. The last step in the sequence is to apply the control procedures that will prevent damage to the fracture-critical parts. The fracture control methods discussed include fatigue design and analysis methods, methods for preventing crack-like defects, fracture mechanics analysis methods, and nondestructive evaluation methods. An example problem is presented for evaluation of the safe-crack-growth capability of the space shuttle crew compartment skin structure.

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

The Safe Yield and Climatic Variability: Implications for Groundwater Management.

PubMed

Loáiciga, Hugo A

2017-05-01

Methods for calculating the safe yield are evaluated in this paper using a high-quality and long historical data set of groundwater recharge, discharge, extraction, and precipitation in a karst aquifer. Consideration is given to the role that climatic variability has on the determination of a climatically representative period with which to evaluate the safe yield. The methods employed to estimate the safe yield are consistent with its definition as a long-term average extraction rate that avoids adverse impacts on groundwater. The safe yield is a useful baseline for groundwater planning; yet, it is herein shown that it is not an operational rule that works well under all climatic conditions. This paper shows that due to the nature of dynamic groundwater processes it may be most appropriate to use an adaptive groundwater management strategy that links groundwater extraction rates to groundwater discharge rates, thus achieving a safe yield that represents an estimated long-term sustainable yield. An example of the calculation of the safe yield of the Edwards Aquifer (Texas) demonstrates that it is about one-half of the average annual recharge. © 2016, National Ground Water Association.

Pregnancy termination in Matlab, Bangladesh: trends and correlates of use of safer and less-safe methods.

PubMed

DaVanzo, Julie; Rahman, Mizanur

2014-09-01

Menstrual regulation (MR), a relatively safe form of pregnancy termination, is legal in Bangladesh during the early stages of pregnancy. However, little is known about the factors associated with whether women who terminate pregnancies choose this method or a less-safe one. Data from the Matlab Demographic Surveillance System on 122,691 pregnancies-5,221 (4.3%) of which were terminated-were used to examine trends between 1989 and 2008 in termination and in use of safer methods (MR or dilation and curettage) and less-safe (all other) methods of pregnancy termination. Logistic and multinomial logistic regressions were used to assess factors associated with whether women terminate pregnancies and whether they use safer methods. Sixty-seven percent of pregnancy terminations were by safer methods and 33% by less-safe means. The proportion of pregnancies that were terminated increased between 1989 and 2008; this increase was entirely due to increased use of safer methods. Women younger than 18 and those 25 or older were more likely than women aged 20-24 to terminate their pregnancies (odds ratios ranged from 1.5 among women aged 16-17 or 25-29 to 26.1 among those aged 45 or older). Among women who terminated their pregnancies, those aged 25-44 were more likely than those aged 20-24 to use a safer method. Compared with women who had no formal education, those with some education were more likely to terminate their pregnancies and to do so using safer methods. A growing proportion of pregnancies in Matlab are terminated, and these terminations are increasingly done using safer methods.

Recovery of Trace and Heavy Metals from Coal Combustion Residues for Reuse and Safe Disposal: A Review

NASA Astrophysics Data System (ADS)

Kumar, Ashvani; Samadder, Sukha Ranjan; Elumalai, Suresh Pandian

2016-09-01

The safe disposal of coal combustion residues (CCRs) will remain a major public issue as long as coal is used as a fuel for energy production. Both dry and wet disposal methods of CCRs create serious environmental problems. The dry disposal method creates air pollution initially, and the wet disposal method creates water pollution as a result of the presence of trace and heavy metals. These leached heavy metals from fly ash may become more hazardous when they form toxic compounds such as arsenic sulfite (As2S3) and lead nitrate (N2O6Pb). The available studies on trace and heavy metals present in CCRs cannot ensure environmentally safe utilization. In this work, a novel approach has been offered for the retrieval of trace and heavy metals from CCRs. If the proposed method becomes successful, then the recovered trace and heavy metals may become a resource and environmentally safe use of CCRs may be possible.

Longitudinal study of pesticide residue levels in human milk from Western Australia during 12 months of lactation: Exposure assessment for infants

PubMed Central

Du, Jian; Gridneva, Zoya; Gay, Melvin C. L.; Lai, Ching T.; Trengove, Robert D.; Hartmann, Peter E.; Geddes, Donna T.

2016-01-01

The presence of pesticides in human milk (HM) is of great concern due to the potential health effects for the breastfed infant. To determine the relationships between HM pesticides and infant growth and development, a longitudinal study was conducted. HM samples (n = 99) from 16 mothers were collected at 2, 5, 9 and 12 months of lactation. A validated QuEChERS method and Gas chromatography-tandem mass spectrometry (GC-MS/MS) were used for the analysis of 88 pesticides in HM. Only p,p’-DDE, p,p’-DDT and β-HCH were detected with a mean concentration (±SD) of 52.25 ± 49.88 ng/g fat, 27.67 ± 20.96 ng/g fat and 48.00 ± 22.46 ng/g fat respectively. The concentrations of the detected pesticides decreased significantly throughout the first year of lactation. No significant relationships between HM p,p’-DDE and infant growth outcomes: weight, length, head circumference and percentage fat mass were detected. The actual daily intake (ADI) of total DDTs in this cohort was 14–1000 times lower than the threshold reference and significantly lower than the estimated daily intake (EDI). Further, the ADI decreased significantly throughout the first 12 months of lactation. PMID:27924835

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.

Longitudinal study of pesticide residue levels in human milk from Western Australia during 12 months of lactation: Exposure assessment for infants

NASA Astrophysics Data System (ADS)

Du, Jian; Gridneva, Zoya; Gay, Melvin C. L.; Lai, Ching T.; Trengove, Robert D.; Hartmann, Peter E.; Geddes, Donna T.

2016-12-01

The presence of pesticides in human milk (HM) is of great concern due to the potential health effects for the breastfed infant. To determine the relationships between HM pesticides and infant growth and development, a longitudinal study was conducted. HM samples (n = 99) from 16 mothers were collected at 2, 5, 9 and 12 months of lactation. A validated QuEChERS method and Gas chromatography-tandem mass spectrometry (GC-MS/MS) were used for the analysis of 88 pesticides in HM. Only p,p’-DDE, p,p’-DDT and β-HCH were detected with a mean concentration (±SD) of 52.25 ± 49.88 ng/g fat, 27.67 ± 20.96 ng/g fat and 48.00 ± 22.46 ng/g fat respectively. The concentrations of the detected pesticides decreased significantly throughout the first year of lactation. No significant relationships between HM p,p’-DDE and infant growth outcomes: weight, length, head circumference and percentage fat mass were detected. The actual daily intake (ADI) of total DDTs in this cohort was 14-1000 times lower than the threshold reference and significantly lower than the estimated daily intake (EDI). Further, the ADI decreased significantly throughout the first 12 months of lactation.

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.

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.

Subscale Validation of the Subsurface Active Filtration of Exhaust (SAFE) Approach to the NTP Ground Testing

NASA Technical Reports Server (NTRS)

Marshall, William M.; Borowski, Stanley K.; Bulman, Mel; Joyner, Russell; Martin, Charles R.

2015-01-01

Nuclear thermal propulsion (NTP) has been recognized as an enabling technology for missions to Mars and beyond. However, one of the key challenges of developing a nuclear thermal rocket is conducting verification and development tests on the ground. A number of ground test options are presented, with the Sub-surface Active Filtration of Exhaust (SAFE) method identified as a preferred path forward for the NTP program. The SAFE concept utilizes the natural soil characteristics present at the Nevada National Security Site to provide a natural filter for nuclear rocket exhaust during ground testing. A validation method of the SAFE concept is presented, utilizing a non-nuclear sub-scale hydrogen/oxygen rocket seeded with detectible radioisotopes. Additionally, some alternative ground test concepts, based upon the SAFE concept, are presented. Finally, an overview of the ongoing discussions of developing a ground test campaign are presented.

Overview of paint removal methods

NASA Astrophysics Data System (ADS)

Foster, Terry

1995-04-01

With the introduction of strict environmental regulations governing the use and disposal of methylene chloride and phenols, major components of chemical paint strippers, there have been many new environmentally safe and effective methods of paint removal developed. The new methods developed for removing coatings from aircraft and aircraft components include: mechanical methods using abrasive media such as plastic, wheat starch, walnut shells, ice and dry ice, environmentally safe chemical strippers and paint softeners, and optical methods such as lasers and flash lamps. Each method has its advantages and disadvantages, and some have unique applications. For example, mechanical and abrasive methods can damage sensitive surfaces such as composite materials and strict control of blast parameters and conditions are required. Optical methods can be slow, leaving paint residues, and chemical methods may not remove all of the coating or require special coating formulations to be effective. As an introduction to environmentally safe and effective methods of paint removal, this paper is an overview of the various methods available. The purpose of this overview is to introduce the various paint removal methods available.

Development of a multiple-class analytical method based on the use of synthetic matrices for the simultaneous determination of commonly used commercial surfactants in wastewater by liquid chromatography-tandem mass spectrometry.

PubMed

Alexandre, Bergé; Barbara, Giroud; Laure, Wiest; Bruno, Domenjoud; Adriana, Gonzalez-Ospina; Emmanuelle, Vulliet

2016-06-10

Discharges of surfactants from wastewater treatment plants are often considered as the principal vector of pollution into the environment. The analysis of complex matrices, such as urban wastewater, suspended solids and biological sludge requires careful preparation of the sample to obtain a sensitive, selective and reproducible analysis. A simple, fast, effective and multi-residue method based on the SPE (water) and QuEChERS (solid matrices) approaches using synthetic matrices for validation and quantification, has been developed for the determination of 16 surfactants in wastewater, suspended solids and biological sludge. This work resulted in an innovative method that was validated to detect and assess several classes of surfactants such as quaternary ammonium compounds, betaïns, alkylphenols and their ethoxylated or sulfated derivatives in urban wastewater and solid matrices. The optimised extraction method exhibited recoveries comprised between 83% and 120% for all the tested compounds in the dissolved matrix and between 50% and 109% for particulate matrix. The limits of quantification of all compounds were comprised between 0.1 and 1.0μg/L for dissolved matrix and between 2 and 1000ng/g (dry weight) in particulate matrix. Linearity was assessed for all compounds within the [LOQ-250LOQ] range. Confidence intervals were also computed in real matrices with less than 15% margin of error for all studied surfactants. This work has confirmed, first and foremost, that surfactants are indeed highly concentrated in urban wastewater. As expected, linear alkylbenzene sulfonates were present at significant concentrations (up to 1-2mg/L). In addition, although biological processing results in significant removal of the total pollution, the residual concentrations at output of WWTP remain significant (up to 100μg/L). Copyright © 2016 Elsevier B.V. All rights reserved.

Method for making a low density polyethylene waste form for safe disposal of low level radioactive material

DOEpatents

Colombo, P.; Kalb, P.D.

1984-06-05

In the method of the invention low density polyethylene pellets are mixed in a predetermined ratio with radioactive particulate material, then the mixture is fed through a screw-type extruder that melts the low density polyethylene under a predetermined pressure and temperature to form a homogeneous matrix that is extruded and separated into solid monolithic waste forms. The solid waste forms are adapted to be safely handled, stored for a short time, and safely disposed of in approved depositories.

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.

Image color reduction method for color-defective observers using a color palette composed of 20 particular colors

NASA Astrophysics Data System (ADS)

Sakamoto, Takashi

2015-01-01

This study describes a color enhancement method that uses a color palette especially designed for protan and deutan defects, commonly known as red-green color blindness. The proposed color reduction method is based on a simple color mapping. Complicated computation and image processing are not required by using the proposed method, and the method can replace protan and deutan confusion (p/d-confusion) colors with protan and deutan safe (p/d-safe) colors. Color palettes for protan and deutan defects proposed by previous studies are composed of few p/d-safe colors. Thus, the colors contained in these palettes are insufficient for replacing colors in photographs. Recently, Ito et al. proposed a p/dsafe color palette composed of 20 particular colors. The author demonstrated that their p/d-safe color palette could be applied to image color reduction in photographs as a means to replace p/d-confusion colors. This study describes the results of the proposed color reduction in photographs that include typical p/d-confusion colors, which can be replaced. After the reduction process is completed, color-defective observers can distinguish these confusion colors.

'Safe passage': pregnant Iranian Kurdish women's choice of childbirth method.

PubMed

Shahoei, Roonak; Riji, Haliza Mohd; Saeedi, Zhila Abed

2011-10-01

This article is a report of a grounded theory study of the influence of emotions on women's selection of a method of childbirth. There is substantial evidence to indicate that a pregnant woman's emotions play an important role in the decision-making process of selecting a child delivery method. Despite this, however, there is a notable lack of research about the relationship between pregnant women's emotions and their choice of a childbirth method in developing countries. A qualitative study using the grounded theory approach was conducted. The data were collected from 22 Iranian Kurdish pregnant women in their third trimester using semi-structured interviews. Concurrent data collection and analysis took place between 2008 and 2009. A cumulative process of theoretical sampling and constant comparison was used to identify concepts and then expand, validate, and clarify them. The substantive grounded theory that was identified from data analysis was 'safe passage'. 'Safe passage' involved five phases that were not mutually exclusive in their occurrence. The five phases of the 'safe passage' theory that were identified from the data analysis were: 'safety of baby', 'fear', 'previous experience', 'social support' and 'faith'. The goal of 'safe passage' was to achieve a healthy delivery and to ensure the health of the newborn. 'Safe passage' was a process used to determine how the emotions of pregnant Iranian Kurdish women influenced their choice of the mode of child delivery. More research is needed in this field to develop a body of knowledge beneficial to midwifery education and practice. © 2011 Blackwell Publishing Ltd.

METHOD OF CONDUCTING A PERSON BETWEEN A SAFE REGION AND A DANGEROUS REGION

DOEpatents

Moulthrop, H.A.

1957-11-12

This invention relates to a method for conducting a person between a safe region and a dangerous or con taminated region so that he may work in the dangerous region without risk to himself or the hinderance of an attached tube, and without danger of contaminating the safe region. A safely suit in which a person is to work is connected by a thermoplastic tube, turned partially inside out, to a hole in the wall separating the dangerous region. The tube is sealed by pressure and separated into two parts at the seal, whereupon the person in the suit may move around freely in the dangerous area. When the person desires to exit the dangerous region, the parts of the tube are resealed, removing a portion of the tube at the seal, and the person leaves the hole whcre he entered, seals the tube to close the hole, and cuts his suit free from the tube. Bands of masking tape inside and outside of the tube at predetermined points simplify the pressure sealing of the tube at the desired points. This patent provides a simple, safe and economical method of freely working in a dangerous region.

Safe sex self-efficacy and safe sex practice in a Southern United States College

PubMed Central

Addoh, Ovuokerie; Sng, Eveleen; Loprinzi, Paul D.

2017-01-01

Background: The purpose of this study was to assess the association between safe sex self-efficacy and safe-sex practice in a Southern college setting. Methods: Multivariable logistic regression models were used to examine the association between safe sex self-efficacy in four domains (mechanics, partner disapproval, assertiveness, intoxicants) and safe sex practice (outcome variable). Results: For every 1-unit increase in the composite condom use self-efficacy score, there was an 8% increase in the odds of being beyond the median safe-sex practice score (odds ration [OR]: 1.08, 95% CI: 1.02-1.15). Additionally, for every 1-unit increase in intoxicants self-efficacy score, there was a 31% increase in the odds of being beyond the median safe-sex practice score (OR: 1.31, 95% CI: 1.08-1.58). Conclusion: A greater degree of safe-sex self-efficacy is associated with increased odds of safe-sex practice. These findings are informative for the development of targeted approaches to foster safe-sex behavior in Southern US colleges. PMID:28326287

50 CFR 216.91 - Dolphin-safe labeling standards.

Code of Federal Regulations, 2013 CFR

2013-10-01

... MAMMALS Dolphin Safe Tuna Labeling § 216.91 Dolphin-safe labeling standards. (a) It is a violation of..., distributor, or seller of any tuna products that are exported from or offered for sale in the United States to... suggests that the tuna contained in the products were harvested using a method of fishing that is not...

50 CFR 216.91 - Dolphin-safe labeling standards.

Code of Federal Regulations, 2010 CFR

2010-10-01

... MAMMALS Dolphin Safe Tuna Labeling § 216.91 Dolphin-safe labeling standards. (a) It is a violation of..., distributor, or seller of any tuna products that are exported from or offered for sale in the United States to... suggests that the tuna contained in the products were harvested using a method of fishing that is not...

50 CFR 216.91 - Dolphin-safe labeling standards.

Code of Federal Regulations, 2012 CFR

2012-10-01

... MAMMALS Dolphin Safe Tuna Labeling § 216.91 Dolphin-safe labeling standards. (a) It is a violation of..., distributor, or seller of any tuna products that are exported from or offered for sale in the United States to... suggests that the tuna contained in the products were harvested using a method of fishing that is not...

50 CFR 216.91 - Dolphin-safe labeling standards.

Code of Federal Regulations, 2014 CFR

2014-10-01

... MAMMALS Dolphin Safe Tuna Labeling § 216.91 Dolphin-safe labeling standards. (a) It is a violation of..., distributor, or seller of any tuna products that are exported from or offered for sale in the United States to... suggests that the tuna contained in the products were harvested using a method of fishing that is not...

50 CFR 216.91 - Dolphin-safe labeling standards.

Code of Federal Regulations, 2011 CFR

2011-10-01

... MAMMALS Dolphin Safe Tuna Labeling § 216.91 Dolphin-safe labeling standards. (a) It is a violation of..., distributor, or seller of any tuna products that are exported from or offered for sale in the United States to... suggests that the tuna contained in the products were harvested using a method of fishing that is not...

Water disinfection in the mountains - state of the art recommendation paper of the Union Internationale des Associations d'Alpinisme Medical Commission.

PubMed

Küpper, Thomas E A H; Schöffl, Volker; Milledge, Jim S

2009-01-01

This paper provides the official recommendation of the Union Internationale des Associations d'Alpinisme (UIAA) Medical Commission to manage the problem of safe drinking water. The recommendation was accepted and authorized for publication by the Medical Commission during their annual meeting at Treplice, Tzechia, 2008. Safe water is essential for mountaineers worldwide in order to balance challenges associated with high altitude dehydration. The paper summarizes the advantages and disadvantages of several procedures used to procure safe drinking water in the mountains or at high altitude. Limitations or critical details, which may cause failure of the methods are mentioned systematically. We differentiate between "conventional" methods, which should be preferred because they produce safe water and "improvisation". The latter does not produce safe water but may be used if conventional methods are not available for any reason. They decrease the concentration of pathogenic microorganisms and by this they reduce the risk of enteral infection. Water filtration using a ceramic filter system or chemical disinfection is recommended as a standard method. Boiling water should be avoided because it is too fuel consuming and has the potential to increase deforestation. Generally, with regard to infections by water or food, all mountaineers should be vaccinated against hepatitis A and poliomyelitis in regions where they may be at-risk.

Helping Clinicians Prevent Pregnancy among Sexually Active Adolescents: U.S. Medical Eligibility Criteria for Contraceptive Use and U.S. Selected Practice Recommendations for Contraceptive Use.

PubMed

Godfrey, Emily M

2015-08-01

The United States has made substantial progress in reducing teenage birth rates in recent decades, but rates remain high. Teen pregnancy can increase the risk of poor health outcomes and lead to decreased educational attainment, increased poverty, and welfare use, as well as increased cost to taxpayers. One of the most effective ways to prevent teenage pregnancy is through the use of effective birth control methods. The Centers for Disease Control (CDC) and Prevention has made the prevention of teenage pregnancy 1 of its 10 winnable battles. The CDC has released 2 evidence-based clinical guideline documents regarding contraceptive use for adolescents and adults. The first guideline, US Medical Eligibility Criteria for Contraceptive Use, 2010, helps clinicians recognize when a contraceptive method may not be safe to use for a particular adolescent but also when not to withhold a contraceptive method that is safe to use. The second document, US Selected Practice Recommendations for Contraceptive Use, 2013, provides guidance for how to use contraceptive methods safely and effectively once they are deemed safe. Health care providers are encouraged to use these documents to provide safe and effective contraceptive care to patients seeking family planning, including adolescents. Copyright © 2015 North American Society for Pediatric and Adolescent Gynecology. All rights reserved.

21 CFR 530.22 - Safe levels and analytical methods for food-producing animals.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Safe levels and analytical methods for food-producing animals. 530.22 Section 530.22 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH... ANIMALS Specific Provisions Relating to Extralabel Use of Animal and Human Drugs in Food-Producing Animals...

A Mixed-Method Exploration of Functioning in Safe Schools/Healthy Students Partnerships

ERIC Educational Resources Information Center

Merrill, Marina L.; Taylor, Nicole L.; Martin, Alison J.; Maxim, Lauren A.; D'Ambrosio, Ryan; Gabriel, Roy M.; Wendt, Staci J.; Mannix, Danyelle; Wells, Michael E.

2012-01-01

This paper presents a mixed-method approach to measuring the functioning of Safe Schools/Healthy Students (SS/HS) Initiative partnerships. The SS/HS national evaluation team developed a survey to collect partners' perceptions of functioning within SS/HS partnerships. Average partnership functioning scores were used to rank each site from lowest to…

Procedures for making gaseous industrial waste safe

NASA Astrophysics Data System (ADS)

Matros, Yu Sh; Noskov, Aleksandr S.

1990-10-01

The application of various methods (adsorption, absorption, thermal afterburning, catalytic purification, and others) for the removal of sulphur and nitrogen oxides, toxic organic compounds, hydrogen sulphide, and carbon monoxide from industrial waste gases is described. Much attention is devoted to the catalytic procedure for making the gases safe using an energy collecting non-stationary method (reversible process). The advantages and limitations of various gas purification methods are considered. The bibliography includes 279 references.

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.

Aware, motivated and striving for a 'safe tan': an exploratory mixed-method study of sun-protection during holidays.

PubMed

Rodrigues, Angela M; Sniehotta, Falko F; Birch-Machin, Mark A; Araujo-Soares, Vera

2017-01-01

Background: This article presents an exploratory study, aiming to explore the correspondence between knowledge, motivation and sun-protection practices during holidays. Methods: Seventeen participants aged 21-62 years old, recruited from community settings took part in individual face-to-face semi-structured interviews, completed sun sensitivity questions and an objective assessment of sunscreen use. Holidaymakers' knowledge about sun-safe messages, intentions and perceptions of barriers and facilitators for sun-protection were assessed. Qualitative data were analysed using thematic analysis and integrated with quantitative data, using a pragmatic theory-informed approach to synthesise the findings. Results: Participants were well informed about sun-safe messages, highly motivated to protect themselves from solar UV radiation (UVR) and they perceived themselves as well protected. However, they did not seem to use effective protective practices. Sunscreen was the preferred method of sun-protection, but most participants used considerably less than the recommended amount and significantly overestimated the amount of time they could be safely exposed. Seeking shade was the least used method of sun-protection and covering-up strategies were mostly implemented as a partial protection (i.e. hats or sunglasses). The desire to reach an optimal balance between getting a tan and using sun-protection to avoid sunburns was preeminent. Several additional barriers and facilitators for sun-protection were identified. Conclusions: Holidaymakers might have a false sense of security when it comes to sun-exposure. They are aware of the need to protect from solar UVR, but the motive for a safe tan, the overreliance on sunscreen, the overestimation of the safe sun-exposure time for their skin type and the insufficient application of sunscreen leaves holidaymakers motivated to protect their skin at significant risk of overexposure, sunburn and skin cancer. Public health messages need to address how to implement effective sun-safe strategies.

Aware, motivated and striving for a ‘safe tan’: an exploratory mixed-method study of sun-protection during holidays

PubMed Central

Rodrigues, Angela M.; Sniehotta, Falko F.; Birch-Machin, Mark A.; Araujo-Soares, Vera

2017-01-01

ABSTRACT Background: This article presents an exploratory study, aiming to explore the correspondence between knowledge, motivation and sun-protection practices during holidays. Methods: Seventeen participants aged 21–62 years old, recruited from community settings took part in individual face-to-face semi-structured interviews, completed sun sensitivity questions and an objective assessment of sunscreen use. Holidaymakers’ knowledge about sun-safe messages, intentions and perceptions of barriers and facilitators for sun-protection were assessed. Qualitative data were analysed using thematic analysis and integrated with quantitative data, using a pragmatic theory-informed approach to synthesise the findings. Results: Participants were well informed about sun-safe messages, highly motivated to protect themselves from solar UV radiation (UVR) and they perceived themselves as well protected. However, they did not seem to use effective protective practices. Sunscreen was the preferred method of sun-protection, but most participants used considerably less than the recommended amount and significantly overestimated the amount of time they could be safely exposed. Seeking shade was the least used method of sun-protection and covering-up strategies were mostly implemented as a partial protection (i.e. hats or sunglasses). The desire to reach an optimal balance between getting a tan and using sun-protection to avoid sunburns was preeminent. Several additional barriers and facilitators for sun-protection were identified. Conclusions: Holidaymakers might have a false sense of security when it comes to sun-exposure. They are aware of the need to protect from solar UVR, but the motive for a safe tan, the overreliance on sunscreen, the overestimation of the safe sun-exposure time for their skin type and the insufficient application of sunscreen leaves holidaymakers motivated to protect their skin at significant risk of overexposure, sunburn and skin cancer. Public health messages need to address how to implement effective sun-safe strategies. PMID:28670503

The case for fire safe cigarettes made through industry documents

PubMed Central

Gunja, M; Wayne, G; Landman, A; Connolly, G; McGuire, A

2002-01-01

Objectives: To examine the extensive research undertaken by the tobacco industry over the past 25 years toward development of a fire safe cigarette. Methods: Research was conducted through a web based search of internal tobacco industry documents made publicly available through the 1998 Master Settlement Agreement. Results: The documents reveal that the tobacco industry produced a fire safe cigarette years ago, but failed to put it on the market. These findings contradict public industry claims that denied the technical feasibility and commercial acceptability of fire safe cigarettes. Internal documents also reveal a decades long, coordinated political strategy used to block proposed legislation and obfuscate the fire safe issue. Conclusions: Federal legislation mandating fire safe cigarettes is needed. PMID:12432160

Interactional Practices Used in the Teaching of Conflict Prevention and Resolution Skills in an Innovative Safe School Program at an Elementary School

ERIC Educational Resources Information Center

Shin, Annalise Grace

2010-01-01

Within the framework of language socialization, this dissertation uses conversation analytic and ethnographic methods to examine the interactional practices used by the adult safe school educator at a progressive elementary school to socialize students into beliefs and practices associated with the school's Cool Tools Safe School Program. Cool…

Flight Control in Complex Environments

DTIC Science & Technology

2016-10-24

that allow insects, with their miniature brains and limited sensory systems to fly safely through cluttered natural environments . The most significant...specialisations that allow insects, with their miniature brains and limited sensory systems to fly safely through cluttered natural environments . The most...bees have developed more accurate or effective methods for flying safely through gaps than species from less complex environments . Fig. 4: The

Using the Method of Water Poverty Index (WPI) to Evaluate the Region Water Security

NASA Astrophysics Data System (ADS)

Fu, Q.; Kachanoski, G.

2008-12-01

Water security is a widely concerned issue in the world nowadays. A new method, water poverty index (WPI), has been used to evaluate the regional water security. Twelve state farms in Heilongjiang Province, Northeastern China were selected to evaluate water security status based on the data of 2006 by using WPI and mean deviation grading method. The method of WPI includes five key indexes, such as resources(R), access (A), capacity(C), utilization (U) and environment (E). Each key index includes several sub-indexes. According to the results of WPI, the grade of each farm has been calculated by using the method of mean deviation grading. Thus, the radar images can be protracted of each farm. From the radar images, the conclusions can be drawn that the WPI values of Farms 853 and Hongqiling were in very safe status, while that of Farm Raohe was in safe status, those of Farms Youyi, 597, 852, 291 and Jiangchuan were in moderate safe status, that of Farm Beixing was in low safe status and those of Farms Shuangyashan, Shuguang and Baoshan were in unsafe status. The results from this study can provide basic information for decision making on rational use of water resources and regulations for regional water safety guarantee system.

A review of evidence for safe abortion care.

PubMed

Kapp, Nathalie; Whyte, Patti; Tang, Jennifer; Jackson, Emily; Brahmi, Dalia

2013-09-01

The provision of safe abortion services to women who need them has the potential to drastically reduce or eliminate maternal deaths due to unsafe abortion. The World Health Organization recently updated its evidence-based guidance for safe and effective clinical practices using data from systematic reviews of the literature. Systematic reviews pertaining to the evidence for safe abortion services, from pre-abortion care, medical and surgical methods of abortion and post-abortion care were evaluated for relevant outcomes, primarily those relating to safety, effectiveness and women's preference. Sixteen systematic reviews were identified and evaluated. The available evidence does not support the use of pre-abortion ultrasound to increase safety. Routine use of cervical preparation with osmotic dilators, mifepristone or misoprostol after 14 weeks gestation reduces complications; at early gestational ages, surgical abortions have very few complications. Prophylactic antibiotics result in lower rates of post-surgical abortion infection. Pain medication such as non-steroidal anti-inflammatories should be offered to women undergoing abortion procedures; acetaminophen, however, is not effective in reducing pain. Women who are eligible should be offered a choice between surgical (vacuum aspiration or dilation and evacuation) and medical methods (mifepristone and misoprostol) of abortion when possible. Modern methods of contraception can be safely initiated immediately following abortion procedures. Evidence-based guidelines assist health care providers and policymakers to utilize the best data available to provide safe abortion care and prevent the millions of deaths and disabilities that result from unsafe abortion. Copyright © 2013 Elsevier Inc. All rights reserved.

Summer trapping method for mule deer. [Nevada Test Site

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

Giles, K.R.

1979-07-01

A summer mule deer trapping method which uses modified Clover traps in a circular corral with water as a bait is described. Drug restraint was used to facilitate safe handling of mule deer by the investigator. Fifteen mule deer were safely captured and outfitted with radio transmitters, ear tags, and reflective markers, and their movements monitored to determine migration patterns.

A method of calculating the safe fatigue life of compact, highly-stressed components

NASA Technical Reports Server (NTRS)

Cardick, Arthur W.; Pike, Vera J.

1994-01-01

This paper describes a method which has been developed for estimating the safe fatigue life of compact, highly-stressed and inaccessible components for aeroplanes and helicopters of the Royal Air Force. It is explained why the Design Requirements for British Military Aircraft do not favor the use of a damage-tolerance approach in these circumstances.

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.

Rock breaking methods to replace blasting

NASA Astrophysics Data System (ADS)

Zhou, Huisheng; Xie, Xinghua; Feng, Yuqing

2018-03-01

The method of breaking rock by blasting has a high efficiency and the cost is relatively low, but the associated vibration, flyrock, production of toxic gases since the 1970’s, the Western developed countries began to study the safety of breaking rock. This paper introduces different methods and their progress to safely break rock. Ideally, safe rock breaking would have little vibration, no fly stone, and no toxic gases, which can be widely used in municipal engineering, road excavation, high-risk mining, quarrying and complex environment.

Risk Assessment and Hierarchical Risk Management of Enterprises in Chemical Industrial Parks Based on Catastrophe Theory

PubMed Central

Chen, Yu; Song, Guobao; Yang, Fenglin; Zhang, Shushen; Zhang, Yun; Liu, Zhenyu

2012-01-01

According to risk systems theory and the characteristics of the chemical industry, an index system was established for risk assessment of enterprises in chemical industrial parks (CIPs) based on the inherent risk of the source, effectiveness of the prevention and control mechanism, and vulnerability of the receptor. A comprehensive risk assessment method based on catastrophe theory was then proposed and used to analyze the risk levels of ten major chemical enterprises in the Songmu Island CIP, China. According to the principle of equal distribution function, the chemical enterprise risk level was divided into the following five levels: 1.0 (very safe), 0.8 (safe), 0.6 (generally recognized as safe, GRAS), 0.4 (unsafe), 0.2 (very unsafe). The results revealed five enterprises (50%) with an unsafe risk level, and another five enterprises (50%) at the generally recognized as safe risk level. This method solves the multi-objective evaluation and decision-making problem. Additionally, this method involves simple calculations and provides an effective technique for risk assessment and hierarchical risk management of enterprises in CIPs. PMID:23208298

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.

Target Trailing With Safe Navigation With Colregs for Maritime Autonomous Surface Vehicles

NASA Technical Reports Server (NTRS)

Kuwata, Yoshiaki (Inventor); Aghazarian, Hrand (Inventor); Huntsberger, Terrance L. (Inventor); Howard, Andrew B. (Inventor); Wolf, Michael T. (Inventor); Zarzhitsky, Dimitri V. (Inventor)

2014-01-01

Systems and methods for operating autonomous waterborne vessels in a safe manner. The systems include hardware for identifying the locations and motions of other vessels, as well as the locations of stationary objects that represent navigation hazards. By applying a computational method that uses a maritime navigation algorithm for avoiding hazards and obeying COLREGS using Velocity Obstacles to the data obtained, the autonomous vessel computes a safe and effective path to be followed in order to accomplish a desired navigational end result, while operating in a manner so as to avoid hazards and to maintain compliance with standard navigational procedures defined by international agreement. The systems and methods have been successfully demonstrated on water with radar and stereo cameras as the perception sensors, and integrated with a higher level planner for trailing a maneuvering target.

Wake vortex separation standards : analysis methods

DOT National Transportation Integrated Search

1997-01-01

Wake vortex separation standards are used to prevent hazardous wake vortex encounters. A "safe" separation model can be used to assess the safety of proposed changes in the standards. A safe separation model can be derived from an encounter hazard mo...

SU-E-I-97: Smart Auto-Planning Framework in An EMR Environment (SAFEE)

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

Zhang, B; Chen, S; Mutaf, Y

2014-06-01

Purpose: Our Radiation Oncology Department uses clinical practice guidelines for patient treatment, including normal tissue sparing and other dosimetric constraints. These practice guidelines were adapted from national guidelines, clinical trials, literature reviews, and practitioner's own experience. Modern treatment planning systems (TPS) have the capability of incorporating these practice guidelines to automatically create radiation therapy treatment plans with little human intervention. We are developing a software infrastructure to integrate clinical practice guidelines and radiation oncology electronic medical record (EMR) system into radiation therapy treatment planning system (TPS) for auto planning. Methods: Our Smart Auto-Planning Framework in an EMR environment (SAFEE) usesmore » a software pipeline framework to integrate practice guidelines,EMR, and TPS together. The SAFEE system starts with retrieving diagnosis information and physician's prescription from the EMR system. After approval of contouring, SAFEE will automatically create plans according to our guidelines. Based on clinical objectives, SAFEE will automatically select treatment delivery techniques (such as, 3DRT/IMRT/VMAT) and optimize plans. When necessary, SAFEE will create multiple treatment plans with different combinations of parameters. SAFEE's pipeline structure makes it very flexible to integrate various techniques, such as, Model-Base Segmentation (MBS) and plan optimization algorithms, e.g., Multi-Criteria Optimization (MCO). In addition, SAFEE uses machine learning, data mining techniques, and an integrated database to create clinical knowledgebase and then answer clinical questions, such as, how to score plan quality or how volume overlap affects physicians' decision in beam and treatment technique selection. Results: In our institution, we use Varian Aria EMR system and RayStation TPS from RaySearch, whose ScriptService API allows control by external programs. These applications are the building blocks of our SAFEE system. Conclusion: SAFEE is a feasible method of integrating clinical information to develop an auto-planning paradigm to improve clinical workflow in cancer patient care.« less

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.

Occurrence and distribution study of residues from pesticides applied under controlled conditions in the field during rice processing.

PubMed

Pareja, Lucía; Colazzo, Marcos; Pérez-Parada, Andrés; Besil, Natalia; Heinzen, Horacio; Böcking, Bernardo; Cesio, Verónica; Fernández-Alba, Amadeo R

2012-05-09

The results of an experiment to study the occurrence and distribution of pesticide residues during rice cropping and processing are reported. Four herbicides, nine fungicides, and two insecticides (azoxystrobin, byspiribac-sodium, carbendazim, clomazone, difenoconazole, epoxiconazole, isoprothiolane, kresoxim-methyl, propanil, quinclorac, tebuconazole, thiamethoxam, tricyclazole, trifloxystrobin, λ-cyhalotrin) were applied to an isolated rice-crop plot under controlled conditions, during the 2009-2010 cropping season in Uruguay. Paddy rice was harvested and industrially processed to brown rice, white rice, and rice bran, which were analyzed for pesticide residues using the original QuEChERS methodology and its citrate variation by LC-MS/MS and GC-MS. The distribution of pesticide residues was uneven among the different matrices. Ten different pesticide residues were found in paddy rice, seven in brown rice, and eight in rice bran. The highest concentrations were detected in paddy rice. These results provide information regarding the fate of pesticides in the rice food chain and its safety for consumers.

Spent Pot Lining Characterization Framework

NASA Astrophysics Data System (ADS)

Ospina, Gustavo; Hassan, Mohamed I.

2017-09-01

Spent pot lining (SPL) management represents a major concern for aluminum smelters. There are two key elements for spent pot lining management: recycling and safe storage. Spent pot lining waste can potentially have beneficial uses in co-firing in cement plants. Also, safe storage of SPL is of utmost importance. Gas generation of SPL reaction with water and ignition sensitivity must be studied. However, determining the feasibility of SPL co-firing and developing the required procedures for safe storage rely on determining experimentally all the necessary SPL properties along with the appropriate test methods, recognized by emissions standards and fire safety design codes. The applicable regulations and relevant SPL properties for this purpose are presented along with the corresponding test methods.

Accurate, safe, and rapid method of intraoperative tumor identification for totally laparoscopic distal gastrectomy: injection of mixed fluid of sodium hyaluronate and patent blue.

PubMed

Nakagawa, Masatoshi; Ehara, Kazuhisa; Ueno, Masaki; Tanaka, Tsuyoshi; Kaida, Sachiko; Udagawa, Harushi

2014-04-01

In totally laparoscopic distal gastrectomy, determining the resection line with safe proximal margins is often difficult, particularly for tumors located in a relatively upper area. This is because, in contrast to open surgery, identifying lesions by palpating or opening the stomach is essentially impossible. This study introduces a useful method of tumor identification that is accurate, safe, and rapid. On the operation day, after inducing general anesthesia, a mixture of sodium hyaluronate and patent blue is injected into the submucosal layer of the proximal margin. When resecting stomach, all marker spots should be on the resected side. In all cases, the proximal margin is examined histologically by using frozen sections during the operation. From October 2009 to September 2011, a prospective study that evaluated this method was performed. A total of 34 patients who underwent totally laparoscopic distal gastrectomy were enrolled in this study. Approximately 5 min was required to complete the procedure. Proximal margins were negative in all cases, and the mean ± standard deviation length of the proximal margin was 23.5 ± 12.8 mm. No side effects, such as allergy, were encountered. As a method of tumor identification for totally laparoscopic distal gastrectomy, this procedure appears accurate, safe, and rapid.

Study of fail-safe abort system for an actively cooled hypersonic aircraft, volume 2

NASA Technical Reports Server (NTRS)

Peeples, M. E.; Herring, R. L.

1976-01-01

Conceptual designs of a fail-safe abort system for hydrogen fueled actively cooled high speed aircraft are examined. The fail-safe concept depends on basically three factors: (1) a reliable method of detecting a failure or malfunction in the active cooling system, (2) the optimization of abort trajectories which minimize the descent heat load to the aircraft, and (3) fail-safe thermostructural concepts to minimize both the weight and the maximum temperature the structure will reach during descent. These factors are examined and promising approaches are evaluated based on weight, reliability, ease of manufacture and cost.

Pushover, Response Spectrum and Time History Analyses of Safe Rooms in a Poor Performance Masonry Building

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

Mazloom, M.

2008-07-08

The idea of safe room has been developed for decreasing the earthquake casualties in masonry buildings. The information obtained from the previous ground motions occurring in seismic zones expresses the lack of enough safety of these buildings against earthquakes. For this reason, an attempt has been made to create some safe areas inside the existing masonry buildings, which are called safe rooms. The practical method for making these safe areas is to install some prefabricated steel frames in some parts of the existing structure. These frames do not carry any service loads before an earthquake. However, if a devastating earthquakemore » happens and the load bearing walls of the building are destroyed, some parts of the floors, which are in the safe areas, will fall on the roof of the installed frames and the occupants who have sheltered there will survive. This paper presents the performance of these frames located in a destroying three storey masonry building with favorable conclusions. In fact, the experimental pushover diagram of the safe room located at the ground-floor level of this building is compared with the analytical results and it is concluded that pushover analysis is a good method for seismic performance evaluation of safe rooms. For time history analysis the 1940 El Centro, the 2003 Bam, and the 1990 Manjil earthquake records with the maximum peak accelerations of 0.35g were utilized. Also the design spectrum of Iranian Standard No. 2800-05 for the ground kind 2 is used for response spectrum analysis. The results of time history, response spectrum and pushover analyses show that the strength and displacement capacity of the steel frames are adequate to accommodate the distortions generated by seismic loads and aftershocks properly.« less

Evaluation of Cognitive and Behavioral Effects of Peer Education Model-Based Intervention to Sun Safe in Children

PubMed Central

HU, Ping; HAN, Lingli; SHARMA, Manoj; ZENG, Huan; ZHANG, Yong; LI, Hui; ZHAO, Yong

2014-01-01

Abstract Background There have been many studies that evidence the health hazards of sunlight exposure, but less study on sun safe intervention model, especially in China. Our aim was to evaluate the cognitive and behavioral effects of a peer education model-based intervention to sun safe in children. Methods Cluster random control intervention was conducted in one district in Chongqing, China. Two primary schools, selected through stratified clustered sampling approach (two grades in each school, three classes in each grade) were designated as intervention (n=304) and control schools (n=305) randomly. 36 students, selected as peer educators in intervention group, were trained for one month. Educational activities such as discussions were organized by peer educator for one month. There was no sun safe education to participants in control school during the project period. The evaluation of changes of sun safe knowledge (the primary outcome), attitude and behavior (the secondary outcome measures) were conducted before intervention and at months of 0, 1 and 6 of the intervention to two groups using quantitative and qualitative methods. Results After the intervention, sun safe knowledge score which gained by the students from intervention group has been remarkably improved, compared to baseline survey (24.48±6.17 vs. 29.51±6.75) (P<0.001), and it kept this high level (29.02±7.96 and. 28.65±8.96), while control group students' scores have made no difference (P=0.410). Most of students have changed their sun safe behavior after the intervention. Conclusion Peer education program is somewhat effective in some dimensions for improving children's understanding of sun safe knowledge and behavior. PMID:25988089

The preparation, mincing and canning of bovine offal (ruminal and intestinal wall) for human consumption.

PubMed

van der Made, H N; van Staden, J J

1975-09-01

The results of a sudy of methods of cleaning and preserving bovine ruminal and intestinal wall by canning are described. Such offal could be converted into a hygienically satisfactory and safe food by laboratory washing and canning, and töe end product had a extended shelf life. Methods are described and suggested as a basis for ensuring safe utilisation of a valuable food product.

Laser Safety Method For Duplex Open Loop Parallel Optical Link

DOEpatents

Baumgartner, Steven John; Hedin, Daniel Scott; Paschal, Matthew James

2003-12-02

A method and apparatus are provided to ensure that laser optical power does not exceed a "safe" level in an open loop parallel optical link in the event that a fiber optic ribbon cable is broken or otherwise severed. A duplex parallel optical link includes a transmitter and receiver pair and a fiber optic ribbon that includes a designated number of channels that cannot be split. The duplex transceiver includes a corresponding transmitter and receiver that are physically attached to each other and cannot be detached therefrom, so as to ensure safe, laser optical power in the event that the fiber optic ribbon cable is broken or severed. Safe optical power is ensured by redundant current and voltage safety checks.

Feeling safe during an inpatient hospitalization: a concept analysis.

PubMed

Mollon, Deene

2014-08-01

This paper aims to explore the critical attributes of the concept feeling safe. The safe delivery of care is a high priority; however; it is not really known what it means to the patient to 'feel safe' during an inpatient hospitalization. This analysis explores the topic of safety from the patient's perspective. Concept analysis. The data bases of CINAHL, Medline, PsychInfo and Google Scholar for the years 1995-2012 were searched using the terms safe and feeling safe. The eight-step concept analysis method of Walker and Avant was used to analyse the concept of feeling safe. Uses and defining attributes, as well as identified antecedents, consequences and empirical referents, are presented. Case examples are provided to assist in the understanding of defining attributes. Feeling safe is defined as an emotional state where perceptions of care contribute to a sense of security and freedom from harm. Four attributes were identified: trust, cared for, presence and knowledge. Relationship, environment and suffering are the antecedents of feeling safe, while control, hope and relaxed or calm are the consequences. Empirical referents and early development of a theory of feeling safe are explored. This analysis begins the work of synthesizing qualitative research already completed around the concept of feeling safe by defining the key attributes of the concept. Support for the importance of developing patient-centred models of care and creating positive environments where patients receive high-quality care and feel safe is provided. © 2014 John Wiley & Sons Ltd.

Keeping Campuses Safe.

ERIC Educational Resources Information Center

Kennedy, Mike

1999-01-01

Describes how colleges and universities are using technology, as well as traditional methods, to keep campuses safe and reduce crime. Topics include using free pizza in a successful contest to teach students about campus safety, installing security cameras, using access-control cards, providing adequate lighting, and creating a bicycle patrol…

Challenging Heteronormativity: Creating a Safe and Inclusive Environment for LGBTQ Students

ERIC Educational Resources Information Center

Steck, Andy K.; Perry, David

2018-01-01

Lesbian, gay, bisexual, transgender, and queer/questioning (LGBTQ) youth face hostile and exclusionary learning environments. A qualitative phenomenographic method involving semistructured interviews of seven secondary school administrators was conducted to identify perceptions of experiences creating a safe and inclusive environment for students…

Study of a fail-safe abort system for an actively cooled hypersonic aircraft. Volume 1: Technical summary

NASA Technical Reports Server (NTRS)

Pirello, C. J.; Herring, R. L.

1976-01-01

Conceptual designs of a fail-safe abort system for hydrogen fueled actively cooled high speed aircraft are examined. The fail-safe concept depends on basically three factors: (1) a reliable method of detecting a failure or malfunction in the active cooling system, (2) the optimization of abort trajectories which minimize the descent heat load to the aircraft, and (3) fail-safe thermostructural concepts to minimize both the weight and the maximum temperature the structure will reach during descent. These factors are examined and promising approaches are evaluated based on weight, reliability, ease of manufacture and cost.

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.

Background Error Covariance Estimation using Information from a Single Model Trajectory with Application to Ocean Data Assimilation into the GEOS-5 Coupled Model

NASA Technical Reports Server (NTRS)

Keppenne, Christian L.; Rienecker, Michele M.; Kovach, Robin M.; Vernieres, Guillaume; Koster, Randal D. (Editor)

2014-01-01

An attractive property of ensemble data assimilation methods is that they provide flow dependent background error covariance estimates which can be used to update fields of observed variables as well as fields of unobserved model variables. Two methods to estimate background error covariances are introduced which share the above property with ensemble data assimilation methods but do not involve the integration of multiple model trajectories. Instead, all the necessary covariance information is obtained from a single model integration. The Space Adaptive Forecast error Estimation (SAFE) algorithm estimates error covariances from the spatial distribution of model variables within a single state vector. The Flow Adaptive error Statistics from a Time series (FAST) method constructs an ensemble sampled from a moving window along a model trajectory. SAFE and FAST are applied to the assimilation of Argo temperature profiles into version 4.1 of the Modular Ocean Model (MOM4.1) coupled to the GEOS-5 atmospheric model and to the CICE sea ice model. The results are validated against unassimilated Argo salinity data. They show that SAFE and FAST are competitive with the ensemble optimal interpolation (EnOI) used by the Global Modeling and Assimilation Office (GMAO) to produce its ocean analysis. Because of their reduced cost, SAFE and FAST hold promise for high-resolution data assimilation applications.

Background Error Covariance Estimation Using Information from a Single Model Trajectory with Application to Ocean Data Assimilation

NASA Technical Reports Server (NTRS)

Keppenne, Christian L.; Rienecker, Michele; Kovach, Robin M.; Vernieres, Guillaume

2014-01-01

An attractive property of ensemble data assimilation methods is that they provide flow dependent background error covariance estimates which can be used to update fields of observed variables as well as fields of unobserved model variables. Two methods to estimate background error covariances are introduced which share the above property with ensemble data assimilation methods but do not involve the integration of multiple model trajectories. Instead, all the necessary covariance information is obtained from a single model integration. The Space Adaptive Forecast error Estimation (SAFE) algorithm estimates error covariances from the spatial distribution of model variables within a single state vector. The Flow Adaptive error Statistics from a Time series (FAST) method constructs an ensemble sampled from a moving window along a model trajectory.SAFE and FAST are applied to the assimilation of Argo temperature profiles into version 4.1 of the Modular Ocean Model (MOM4.1) coupled to the GEOS-5 atmospheric model and to the CICE sea ice model. The results are validated against unassimilated Argo salinity data. They show that SAFE and FAST are competitive with the ensemble optimal interpolation (EnOI) used by the Global Modeling and Assimilation Office (GMAO) to produce its ocean analysis. Because of their reduced cost, SAFE and FAST hold promise for high-resolution data assimilation applications.

49 CFR 240.125 - Criteria for testing knowledge.

Code of Federal Regulations, 2010 CFR

2010-10-01

... practices for the safe operation of trains. (c) The testing methods selected by the railroad shall be: (1) Designed to examine a person's knowledge of the railroad's rules and practices for the safe operation of...) Personal safety practices; (ii) Operating practices; (iii) Equipment inspection practices; (iv) Train...

SFTYCHEF: A Consultative, Diagnostic Expert System for Trench Excavation Safety Analysis on Light Commercial Construction Projects.

DTIC Science & Technology

1987-03-30

Safe Trench Excavation ...... 2 Applicability to Solution via Expert System. 3 Background: Expert Systems ..................... 4 Definition of an...trench, drownings in the trench, and other mishaps which are the result of a lack of S C- proper consideration for safe construction practices. Although...the problem is not a new one, there is as yet no *" obvious method that will guarantee a safe trench. In addition, the expertise needed to provide case

Safe Life Propulsion Design Technologies (3rd Generation Propulsion Research and Technology)

NASA Technical Reports Server (NTRS)

Ellis, Rod

2000-01-01

The tasks outlined in this viewgraph presentation on safe life propulsion design technologies (third generation propulsion research and technology) include the following: (1) Ceramic matrix composite (CMC) life prediction methods; (2) Life prediction methods for ultra high temperature polymer matrix composites for reusable launch vehicle (RLV) airframe and engine application; (3) Enabling design and life prediction technology for cost effective large-scale utilization of MMCs and innovative metallic material concepts; (4) Probabilistic analysis methods for brittle materials and structures; (5) Damage assessment in CMC propulsion components using nondestructive characterization techniques; and (6) High temperature structural seals for RLV applications.

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.

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.

Safe Space Oddity: Revisiting Critical Pedagogy

ERIC Educational Resources Information Center

Redmond, Melissa

2010-01-01

Inspired by an incident in a social work graduate classroom in which she was a teaching assistant, the author reflects on her commitment to constructivist teaching methods, critical theory, and critical pedagogy. Exploring the educational utility of notions such as public space and safe space, the author employs this personal experience to examine…

Designing, Implementing and Evaluating Preclinical Simulation Lab for Maternity Nursing Course

ERIC Educational Resources Information Center

ALFozan, Haya; El Sayed, Yousria; Habib, Farida

2015-01-01

Background: The opportunity for students to deliver care safely in today's, complex health care environment is limited. Simulation allows students to practice skills in a safe environment. Purpose: to assess the students' perception, satisfaction, and learning outcomes after a simulation based maternity course. Method: a quasi experimental design…

Pushed Out

ERIC Educational Resources Information Center

Brownstein, Rhonda

2010-01-01

Significant numbers of students are being pushed out of school as a result of "zero tolerance" school discipline policies. While nobody questions the need to keep schools safe, teachers, students, and parents are questioning the methods being used in pursuit of that goal. Zero tolerance policies were initially aimed at making schools safe. The…

Safe Surgery Trainer Project Management Plan (PMP), Version 1.0

DTIC Science & Technology

2014-05-30

Methodology including SCRUM (see http://en.wikipedia.org/wiki/Scrum_(management) for more info). Although this Safe Surgery Trainer - PMP Version 1.0 5...Agile method similar to Scrum . The internal development team works on a minor iteration cycle that begins/ends on Wednesday. At the beginning of

Microelectromechanical safe arm device

DOEpatents

Roesler, Alexander W [Tijeras, NM

2012-06-05

Microelectromechanical (MEM) apparatus and methods for operating, for preventing unintentional detonation of energetic components comprising pyrotechnic and explosive materials, such as air bag deployment systems, munitions and pyrotechnics. The MEM apparatus comprises an interrupting member that can be moved to block (interrupt) or complete (uninterrupt) an explosive train that is part of an energetic component. One or more latching members are provided that engage and prevent the movement of the interrupting member, until the one or more latching members are disengaged from the interrupting member. The MEM apparatus can be utilized as a safe and arm device (SAD) and electronic safe and arm device (ESAD) in preventing unintentional detonations. Methods for operating the MEM apparatus include independently applying drive signals to the actuators coupled to the latching members, and an actuator coupled to the interrupting member.

Application of Solid Phase Microextraction with Gas Chromatography-Mass Spectrometry as a Rapid, Reliable, and Safe Method for Field Sampling and Analysis of Chemical Warfare Agent Precursors

DTIC Science & Technology

2005-03-01

in hair samples with analysis by GC-MS [41,42]. The research discussed here examined a polydimethylsiloxane polymer with 10% activated charcoal (PDMS...Field Sampling and Analysis of Chemical Warfare Agent Precursors” Name of Candidate: LT Douglas Parrish Doctor of Philosophy, Environmental...Microextraction with Gas Chromatography-Mass Spectrometry as a Rapid, Reliable, and Safe Method for Field Sampling and Analysis of Chemical Warfare

Safely Intake Number of Macridiscus sp. (Kerang Ceplos) from Tambak Lorok Waters, Semarang, Central Java, Indonesia

NASA Astrophysics Data System (ADS)

Meirenno Tielman, Eduard; Suprijanto, Jusup; Widowati, Ita

2018-02-01

The dynamics pollution that supposed to be derived from industrial activities around Tambak Lorok waters will affect the quality of waters, and also biota such as Macridiscus sp. mussels (Kerang Ceplos) that live and accumulate pollutants such as heavy metals (Pb, Cu, Al, Mn and Fe). However, Macridiscus sp. mussels which have been contaminated by heavy metals is usually sold for consumption by the people and if they consume it in excess, it will be toxic in the people’s body. So that, this study was to analyze Safely Intake Number of Macridiscus sp. from Tambak Lorok waters. This study used AAS (Atomic Absorption Spectrophotometry) method to analyze the accumulation number of the pollutant (Pb, Cu, Al, Mn and Fe). Safely Intake Number calculation is used MWI (Maximal Weekly Intake) and MTI (Maximal Tolerable Intake) calculation method. The results of AAS showed that the highest numbers of pollutant was Al (reached 534,51 mg/kg in the body of Macridiscus sp. that taken in February, 2016) and has exceeded the safely intake number (MWI Al = 1 mg/kg, based on WHO/FAO) so that it’s MTI values was low (0,08 kg/week/person). It means that Macridiscus sp. was not safe to be consumed excessively at that time.

A safe and accurate method to perform esthetic mandibular contouring surgery for Far Eastern Asians.

PubMed

Hsieh, A M-C; Huon, L-K; Jiang, H-R; Liu, S Y-C

2017-05-01

A tapered mandibular contour is popular with Far Eastern Asians. This study describes a safe and accurate method of using preoperative virtual surgical planning (VSP) and an intraoperative ostectomy guide to maximize the esthetic outcomes of mandibular symmetry and tapering while mitigating injury to the inferior alveolar nerve (IAN). Twelve subjects with chief complaints of a wide and square lower face underwent this protocol from January to June 2015. VSP was used to confirm symmetry and preserve the IAN while maximizing the surgeon's ability to taper the lower face via mandibular inferior border ostectomy. The accuracy of this method was confirmed by superimposition of the perioperative computed tomography scans in all subjects. No subjects complained of prolonged paresthesia after 3 months. A safe and accurate protocol for achieving an esthetic lower face in indicated Far Eastern individuals is described. Copyright © 2016 International Association of Oral and Maxillofacial Surgeons. Published by Elsevier Ltd. All rights reserved.

Quick, easy, cheap, effective, rugged, and safe sample preparation approach for pesticide residue analysis using traditional detectors in chromatography: A review.

PubMed

Rahman, Md Musfiqur; Abd El-Aty, A M; Kim, Sung-Woo; Shin, Sung Chul; Shin, Ho-Chul; Shim, Jae-Han

2017-01-01

In pesticide residue analysis, relatively low-sensitivity traditional detectors, such as UV, diode array, electron-capture, flame photometric, and nitrogen-phosphorus detectors, have been used following classical sample preparation (liquid-liquid extraction and open glass column cleanup); however, the extraction method is laborious, time-consuming, and requires large volumes of toxic organic solvents. A quick, easy, cheap, effective, rugged, and safe method was introduced in 2003 and coupled with selective and sensitive mass detectors to overcome the aforementioned drawbacks. Compared to traditional detectors, mass spectrometers are still far more expensive and not available in most modestly equipped laboratories, owing to maintenance and cost-related issues. Even available, traditional detectors are still being used for analysis of residues in agricultural commodities. It is widely known that the quick, easy, cheap, effective, rugged, and safe method is incompatible with conventional detectors owing to matrix complexity and low sensitivity. Therefore, modifications using column/cartridge-based solid-phase extraction instead of dispersive solid-phase extraction for cleanup have been applied in most cases to compensate and enable the adaptation of the extraction method to conventional detectors. In gas chromatography, the matrix enhancement effect of some analytes has been observed, which lowers the limit of detection and, therefore, enables gas chromatography to be compatible with the quick, easy, cheap, effective, rugged, and safe extraction method. For liquid chromatography with a UV detector, a combination of column/cartridge-based solid-phase extraction and dispersive solid-phase extraction was found to reduce the matrix interference and increase the sensitivity. A suitable double-layer column/cartridge-based solid-phase extraction might be the perfect solution, instead of a time-consuming combination of column/cartridge-based solid-phase extraction and dispersive solid-phase extraction. Therefore, replacing dispersive solid-phase extraction with column/cartridge-based solid-phase extraction in the cleanup step can make the quick, easy, cheap, effective, rugged, and safe extraction method compatible with traditional detectors for more sensitive, effective, and green analysis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Large optics inspection, tilting, and washing stand

DOEpatents

Ayers, Marion Jay [Brentwood, CA; Ayers, Shannon Lee [Brentwood, CA

2010-08-24

A large optics stand provides a risk free means of safely tilting large optics with ease and a method of safely tilting large optics with ease. The optics are supported in the horizontal position by pads. In the vertical plane the optics are supported by saddles that evenly distribute the optics weight over a large area.

Large optics inspection, tilting, and washing stand

DOEpatents

Ayers, Marion Jay; Ayers, Shannon Lee

2012-10-09

A large optics stand provides a risk free means of safely tilting large optics with ease and a method of safely tilting large optics with ease. The optics are supported in the horizontal position by pads. In the vertical plane the optics are supported by saddles that evenly distribute the optics weight over a large area.

Using Interactive Multimedia to Teach Pedestrian Safety: An Exploratory Study

ERIC Educational Resources Information Center

Glang, Ann; Noell, John; Ary, Dennis; Swartz, Lynne

2005-01-01

Objectives: To evaluate an interactive multimedia (IMM) program that teaches young children safe pedestrian skills. Methods: The program uses IMM (animation and video) to teach children critical skills for crossing streets safely. A computer-delivered video assessment and a real-life street simulation were used to measure the effectiveness of the…

Injury and Illness Costs in the Certified Safe Farm Study

ERIC Educational Resources Information Center

Donham, Kelley J.; Rautiainen, Risto H.; Lange, Jeffrey L.; Schneiders, Sara

2007-01-01

Context: The Certified Safe Farm (CSF) intervention program aims to reduce occupational injuries and illnesses, and promote wellness to reduce health care and related costs to farmers, insurers, and other stakeholders. Purpose: To evaluate the cost effectiveness of CSF. Methods: Farms (316) located in a 9-county area of northwestern Iowa were…

Safety Early Warning Research for Highway Construction Based on Case-Based Reasoning and Variable Fuzzy Sets

PubMed Central

Liu, Yan; Xu, Zhen-Jun

2013-01-01

As a high-risk subindustry involved in construction projects, highway construction safety has experienced major developments in the past 20 years, mainly due to the lack of safe early warnings in Chinese construction projects. By combining the current state of early warning technology with the requirements of the State Administration of Work Safety and using case-based reasoning (CBR), this paper expounds on the concept and flow of highway construction safety early warnings based on CBR. The present study provides solutions to three key issues, index selection, accident cause association analysis, and warning degree forecasting implementation, through the use of association rule mining, support vector machine classifiers, and variable fuzzy qualitative and quantitative change criterion modes, which fully cover the needs of safe early warning systems. Using a detailed description of the principles and advantages of each method and by proving the methods' effectiveness and ability to act together in safe early warning applications, effective means and intelligent technology for a safe highway construction early warning system are established. PMID:24191134

Safety early warning research for highway construction based on case-based reasoning and variable fuzzy sets.

PubMed

Liu, Yan; Yi, Ting-Hua; Xu, Zhen-Jun

2013-01-01

As a high-risk subindustry involved in construction projects, highway construction safety has experienced major developments in the past 20 years, mainly due to the lack of safe early warnings in Chinese construction projects. By combining the current state of early warning technology with the requirements of the State Administration of Work Safety and using case-based reasoning (CBR), this paper expounds on the concept and flow of highway construction safety early warnings based on CBR. The present study provides solutions to three key issues, index selection, accident cause association analysis, and warning degree forecasting implementation, through the use of association rule mining, support vector machine classifiers, and variable fuzzy qualitative and quantitative change criterion modes, which fully cover the needs of safe early warning systems. Using a detailed description of the principles and advantages of each method and by proving the methods' effectiveness and ability to act together in safe early warning applications, effective means and intelligent technology for a safe highway construction early warning system are established.

A novel pretreatment method combining sealing technique with direct injection technique applied for improving biosafety.

PubMed

Wang, Xinyu; Gao, Jing-Lin; Du, Chaohui; An, Jing; Li, MengJiao; Ma, Haiyan; Zhang, Lina; Jiang, Ye

2017-01-01

People today have a stronger interest in the risk of biosafety in clinical bioanalysis. A safe, simple, effective method of preparation is needed urgently. To improve biosafety of clinical analysis, we used antiviral drugs of adefovir and tenofovir as model drugs and developed a safe pretreatment method combining sealing technique with direct injection technique. The inter- and intraday precision (RSD %) of the method were <4%, and the extraction recoveries ranged from 99.4 to 100.7%. Meanwhile, the results showed that standard solution could be used to prepare calibration curve instead of spiking plasma, acquiring more accuracy result. Compared with traditional methods, the novel method not only improved biosecurity of the pretreatment method significantly, but also achieved several advantages including higher precision, favorable sensitivity and satisfactory recovery. With these highly practical and desirable characteristics, the novel method may become a feasible platform in bioanalysis.

Method and device for landing aircraft dependent on runway occupancy time

NASA Technical Reports Server (NTRS)

Ghalebsaz Jeddi, Babak (Inventor)

2012-01-01

A technique for landing aircraft using an aircraft landing accident avoidance device is disclosed. The technique includes determining at least two probability distribution functions; determining a safe lower limit on a separation between a lead aircraft and a trail aircraft on a glide slope to the runway; determining a maximum sustainable safe attempt-to-land rate on the runway based on the safe lower limit and the probability distribution functions; directing the trail aircraft to enter the glide slope with a target separation from the lead aircraft corresponding to the maximum sustainable safe attempt-to-land rate; while the trail aircraft is in the glide slope, determining an actual separation between the lead aircraft and the trail aircraft; and directing the trail aircraft to execute a go-around maneuver if the actual separation approaches the safe lower limit. Probability distribution functions include runway occupancy time, and landing time interval and/or inter-arrival distance.

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.

78 FR 32558 - Expedited Approval of Alternative Test Procedures for the Analysis of Contaminants Under the Safe...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-05-31

...This action announces the U.S. Environmental Protection Agency's (EPA's) approval of alternative testing methods for use in measuring the levels of contaminants in drinking water and determining compliance with national primary drinking water regulations. The Safe Drinking Water Act (SDWA) authorizes EPA to approve the use of alternative testing methods through publication in the Federal Register. EPA is using this streamlined authority to make 84 additional methods available for analyzing drinking water samples. This expedited approach provides public water systems, laboratories, and primacy agencies with more timely access to new measurement techniques and greater flexibility in the selection of analytical methods, thereby reducing monitoring costs while maintaining public health protection.

Enantioselective Dissipation of Acephate and Its Metabolite, Methamidophos, during Tea Cultivation, Manufacturing, and Infusion.

PubMed

Pan, Rong; Chen, Hongping; Wang, Chen; Wang, Qinghua; Jiang, Ying; Liu, Xin

2015-02-04

The enantioselective dissipation of acephate and its metabolite, methamidophos, was investigated during tea cultivation, manufacturing, and infusion, using QuEChERS sample preparation technique and gas chromatography coupled with a BGB-176 chiral column. Results showed that (+)-acephate and (-)-acephate dissipated following first-order kinetics in fresh tea leaves with half-lives of 1.8 and 1.9 days, respectively. Acephate was degraded into a more toxic metabolite, methamidophos. Preferential dissipation and translocation of (+)-acephate may exist in tea shoots, and (-)-methamidophos was degraded more rapidly than (+)-methamidophos. During tea manufacturing, drying and spreading (or withering) played important roles in the dissipation of acephate enantiomers. The enantiometic fractions of acephate changed from 0.495-0.496 to 0.479-0.486 (P ≤ 0.0081), whereas those of methamidophos changed from 0.576-0.630 to 0.568-0.645 (P ≤ 0.0366 except for green tea manufacturing on day 1), from fresh tea leaves to made tea. In addition, high transfer rates (>80%) and significant enantioselectivity (P ≤ 0.0042) of both acephate and its metabolite occurred during tea brewing.

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

Evaluating "The Safe Living Guide": A Home Hazard Checklist for Seniors

ERIC Educational Resources Information Center

Sorcinelli, Andrea; Shaw, Lynn; Freeman, Andrew; Cooper, Kim

2007-01-01

Purpose: The purpose of this study was to evaluate the utility and reliability of a home hazard checklist published in Health Canada, "The Safe Living Guide: A Guide to Home Safety for Seniors" (2003). Methods: 76 community-dwelling seniors evaluated the guide, and inter-rater reliability was determined through comparison of ratings of…

Reliability and Validity of a Questionnaire to Measure Consumer Knowledge regarding Safe Practices to Prevent Microbiological Contamination in Restaurants

ERIC Educational Resources Information Center

Uggioni, Paula Lazzarin; Salay, Elisabette

2013-01-01

Objective: The objective of this study was to develop a validated and reliable questionnaire to measure consumer knowledge regarding safe practices to prevent microbiological contamination in restaurants and commercial kitchens. Methods: Non-probabilistic samples of individuals were interviewed in the city of Campinas, Brazil. Questionnaire items…

78 FR 68735 - Reduction or Suspension of Safe Harbor Contributions

Federal Register 2010, 2011, 2012, 2013, 2014

2013-11-15

... forth in section 401(k)(3), called the actual deferral percentage (ADP) test, or one of the design-based... design-based safe harbor method under which a CODA is treated as satisfying the ADP test if the... the design-based alternatives in section 401(m)(10), 401(m)(11), or 401(m)(12). The ACP test in...

Adoption of Safe Routes to School in Canadian and the United States Contexts: Best Practices and Recommendations

ERIC Educational Resources Information Center

Macridis, Soultana; García Bengoechea, Enrique

2015-01-01

Background: Declines in physical activity (PA) in children and youth have contributed to increases in childhood overweight and obesity. The Safe Routes to School (SRTS) program was developed to promote school active transportation (AT) and reverse the trend. Methods: Adopting concepts of a realist approach, this article seeks to understand…

Evaluation of the Solar Water Disinfection Method Using an Ultraviolet Measurement Device

NASA Astrophysics Data System (ADS)

Leung, H.

2015-12-01

Drinking water security is a growing problem for the population of planet Earth. According to WHO, more than 750 million people on our planet lack access to safe drinking water, resulting in approximately 502,000 diarrhoea deaths in 2012. In order to solve this problem, the Swiss water research institute, Eawag, has developed a method of solar water disinfection, called, "SODIS" The theory of SODIS is simple to understand: a clear plastic bottle filled with water is placed under full sunlight for at least 6 hours. The ultraviolet radiation kills the pathogens in the water, making the originally contaminated water safe for drinking. In order to improve this method, Helioz, an Austrian social enterprise, has created the WADI, a UV measurement device which determines when water is safe for drinking using the SODIS method. When using the WADI, the device should be placed under the sun and surrounded with bottles of water that need to be decontaminated. There is a UV sensor on the WADI, and since the bottles of water and the WADI will have equal exposure to sunlight, the WADI will be able to measure the impact of the sunlight on the contaminated water. This experiment tests the accuracy of the WADI device regarding the time interval needed for contaminated water to be disinfected. The experiment involves using the SODIS method to purify bottles of water contaminated with controlled samples of E. coli. Samples of the water are taken at different time intervals, and the E. coli levels are determined by growing the bacteria from the water samples on agar plates. Ultimately, this helps determine when the water is safe for drinking, and are compared against the WADI's measurements to test the reliability of the device.

Reducing Risk of Salmonellosis through Egg Decontamination Processes.

PubMed

Keerthirathne, Thilini Piushani; Ross, Kirstin; Fallowfield, Howard; Whiley, Harriet

2017-03-22

Eggs have a high nutritional value and are an important ingredient in many food products. Worldwide foodborne illnesses, such as salmonellosis linked to the consumption of eggs and raw egg products, are a major public health concern. This review focuses on previous studies that have investigated the procedures for the production of microbiologically safe eggs. Studies exploring pasteurization and decontamination methods were investigated. Gamma irradiation, freeze drying, hot air, hot water, infra-red, atmospheric steam, microwave heating and radiofrequency heating are all different decontamination methods currently considered for the production of microbiologically safe eggs. However, each decontamination procedure has different effects on the properties and constituents of the egg. The pasteurization processes are the most widely used and best understood; however, they influence the coagulation, foaming and emulsifying properties of the egg. Future studies are needed to explore combinations of different decontamination methods to produce safe eggs without impacting the protein structure and usability. Currently, eggs which have undergone decontamination processes are primarily used in food prepared for vulnerable populations. However, the development of a decontamination method that does not affect egg properties and functionality could be used in food prepared for the general population to provide greater public health protection.

Reducing Risk of Salmonellosis through Egg Decontamination Processes

PubMed Central

Keerthirathne, Thilini Piushani; Ross, Kirstin; Fallowfield, Howard; Whiley, Harriet

2017-01-01

Eggs have a high nutritional value and are an important ingredient in many food products. Worldwide foodborne illnesses, such as salmonellosis linked to the consumption of eggs and raw egg products, are a major public health concern. This review focuses on previous studies that have investigated the procedures for the production of microbiologically safe eggs. Studies exploring pasteurization and decontamination methods were investigated. Gamma irradiation, freeze drying, hot air, hot water, infra-red, atmospheric steam, microwave heating and radiofrequency heating are all different decontamination methods currently considered for the production of microbiologically safe eggs. However, each decontamination procedure has different effects on the properties and constituents of the egg. The pasteurization processes are the most widely used and best understood; however, they influence the coagulation, foaming and emulsifying properties of the egg. Future studies are needed to explore combinations of different decontamination methods to produce safe eggs without impacting the protein structure and usability. Currently, eggs which have undergone decontamination processes are primarily used in food prepared for vulnerable populations. However, the development of a decontamination method that does not affect egg properties and functionality could be used in food prepared for the general population to provide greater public health protection. PMID:28327524

Medical abortion: understanding perspectives of rural and marginalized women from rural South India.

PubMed

Sri, B Subha; Ravindran, T K Sundari

2012-09-01

To understand how rural and other groups of marginalized women define safe abortion; their perspectives and concerns regarding medical abortion (MA); and what factors affect their access to safe abortion. Focus group discussions were held with various groups of rural and marginalized women in Tamil Nadu to understand their perspectives and concerns on abortion, especially MA. Nearly a decade after mifepristone was approved for abortion in India, most study participants had never heard of MA. When they learned of the method, most preferred it over other methods of abortion. The women also had questions and concerns about the method and recommendations on how services should be provided. Their definition of a "safe abortion" included criteria beyond medical safety. They placed a high priority on "social safety," including confidentiality and privacy. In their view, factors affecting access to safe abortion and choice of provider included cost, assurance of secrecy, promptness of service provision, and absence of provider gatekeeping and provider-imposed conditions for receiving services. Women's preference for MA shows the potential of this technology to address the problem of unsafe abortion in India. Women need better access to information and services to realize this potential, however. Women's preferences regarding information dissemination and service provision need to be taken into account if policies and programs are to be truly responsive to the needs of marginalized women. Copyright © 2012. Published by Elsevier Ireland Ltd.

Patient Involvement in Safe Delivery: A Qualitative Study.

PubMed

Olfati, Forozun; Asefzadeh, Saeid; Changizi, Nasrin; Keramat, Afsaneh; Yunesian, Masud

2015-09-28

Patient involvement in safe delivery planning is considered important yet not widely practiced. The present study aimed at identifythe factors that affect patient involvementin safe delivery, as recommended by parturient women. This study was part of a qualitative research conducted by content analysis method and purposive sampling in 2013.The data were collected through 63 semi-structured interviews in4 hospitalsand analyzed using thematic content analysis. The participants in this research were women before discharge and after delivery. Findings were analyzed using Colaizzi's method. Four categories of factors that could affect patient involvement in safe delivery emerged from our analysis: patient-related (true and false beliefs, literacy, privacy, respect for patient), illness-related (pain, type of delivery, patient safety incidents), health care professional-relatedand task-related factors (behavior, monitoring &training), health care setting-related (financial aspects, facilities). More research is needed to explore the factors affecting the participation of mothers. It is therefore, recommended to: 1) take notice of mother education, their husbands, midwives and specialists; 2) provide pregnant women with insurance coverage from the outset of pregnancy, especially during prenatal period; 3) form a labor pain committee consisting of midwives, obstetricians, and anesthesiologists in order to identify the preferred painless labor methods based on the existing facilities and conditions, 4) carry out research on observing patients' privacy and dignity; 5) pay more attention on the factors affecting cesarean.

Safety and efficacy of endoscopic submucosal dissection using IT knife nano with clip traction method for early esophageal squamous cell carcinoma.

PubMed

Kitagawa, Yoshiyasu; Suzuki, Takuto; Hara, Taro; Yamaguchi, Taketo

2018-01-01

Although endoscopic submucosal dissection (ESD) is an accepted and established treatment for early esophageal squamous cell carcinoma (EESCC), it is technically difficult, time consuming, and less safe than endoscopic mucosal resection. To perform ESD safely and more efficiently, we proposed a new technique of esophageal ESD using an IT knife nano with the clip traction method. This study aimed to evaluate the efficacy and safety of ESD using this new technique. We retrospectively reviewed all consecutive cases of esophageal ESD performed using an IT knife nano with the clip traction method at our hospital between March 2013 and January 2017. Therapeutic efficacy and safety were also assessed. A total of 103 patients underwent esophageal ESD using the IT knife nano with the clip traction method. In all cases, we performed en bloc resection. Complete resection was achieved in 100 cases (97.1%). The median operating time was 40 (range 13-230) min. No cases of perforation or delayed bleeding occurred. Although two cases (2.0%) of mediastinal emphysema occurred without visible perforation at endoscopy, all were successfully managed conservatively. The new technique of esophageal ESD using the IT knife nano with the clip traction method appears to be feasible, effective, and safe for EESCC treatment.

"From safe source to safe sink" development of colorimetric assay for gabapentin in bulk drug and capsules using naturally derived genipin.

PubMed

Winotapun, Weerapath; Kongpakwattana, Khachen; Dejpittayanunt, Sirirat; Pathomcharoensukchai, Suwaparp; Suksaran, Udomluck; Nuntharatanapong, Nopparat; Rojanarata, Theerasak

2012-09-15

A novel colorimetric assay for gabapentin in bulk drug and capsules has been developed via a safety-and-sustainability concerning concept. The method relied on the reaction of primary amino group of drug with non-toxic and eco-friendly genipin in totally aqueous medium to form the blue product which was subsequently measured by visible spectrophotometry at 590 nm. Under the optimized conditions, Beer's law was obeyed in the concentration range of 0.15-0.50 mM (r(2)=0.9998). It was accurate, precise and insensitive to the interferences from all related compounds specified in the United States Pharmacopeia as well as commonly used excipients. Furthermore, it gave the assay results in agreement with the pharmacopeial chromatographic method. Owing to the environmental concern and responsibility, a fast and facile method was also proposed for the treatment of waste generated from the assay based on the decoloration by using gypsum as a cheap and commonly available adsorbent. After the treatment, more than 95% of the initial blue product was removed from the waste solution and the treated waste was proven to be safe for aquatic organisms, as studied in brine shrimp and guppy fishes. Therefore, this work not only reports for the first time the application of naturally derived genipin to drug analysis, but also presents a new and contemporary paradigm that illustrates the fully benign-by-design development of the analytical methodologies in the era of Green Chemistry, starting from the safe source of reagents toward the safe sink when waste is released into the environment. Copyright © 2012 Elsevier B.V. All rights reserved.

Safe teleradiology: information assurance as project planning methodology

NASA Astrophysics Data System (ADS)

Collmann, Jeff R.; Alaoui, Adil; Nguyen, Dan; Lindisch, David

2003-05-01

This project demonstrates use of OCTAVE, an information security risk assessment method, as an approach to the safe design and planning of a teleradiology system. By adopting this approach to project planning, we intended to provide evidence that including information security as an intrinsic component of project planning improves information assurance and that using information assurance as a planning tool produces and improves the general system management plan. Several considerations justify this approach to planning a safe teleradiology system. First, because OCTAVE was designed as a method for retrospectively assessing and proposing enhancements for the security of existing information management systems, it should function well as a guide to prospectively designing and deploying a secure information system such as teleradiology. Second, because OCTAVE provides assessment and planning tools for use primarily by interdisciplinary teams from user organizations, not consultants, it should enhance the ability of such teams at the local level to plan safe information systems. Third, from the perspective of sociological theory, OCTAVE explicitly attempts to enhance organizational conditions identified as necessary to safely manage complex technologies. Approaching information system design from the perspective of information security risk management proactively integrates health information assurance into a project"s core. This contrasts with typical approaches that perceive "security" as a secondary attribute to be "added" after designing the system and with approaches that identify information assurance only with security devices and user training. The perspective of health information assurance embraces so many dimensions of a computerized health information system"s design that one may successfully deploy a method for retrospectively assessing information security risk as a prospective planning tool. From a sociological perspective, this approach enhances the general conditions as well as establishes specific policies and procedures for reliable performance of health information assurance.

Polymer adhesion predictions for oral dosage forms to enhance drug administration safety. Part 2: In vitro approach using mechanical force methods.

PubMed

Drumond, Nélio; Stegemann, Sven

2018-06-01

Predicting the potential for unintended adhesion of solid oral dosage forms (SODF) to mucosal tissue is an important aspect that should be considered during drug product development. Previous investigations into low strength mucoadhesion based on particle interactions methods provided evidence that rheological measurements could be used to obtain valid predictions for the development of SODF coatings that can be safely swallowed. The aim of this second work was to estimate the low mucoadhesive strength properties of different polymers using in vitro methods based on mechanical forces and to identify which methods are more precise when measuring reduced mucoadhesion. Another aim was to compare the obtained results to the ones achieved with in vitro particle interaction methods in order to evaluate which methodology can provide stronger predictions. The combined results correlate between particle interaction methods and mechanical force measurements. The polyethylene glycol grades (PEG) and carnauba wax showed the lowest adhesive potential and are predicted to support safe swallowing. Hydroxypropyl methylcellulose (HPMC) along with high molecular grades of polyvinylpyrrolidone (PVP) and polyvinyl alcohol (PVA) exhibited strong in vitro mucoadhesive strength. The combination of rheological and force tensiometer measurements should be considered when assessing the reduced mucoadhesion of polymer coatings to support safe swallowing of SODF. Copyright © 2018 Elsevier B.V. All rights reserved.

Safe and inclusive research practices for qualitative research involving people with dementia: A review of key issues and strategies.

PubMed

Novek, Sheila; Wilkinson, Heather

2017-01-01

Aim Developing strategies to ensure the safe participation of people with dementia in research is critical to support their wider inclusion in research and to advance knowledge in the areas of dementia policy and practice. Objectives This literature review synthesizes and critically appraises different approaches to promote the safe participation of people with dementia in qualitative research. Methods Two databases were searched for articles that discuss the methodological or ethical aspects of qualitative research involving people with dementia. We did not focus on informed consent or ethical review processes as these have been reviewed elsewhere. Findings Key issues that impact participant safety include: language, gatekeepers, the research relationship, communication, dealing with distress, knowledge dissemination, and researcher skills. Conclusion By synthesizing different approaches to safety and highlighting areas of debate, we hope to advance discussion and to contribute to the development of inclusive research methods.

An exploratory study of the role of trust in medication management within mental health services.

PubMed

Maidment, Ian D; Brown, Patrick; Calnan, Michael

2011-08-01

To develop understandings of the nature and influence of trust in the safe management of medication within mental health services. Mental health services in the UK. Qualitative methods were applied through focus groups across three different categories of service user--older adult, adults living in the community and forensic services. An inductive thematic analysis was carried out, using the method of constant comparison derived from grounded theory. Participants' views on the key factors influencing trust and the role of trust in safe medication management. The salient factors impacting trust were: the therapeutic relationship; uncertainty and vulnerability; and social control. Users of mental health services may be particularly vulnerable to adverse events and these can damage trust. Safe management of medication is facilitated by trust. However, this trust may be difficult to develop and maintain, exposing service users to adverse events and worsening adherence. Practice and policy should be oriented towards developing trust.

Unsafe abortion: the silent scourge.

PubMed

Grimes, David A

2003-01-01

An estimated 19 million unsafe abortions occur worldwide each year, resulting in the deaths of about 70,000 women. Legalization of abortion is a necessary but insufficient step toward improving women's health. Without skilled providers, adequate facilities and easy access, the promise of safe, legal abortion will remain unfulfilled, as in India and Zambia. Both suction curettage and pharmacological abortion are safe methods in early pregnancy; sharp curettage is inferior and should be abandoned. For later abortions, either dilation and evacuation or labour induction are appropriate. Hysterotomy should not be used. Timely and appropriate management of complications can reduce morbidity and prevent mortality. Treatment delays are dangerous, regardless of their origin. Misoprostol may reduce the risks of unsafe abortion by providing a safer alternative to traditional clandestine abortion methods. While the debate over abortion will continue, the public health record is settled: safe, legal, accessible abortion improves health.

The ‘cut and push’ technique: is it really safe?

PubMed Central

Peacock, Oliver; Singh, Rajeev; Cole, Andrew; Speake, William

2012-01-01

Percutaneous endoscopic gastrostomy (PEG) feeding is routinely used as an endoscopic and effective method for providing enteral nutrition in those whose oral access has been diminished or lost. One technique for removal of the PEG is cutting the tube at the skin level and allowing the tube and internal flange to pass spontaneously. This is known as the ‘cut and push’ method. Several studies have concluded that the ‘cut and push’ method is a safe and cost-effective method. This case demonstrates a rare cause of small bowel obstruction following the ‘cut and push’ method for PEG replacement, with only a few other cases been reported. This method of removal should be avoided in patients with previous abdominal surgery. It is important that the PEG flange is retrieved endoscopically or an alternative PEG tube (designed to be completely removed through the skin) is used to prevent this complication occurring in such individuals. PMID:22847571

Counter traction makes endoscopic submucosal dissection easier.

PubMed

Oyama, Tsuneo

2012-11-01

Poor counter traction and poor field of vision make endoscopic submucosal dissection (ESD) difficult. Good counter traction allows dissections to be performed more quickly and safely. Position change, which utilizes gravity, is the simplest method to create a clear field of vision. It is useful especially for esophageal and colon ESD. The second easiest method is clip with line method. Counter traction made by clip with line accomplishes the creation of a clear field of vision and suitable counter traction thereby making ESD more efficient and safe. The author published this method in 2002. The name ESD was not established in those days; the name cutting endoscopic mucosal resection (EMR) or EMR with hook knife was used. The other traction methods such as external grasping forceps, internal traction, double channel scope, and double scopes method are introduced in this paper. A good strategy for creating counter traction makes ESD easier.

C-SAFE: A Computer-Delivered Sexual Health Promotion Program for Latinas.

PubMed

Klein, Charles H; Kuhn, Tamara; Altamirano, Midori; Lomonaco, Carmela

2017-07-01

This article describes the development and evaluation of C-SAFE (Sexual Awareness for Everyone), a computer-delivered sexual health promotion program for Latinas. We first describe the process of adapting an evidence-based, group-level intervention into an individually administered computer-delivered program. We then present the methods and results of a randomized control trial with 321 Latinas in California and Florida to test C-SAFE's preliminary efficacy in reducing sexual health risk. We found no statistically significant differences between the two conditions at a six-month follow-up in terms of sexual behaviors or attitudes toward sexually transmitted infections and condoms, although C-SAFE women reported fewer days in the past month when their mental health was not good (p = .02). C-SAFE condition women also reported more satisfaction than control condition women in their assessment of information presentation (on a scale of 1 = poor and 5 = excellent; C-SAFE = 4.45 vs. control = 4.25, p = .053) and having learned something new (C-SAFE = 95.1% vs. control = 79.3%, χ 2 < 0.001), with utility of content for Latinas approaching significance (C-SAFE = 4.50 vs. control = 4.31, p = .058). In conclusion we discuss the importance of teachable moments, matching of delivery modalities to implementation contexts, and possible directions for evidence-based sexual health promotion programs given the current sexual health landscape.

Thermal injury through intraradicular heat transfer using ultrasonic devices: precautions and practical preventive strategies.

PubMed

Gluskin, Alan H; Ruddle, Clifford J; Zinman, Edwin J

2005-09-01

The use of ultrasonic energy is a highly efficient method of removing obstructions and cements within the root canal space when re-treatment or rehabilitation of that ultrasonic energy dislodges and removes cemented objects from the bonded interface of the canal wall. When using this method, there is less potential for structural loss or root damage and significantly less operator stress than when using other methods. There is little evidence in published research of the considerable heat transfer that occurs during use of ultrasonic devices to remove posts, pastes and separated instruments in teeth. The authors present three cases of patients who experienced serious burn injuries during application of ultrasonic energy for restorative dentistry. The authors also offer techniques and strategies for safe and effective use of ultrasonic devices. On the basis of the best available evidence, the authors recommend strategies to provide safe and effective therapy while using ultrasonic devices in intraradicular obstruction removal. The intent of the suggested protocols is to provide advanced and sophisticated therapies in a safe and regulated manner with patient safety as an overriding priority.

Endoscopic ampullectomy: a practical guide

PubMed Central

Bassan, Milan

2012-01-01

Endoscopic ampullectomy is a minimally invasive method of treating superficial lesions of the ampulla of Vater. With careful patient selection and lesion assessment it is a safe and efficacious therapeutic procedure that can obviate the need for potentially major surgical intervention. Strategies for safe and successful endoscopic ampullectomy with a focus on resection technique and recognition and management of complications are presented. PMID:22586547

What's Wrong with Bribery? An Example Utilizing Access to Safe Drinking Water

ERIC Educational Resources Information Center

Dhooge, Lucien J.

2013-01-01

This case study examines the role of bribery in the global marketplace through an example involving access to safe drinking water in the developing world. Parts II and III set out the objectives and methods of classroom delivery for the case study. Part IV is the background reading relating to bribery with particular emphasis on the Foreign…

Solvent cleaning system and method for removing contaminants from solvent used in resin recycling

DOEpatents

Bohnert, George W [Harrisonville, MO; Hand, Thomas E [Lee's Summit, MO; DeLaurentiis, Gary M [Jamestown, CA

2009-01-06

A two step solvent and carbon dioxide based system that produces essentially contaminant-free synthetic resin material and which further includes a solvent cleaning system for periodically removing the contaminants from the solvent so that the solvent can be reused and the contaminants can be collected and safely discarded in an environmentally safe manner.

Healthy and Safe School Environment, Part I: Results from the School Health Policies and Programs Study 2006

ERIC Educational Resources Information Center

Jones, Sherry Everett; Fisher, Carolyn J.; Greene, Brenda Z.; Hertz, Marci F.; Pritzl, Jane

2007-01-01

Background: Policies set at the state, district, and school levels can support and enhance a healthy and safe school environment. Methods: The Centers for Disease Control and Prevention conducts the School Health Policies and Programs Study every 6 years. In 2006, computer-assisted telephone interviews or self-administered mail questionnaires were…

Using Floquet periodicity to easily calculate dispersion curves and wave structures of homogeneous waveguides

NASA Astrophysics Data System (ADS)

Hakoda, Christopher; Rose, Joseph; Shokouhi, Parisa; Lissenden, Clifford

2018-04-01

Dispersion curves are essential to any guided-wave-related project. The Semi-Analytical Finite Element (SAFE) method has become the conventional way to compute dispersion curves for homogeneous waveguides. However, only recently has a general SAFE formulation for commercial and open-source software become available, meaning that until now SAFE analyses have been variable and more time consuming than desirable. Likewise, the Floquet boundary conditions enable analysis of waveguides with periodicity and have been an integral part of the development of metamaterials. In fact, we have found the use of Floquet boundary conditions to be an extremely powerful tool for homogeneous waveguides, too. The nuances of using periodic boundary conditions for homogeneous waveguides that do not exhibit periodicity are discussed. Comparisons between this method and SAFE are made for selected homogeneous waveguide applications. The COMSOL Multiphysics software is used for the results shown, but any standard finite element software that can implement Floquet periodicity (user-defined or built-in) should suffice. Finally, we identify a number of complex waveguides for which dispersion curves can be found with relative ease by using the periodicity inherent to the Floquet boundary conditions.

Safe and Affordable Drinking Water for Developing Countries

NASA Astrophysics Data System (ADS)

Gadgil, Ashok

2008-09-01

Safe drinking water remains inaccessible for about 1.2 billion people in the world, and the hourly toll from biological contamination of drinking water is 200 deaths mostly among children under five years of age. This chapter summarizes the need for safe drinking water, the scale of the global problem, and various methods tried to address it. Then it gives the history and current status of an innovation ("UV Waterworks™") developed to address this major public health challenge. It reviews water disinfection technologies applicable to achieve the desired quality of drinking water in developing countries, and specifically, the limitations overcome by one particular invention: UV Waterworks. It then briefly describes the business model and financing option than is accelerating its implementation for affordable access to safe drinking water to the unserved populations in these countries. Thus this chapter describes not only the innovation in design of a UV water disinfection system, but also innovation in the delivery model for safe drinking water, with potential for long term growth and sustainability.

Safe Manual Jettison

NASA Technical Reports Server (NTRS)

Barton, Jay

2008-01-01

In space, the controlled release of certain cargoes is no less useful than the maritime jettisons from which they take their name but is also much more dangerous. Experience has shown that jettisons can be performed safely, but the process is complicated with the path to performing a jettison taking months or even years. In the background, time is also required to write procedures, train the crew, configure the vehicle, and many other activities. This paper outlines the current process used by the National Aeronautics and Space Administration (NASA) for manual jettisons, detailing the methods used to assure that the jettisons and the jettisoned objects are as safe as achievable and that the crew is adequately trained to be able to affect the safe jettison. The goal of this paper is not only to capture what it takes to perform safe jettisons in the near Earth environment but to extrapolate this knowledge to future space exploration scenarios that will likely have Extravehicular Activity (EVA) and International Partner (IP) interfaces.

Can active proton interrogation find shielded nuclear threats at human-safe radiation levels?

NASA Astrophysics Data System (ADS)

Liew, Seth Van

2017-05-01

A new method of low-dose proton radiography is presented. The system is composed of an 800 MeV proton source, bending magnets, and compact detectors, and is designed for drive-through cargo scanning. The system has been simulated using GEANT4. Material identification algorithms and pixel sorting methods are presented that allow the system to perform imaging at doses low enough to scan passenger vehicles and people. Results are presented on imaging efficacy of various materials and cluttered cargoes. The identification of shielded nuclear materials at human-safe doses has been demonstrated.

Improving safety climate through a communication and recognition program for construction: a mixed-methods study

PubMed Central

Sparer, Emily H; Catalano, Paul J; Herrick, Robert F; Dennerlein, Jack T

2016-01-01

Objectives This study aimed to evaluate the efficacy of a safety communication and recognition program (B-SAFE), designed to encourage improvement of physical working conditions and hazard reduction in construction. Methods A matched pair cluster randomized controlled trial was conducted on eight worksites (four received the B-SAFE intervention, four served as control sites) for approximately five months per site. Pre- and post-exposure worker surveys were collected at all sites (N=615, pre-exposure response rate of 74%, post-exposure response rate of 88%). Multi-level mixed-effect regression models evaluated the effect of B-SAFE on safety climate as assessed from surveys. Focus groups (N=6–8 workers/site) were conducted following data collection. Transcripts were coded and analyzed for thematic content using Atlas.ti (version 6). Results The mean safety climate score at intervention sites, as measured on a 0–50 point scale, increased 0.5 points (1%) between pre- and post-B-SAFE exposure, compared to control sites that decreased 0.8 points (1.6%). The intervention effect size was 1.64 (3.28%) (P-value=0.01) when adjusted for month the worker started on-site, total length of time on-site, as well as individual characteristics (trade, title, age, and race/ethnicity). At intervention sites, workers noted increased levels of safety awareness, communication, and teamwork compared to control sites. Conclusions B-SAFE led to many positive changes, including an improvement in safety climate, awareness, teambuilding, and communication. B-SAFE was a simple intervention that engaged workers through effective communication infrastructures and had a significant, positive effect on worksite safety. PMID:27158914

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.

Occurrence and exposure to polycyclic aromatic hydrocarbons in kindling-free-charcoal grilled meat products in Taiwan.

PubMed

Kao, Tsai Hua; Chen, Shaun; Huang, Chun Wei; Chen, Chia Ju; Chen, Bing Huei

2014-09-01

This study aimed to determine the contents of 16 PAHs in kindling-free-charcoal grilled meat and seafood products by GC-MS coupled with a QuEChERS method, and estimate the potential risk associated with consumption of those products in Taiwan. Results showed that the total PAHs contents ranged from 6.3±0.9 to 238.8±8.3 ng/g in poultry meat, 0.1±0.0-547.5±12.2 ng/g in red meat, and 6.6±1.4-249.7±6.4 ng/g in seafood products. Among various PAHs, the highly carcinogenic benzo[a]pyrene was detected in chicken breast grilled at 84°C (30 min), chicken heart at 100°C (26 min), chicken drumstick at 74°C (20 min), duck drumstick at 85°C (40 min), and lamb steak at 88°C (12 min), with its level amounting to 1.3±0.0, 2.4±0.1, 4.0±1.3, 3.1±0.0, and 5.8±0.5 ng/g, respectively. The generation of PAHs was associated with grilling time, temperature and fat content. Risk assessment of dietary exposure to PAHs revealed toxicity equivalent to range from ND - 6.174±0.505 μg/g and margin of exposure was >10,000, which agreed with the EFSA's definition of low public health concern. The lifelong average daily PAHs intake was higher for adults than for elderly people in Taiwan, however, consumption of kindling-free-charcoal grilled meat should not be a public health concern based on cancer risk potency. Copyright © 2014 Elsevier Ltd. All rights reserved.

Positive effects of an oil adjuvant on efficacy, dissipation and safety of pyrimethanil and boscalid on greenhouse strawberry.

PubMed

Wang, Zhiwei; Wang, Xinquan; Cang, Tao; Zhao, Xueping; Wu, Shenggan; Qi, Peipei; Wang, Xiangyun; Xu, Xiahong; Wang, Qiang

2018-05-21

Methylated vegetable oil adjuvants can enhance initial deposition and decrease the required dosages of pesticides sprayed on plants, so an oil adjuvant mixed with fungicides were used to prevent and control gray mold in greenhouse strawberry. As the persistence and dietary exposure risks from fungicides on strawberries after using adjuvants have not been assessed, the efficacy, dissipation and safety of pyrimethanil and boscalid in the presence and absence of a methylated vegetable oil adjuvant were evaluated. To better describe the actual use of fungicides in greenhouse strawberry, twice repeated application of fungicides were conducted follower by an optimized QuEChERS pre-treatment method. When applied at 60% of their recommended dosages with the adjuvant, the efficacy of pyrimethanil and boscalid for gray mold was similar to that shown by the treatment of 100% fungicides in absence of the adjuvant based on Duncan's Multiple-Range test, and their average residues increased to 89.0% and 89.3%, respectively. The adjuvant enhanced the accumulation effect of pyrimethanil residue by 31.7% after repeated applications, and the half-lives were similar (5.2 and 4.2 d). The adjuvant had comparable accumulation effects (1.75 and 1.83) and similar half-lives (5.4 and 5.5 d) for boscalid. In absence of adjuvant, the risk quotients (RQs) of pyrimethanil (0.41 and 0.33) and boscalid (0.49 and 0.63) after twice applications at pre-harvest interval were lower than 1. Adding the methylated vegetable oil adjuvant to fungicides would result in unprolonging half-life and acceptably low dietary exposure risk on strawberries, but lower dosage of fungicides were used. Copyright © 2018. Published by Elsevier Inc.

Dietary exposure to pesticide residues from foods of plant origin and drinks in Lebanon.

PubMed

Nasreddine, Lara; Rehaime, Maria; Kassaify, Zeina; Rechmany, Roula; Jaber, Farouk

2016-08-01

This study assesses the dietary exposure of Lebanese adults to 47 pesticide residues from both foods of plant origin and drinks. The study was conducted using the Total Diet Study protocol in two different areas of Lebanon: Greater Beirut (urban) and Keserwan (semi-rural). A total of 1860 individual foods were collected, prepared, and cooked prior to analysis. Composite samples of similar foods were analyzed, following the QuEChERS Multiresidue method. Eighteen residues were detected/quantified on at least one composite sample, with 66.7 % of the results being quantifiable and 33.3 % detectable. Quantifiable levels ranged between 10.3 and 208 μg/kg. For the composite samples where residues were detected, 55 % had one residue, while 45 % had 2-4 residues. The most frequently detected/quantified pesticide residues included Chlorpyrifos, Procymidone, Primiphos methyl, Dimethoate, and Dieldrin. The dietary exposure assessment was conducted using the deterministic approach with two scenarios: (1) the lower bound (LB) approach and (2) the upper bound (UB) approach. Using the LB approach, mean estimated daily exposures were far below the acceptable daily intakes (ADIs) for all investigated residues. Using the UB approach, which tends to overestimate exposure, mean estimated daily exposures were below the ADIs for all residues except for Dieldrin (semi-rural: 128.7 % ADI; urban: 100.7 % ADI). Estimates of mean exposure to Diazinon reached 50.3 % of ADI in the urban diet and 61.9 % in the semi-rural diet. Findings of this study identify specific pesticide residues as monitoring priorities for which more comprehensive and sensitive analyses are needed in order to refine exposure assessment.

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.

Safe Sleep Practices of Kansas Birthing Hospitals

PubMed Central

Ahlers-Schmidt, Carolyn R.; Schunn, Christy; Sage, Cherie; Engel, Matthew; Benton, Mary

2018-01-01

Background Sleep-related death is tied with congenital anomalies as the leading cause of infant mortality in Kansas, and external risk factors are present in 83% of these deaths. Hospitals can impact caregiver intentions to follow risk-reduction strategies. This project assessed the current practices and policies of Kansas hospitals with regard to safe sleep. Methods A cross-sectional survey of existing safe sleep practices and policies in Kansas hospitals was performed. Hospitals were categorized based on reported delivery volume and data were compared across hospital sizes. Results Thirty-one of 73 (42%) contacted hospitals responded. Individual survey respondents represented various hospital departments including newborn/well-baby (68%), neonatal intensive care unit (3%) and other non-nursery departments or administration (29%). Fifty-eight percent of respondents reported staff were trained on infant safe sleep; 44% of these held trainings annually. High volume hospitals tended to have more annual training than low or mid volume birth hospitals. Thirty-nine percent reported a safe sleep policy, though most of these (67%) reported never auditing compliance. The top barrier to safe sleep education, regardless of delivery volume, was conflicting patient and family member beliefs. Conclusions Hospital promotion of infant safe sleep is being conducted in Kansas to varying degrees. High and mid volume birth hospitals may need to work more on formal auditing of safe sleep practices, while low volume hospitals may need more staff training. Low volume hospitals also may benefit from access to additional caregiver education materials. Finally, it is important to note hospitals should not be solely responsible for safe sleep education. PMID:29844848

The Oxygen Flask Method

ERIC Educational Resources Information Center

Boulton, L. H.

1973-01-01

Discusses application of Schoniger's method of quantitative organic elemental analysis in teaching of qualitative analysis of the halogens, nitrogen, sulphur, and phosphorus. Indicates that the oxygen flask method is safe and suitable for both high school and college courses because of simple apparatus requirements. (CC)

Women's perceptions about abortion in their communities: perspectives from western Kenya.

PubMed

Marlow, Heather M; Wamugi, Sylvia; Yegon, Erick; Fetters, Tamara; Wanaswa, Leah; Msipa-Ndebele, Sinikiwe

2014-05-01

Unsafe abortion in Kenya is a leading cause of maternal morbidity and mortality. In October 2012, we sought to understand the methods married women aged 24-49 and young, unmarried women aged ≤ 20 used to induce abortion, the providers they utilized and the social, economic and cultural norms that influenced women's access to safe abortion services in Bungoma and Trans Nzoia counties in western Kenya. We conducted five focus groups with young women and five with married women in rural and urban communities in each county. We trained local facilitators to conduct the focus groups in Swahili or English. All focus groups were audiotaped, transcribed, translated, computerized, and coded for analysis. Abortion outside public health facilities was mentioned frequently. Because of the need for secrecy to avoid condemnation, uncertainty about the law, and perceived higher cost of safer abortion methods, women sought unsafe abortions from community midwives, drug sellers and/or untrained providers at lower cost. Many groups believed that abortion was safer at higher gestational ages, but that there was no such thing as a safe abortion method. Our aim was to inform the design of a community-based intervention on safe abortion for women. Barriers to seeking safe services such as high cost, perceived illegality, and fear of insults and abuse at public facilities among both age groups must be addressed. Copyright © 2014 Reproductive Health Matters. Published by Elsevier Ltd. All rights reserved.

The Nelaton Catheter Guard for Safe and Effective Placement of Subdural Drain for Two-Burr-Hole Trephination in Chronic Subdural Hematoma: A Technical Note.

PubMed

Fichtner, Jens; Beck, Jürgen; Raabe, A; Stieglitz, Lennart Henning

2015-09-01

For chronic subdural hematoma, placement of a Blake drain with a two-burr-hole craniotomy is often preferred. However, the placement of such drains carries the risk of penetrating the brain surface or damaging superficial venous structures. To describe the use of a Nelaton catheter for the placement of a subdural drain in two-burr-hole trephination for chronic subdural hematoma. A Nelaton catheter was used to guide placement of a Blake drain into the subdural hematoma cavity and provide irrigation of the hematoma cavity. With the two-burr-hole method, the Nelaton catheter could be removed easily via the frontal burr hole after the Blake drain was in place. We used the Nelaton catheters in many surgical procedures and found it a safe and easy technique. This method allows the surgeon to safely direct the catheter into the correct position in the subdural space. This tool has two advantages. First, the use of a small and flexible Nelaton catheter is a safe method for irrigation of a chronic subdural hematoma cavity. Second, in comparison with insertion of subdural drainage alone through a burr hole, the placement of the Nelaton catheter in subdural space is easier and the risk of damaging relevant structures such as cortical tissue or bridging veins is lower. Thus this technique may help to avoid complications when placing a subdural drain. Georg Thieme Verlag KG Stuttgart · New York.

Cost-effectiveness analyses of self-harm strategies aimed at reducing the mortality of pesticide self-poisonings in Sri Lanka: a study protocol

PubMed Central

Madsen, Lizell Bustamante; Eddleston, Michael; Hansen, Kristian Schultz; Pearson, Melissa; Agampodi, Suneth; Jayamanne, Shaluka; Konradsen, Flemming

2015-01-01

Introduction An estimated 803 900 people worldwide died as a result of self-harm in 2012. The deliberate ingestion of pesticides has been identified as the method most frequently used to commit fatal self-harm globally. In Sri Lanka, it is estimated that up to 60% of all suicides are committed using this method. The aim of the present study is to assess the cost-effectiveness of an ongoing safe storage intervention currently taking place in a rural Sri Lankan district and to model the cost-effectiveness of implementing the safe storage intervention as well as four potential interventions (legislative, medical management, follow-up contact and mobile phone contact) on a national level. Methods and analysis Study design for all the strategies is a cost-effectiveness analysis. A governmental perspective is adopted. The time horizon for tracking the associated costs and health outcomes of the safe storage intervention on district level runs over 3 years. The time horizon is extended to 5 years when modelling a full national roll-out of the respective interventions. The discounting of costs and health outcomes are undertaken at the recommended real rate of 3%. Threshold analyses of the modelled strategies are employed to assess the strategies potential for cost-effectiveness, running scenarios with health outcome improvements ranging from 1% to 100%. Sensitivity analyses are also performed. The main outcome measures of the safe storage intervention are incremental cost-effectiveness ratios. Ethics and dissemination Ethical approval was granted for the safe storage project from the University of Peradeniya, Sri Lanka, in March of 2008. An amendment for the present study was granted from Rajarata University of Sri Lanka in November of 2013. Findings will be disseminated to public and private stakeholders in local and national government in Sri Lanka as well as the wider academic audience through peer-reviewed publications and international conferences. Trial registration number The safe storage cluster trial is registered with the Clinical Trials, ref: NCT1146496 (http://clinicaltrialsfeeds.org/clinical-trials/show/NCT1146496). PMID:25724984

Safe Injection Practices in Primary Health Care Settings of Naxalbari Block, Darjeeling District, West Bengal.

PubMed

Chaudhuri, Sudip Banik; Ray, Kuntala

2016-01-01

Unsafe injection can transmit many diseases to patients, injection providers and healthy people of community. To find out critical steps whether executed according to recommended best practice methods, availability of equipments in health facilities for safe injection practices and some important steps of waste disposal methods. This facility-based cross-sectional observational study was conducted among 30 Auxiliary nurse midwives (ANM) & 27 nursing staffs (NS) to assess certain aspects of their practice while administrating injection and disposal of the disposables. Health facilities were also observed to asses necessary equipments of safe injection and waste disposal methods. Among the health workers 93.3% ANM and 100% NS took sterile syringe from sterile unopened packet, all of the study subjects washed hand before giving injection, 13.3% of ANMs and 8% of NS are fully vaccinated against Hep B, 53.3% of ANM and all NS are practices non recapping. Only 13.33% sub centres along with PHC & BPHC had at least one puncture resistant leak proof container, 86.7% sub centres, PHC are free from loose needles. Transport for off side treatment is the method of waste disposal in case of 73.3% cases sub centres, PHC & BPHC. There is need to educate, train and motivate service providers in proper methods of giving injection along with improve the adequacy of supply of required equipments.

A Survey of Knowledge, Attitude, and Practice of Consumers at a Tertiary Care Hospital Regarding the Disposal of Unused Medicines

PubMed Central

Sonowal, Supriya; Desai, Chetna; Kapadia, Jigar D.; Desai, Mira K.

2016-01-01

Objectives: To evaluate the knowledge, attitude and practice of consumers in India about disposal of unused medicines. Materials and Methods: A questionnaire comprising 11 questions evaluating the Knowledge (2), Attitude (3) and Practice (6) of unused medicines was prepared and pre validated before administering to 200 consumers of medicines attending the outpatient department of Civil Hospital Ahmedabad, a tertiary care teaching hospital in Western India. Requisite permissions from Institutional Ethics Committee and informed consent were obtained prior to recruiting them for the study. Responses were recorded, in Microsoft Excel® spreadsheet and evaluated for percentage response. Results: Majority of the respondents (136, 68%) stored unused medicines at home. Analgesics (26.5%) were the most common unused medicine stored. Safe disposal of medicine was considered necessary by majority respondents (160, 80%) for different reasons like prevention of illegal/unintended use (84, 42%), prevention of environmental pollution (32, 16%) or possible ADR caused by old drugs (54, 27%). Only 78 (39%) respondents were aware of appropriate methods of disposal. Disposal in household trash (61, 30.5%) was the most common method used. Majority of respondents felt the need for a facility or programme to collect unused medicines (152, 76%) and an increased awareness among consumers regarding hazards and methods of disposal of unused medicines (154, 77%). Conclusion: Majority of consumers are aware about the need for safe disposal of unused medicines. But the right attitude for and practice of safe disposal of medicines is lacking. A need for increased awareness regarding safe disposal of medicines is acknowledged by majority of consumers. PMID:28104967

Determination of cyclic volatile methylsiloxanes in personal care products by gas chromatography.

PubMed

Brothers, H M; Boehmer, T; Campbell, R A; Dorn, S; Kerbleski, J J; Lewis, S; Mund, C; Pero, D; Saito, K; Wieser, M; Zoller, W

2017-12-01

Organosiloxanes are prevalent in personal care products (PCPs) due to the desired properties they impart in the usage and application of such products. However, the European Chemical Agency (ECHA) has recently published restriction proposals on the amount of two cyclic siloxanes, octamethylcyclotetrasiloxane (D4) and decamethylcyclotetrasiloxane (D5), allowed in wash off products such as shampoos and conditioners which are discharged down the drain during consumer use. This legislation will require that reliable analytical methods are available for manufacturers and government agencies to use in documenting compliance with the restrictions. This article proposes a simple analytical method to enable accurate measurement of these compounds down to the circa 0.1 weight per cent level in PCPs. Although gas chromatography methods are reported in the literature for quantitation of D4 and D5 in several matrices including PCPs, the potential for generation of false positives due to contamination, co-elution and in situ generation of cyclic volatile methylsiloxanes (cVMS) is always present and needs to be controlled. This report demonstrates the applicability of using a combination of emulsion break, liquid-liquid extraction and silylation sample preparation followed by GC-FID analysis as a suitable means of analysing PCPs for specific cVMS. The reliability and limitations of such methodology were demonstrated through several round-robin studies conducted in the laboratories of a consortium of silicone manufacturers. In addition, this report presents examples of false positives encountered during development of the method and presents a comparative analysis between this method and a published QuEChERS sample preparation procedure to illustrate the potential for generation of false positives when an inappropriate approach is applied to determination of cVMS in personal care products. This report demonstrates that an approach to determine cVMS levels in personal care products is to perform an emulsion break on the sample, isolate the non-polar phase from the emulsion break and treat with a silylation reagent to abate potential in situ formation of cyclics during the course of GC-FID analysis. Round-robin studies conducted in laboratories representing multiple siloxane manufacturers demonstrated the reliability of the GC-FID method when measuring cVMS in PCPs down to circa 0.1%. © 2017 CES - Silicones Europe. International Journal of Cosmetic Science published by John Wiley & Sons Ltd on behalf of Society of Cosmetic Scientists and the Société Française de Cosmétologie.

Prediction of safe driving Behaviours based on health belief model: the case of taxi drivers in Bandar Abbas, Iran.

PubMed

Razmara, Asghar; Aghamolaei, Teamur; Madani, Abdoulhossain; Hosseini, Zahra; Zare, Shahram

2018-03-20

Road accidents are among the main causes of mortality. As safe and secure driving is a key strategy to reduce car injuries and offenses, the present research aimed to explore safe driving behaviours among taxi drivers based on the Health Belief Model (HBM). This study was conducted on 184 taxi drivers in Bandar Abbas who were selected based on a multiple stratified sampling method. Data were collected by a questionnaire comprised of a demographic information section along with the constructs of the HBM. Data were analysed by SPSS ver19 via a Pearson's correlation coefficient and multiple regressions. The mean age of the participants was 45.1 years (SD = 11.1). They all had, on average, 10.3 (SD = 7/5) years of taxi driving experience. Among the HBM components, cues to action and perceived benefits were shown to be positively correlated with safe driving behaviours, while perceived barriers were negatively correlated. Cues to action, perceived barriers and perceived benefits were shown to be the strongest predictors of a safe drivers' behaviour. Based on the results of this study in designing health promotion programmes to improve safe driving behaviours among taxi drivers, cues to action, perceived benefits and perceived barriers are important. Therefore, advertising, the design of information campaigns, emphasis on the benefits of safe driving behaviours and modification barriers are recommended.

Prioritization for conservation of northern European cattle breeds based on analysis of microsatellite data.

PubMed

Tapio, I; Värv, S; Bennewitz, J; Maleviciute, J; Fimland, E; Grislis, Z; Meuwissen, T H E; Miceikiene, I; Olsaker, I; Viinalass, H; Vilkki, J; Kantanen, J

2006-12-01

Northern European indigenous cattle breeds are currently endangered and at a risk of becoming extinct. We analyzed variation at 20 microsatellite loci in 23 indigenous, 3 old imported, and 9 modern commercial cattle breeds that are presently distributed in northern Europe. We measured the breeds' allelic richness and heterozygosity, and studied their genetic relationships with a neighbor-joining tree based on the Chord genetic distance matrix. We used the Weitzman approach and the core set diversity measure of Eding et al. (2002) to quantify the contribution of each breed to the maximum amount of genetic diversity and to identify breeds important for the conservation of genetic diversity. We defined 11 breeds as a "safe set" of breeds (not endangered) and estimated a reduction in genetic diversity if all nonsafe (endangered) breeds were lost. We then calculated the increase in genetic diversity by adding one by one each of the nonsafe breeds to the safe set (the safe-set-plus-one approach). The neighbor-joining tree grouped the northern European cattle breeds into Black-and-White type, Baltic Red, and Nordic cattle groups. Väne cattle, Bohus Poll, and Danish Jersey had the highest relative contribution to the maximum amount of genetic diversity when the diversity was quantified by the Weitzman diversity measure. These breeds not only showed phylogenetic distinctiveness but also low within-population variation. When the Eding et al. method was applied, Eastern Finncattle and Lithuanian White Backed cattle contributed most of the genetic variation. If the loss of the nonsafe set of breeds happens, the reduction in genetic diversity would be substantial (72%) based on the Weitzman approach, but relatively small (1.81%) based on the Eding et al. method. The safe set contained only 66% of the observed microsatellite alleles. The safe-set-plus-one approach indicated that Bohus Poll and Väne cattle contributed most to the Weitzman diversity, whereas the Eastern Finncattle contribution was the highest according to the Eding et al. method. Our results indicate that both methods of Weitzman and Eding et al. recognize the importance of local populations as a valuable resource of genetic variation.

Changes in Suicide Methods in Quebec between 1987 and 2000: The Possible Impact of Bill C-17 Requiring Safe Storage of Firearms

ERIC Educational Resources Information Center

Caron, Jean; Julien, Marie; Huang, Jean Hua

2008-01-01

This study presents the changes in the overall and firearm suicide rates for Quebec (Canada) before and after Bill C-17, which was implemented to secure safe storage of firearms. It covers 20,009 suicide cases reported to the coroner's office. Interrupted time series analysis is used to compare suicide rates in the two periods. Firearm suicide…

Design and Testing of a Novel, Protective Human-Baited Tent Trap for the Collection of Anthropophilic Disease Vectors

PubMed Central

KRAJACICH, BENJAMIN J.; SLADE, JEREMIAH R.; MULLIGAN, ROBERT T.; LABRECQUE, BRENDAN; KOBYLINSKI, KEVIN C.; GRAY, MEG; KUKLINSKI, WOJTEK S.; BURTON, TIMOTHY A.; SEAMAN, JONATHAN A.; SYLLA, MASSAMBA; FOY, BRIAN D.

2014-01-01

Currently, there exists a deficit of safe, active trapping methods for the collection of host-seeking Anopheles and other disease-causing arthropod vectors. The gold-standard approach for mosquito collection is that of human landing catch (HLC), in which an individual exposes bare skin to possibly infected vectors. Here, we present the development of a new method for mosquito collection, the Infoscitex tent, which uses modern tent materials coupled with a novel trap design. This provides an efficacious, a non-labor-intensive, and a safe method for vector collection. In these initial studies, we found it collected an average of 27.7 Anophelesgambiae s.l. per trap per night in rural villages in southeastern Senegal, and 43.8 Culex group V per trap per night in the semiurban town of Kedougou, Senegal. In direct comparisons with HLC, the tent was not statistically different for collection of Culex quinquefasciatus in crepuscular sampling, but was significantly less efficacious at trapping the highly motile dusk-biter Aedes aegypti. These studies suggest that the Infoscitex tent is a viable and safe alternative to HLC for Anopheles and Culex sampling in areas of high vector-borne disease infection risk. PMID:24605476

Rapid Bedside Inactivation of Ebola Virus for Safe Nucleic Acid Tests.

PubMed

Rosenstierne, Maiken Worsøe; Karlberg, Helen; Bragstad, Karoline; Lindegren, Gunnel; Stoltz, Malin Lundahl; Salata, Cristiano; Kran, Anne-Marte Bakken; Dudman, Susanne Gjeruldsen; Mirazimi, Ali; Fomsgaard, Anders

2016-10-01

Rapid bedside inactivation of Ebola virus would be a solution for the safety of medical and technical staff, risk containment, sample transport, and high-throughput or rapid diagnostic testing during an outbreak. We show that the commercially available Magna Pure lysis/binding buffer used for nucleic acid extraction inactivates Ebola virus. A rapid bedside inactivation method for nucleic acid tests is obtained by simply adding Magna Pure lysis/binding buffer directly into vacuum blood collection EDTA tubes using a thin needle and syringe prior to sampling. The ready-to-use inactivation vacuum tubes are stable for more than 4 months, and Ebola virus RNA is preserved in the Magna Pure lysis/binding buffer for at least 5 weeks independent of the storage temperature. We also show that Ebola virus RNA can be manually extracted from Magna Pure lysis/binding buffer-inactivated samples using the QIAamp viral RNA minikit. We present an easy and convenient method for bedside inactivation using available blood collection vacuum tubes and reagents. We propose to use this simple method for fast, safe, and easy bedside inactivation of Ebola virus for safe transport and routine nucleic acid detection. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

The Naturoptic Method for Safe Recovery of Vision: Mentored Tutoring, Earnings, Academic Entity Financial Resources Tool

NASA Astrophysics Data System (ADS)

Sambursky, Nicole D.; McLeod, Roger David; Silva, Sandra Helena

2009-05-01

This is a novel method for safely and naturally improving vision. with applications for minority, female, and academic entity, financial advantages. The patented Naturoptic Method is a simple system designed to work quickly, requiring only a minimal number of sessions for improvement. Our mentored and unique activities investigated these claims by implementing the Naturoptic method on ourselves over a period of time. Research was conducted at off campus locations with the inventor of the Naturoptic Method. Initial visual acuity and subsequent progress is self assessed, using standard Snellen Eye Charts. Research is designed to document improvements in vision with successive uses of the Naturoptic Method, as mentored teachers or Awardees of ``The Kaan Balam Matagamon Memorial Award,'' with net earnings shared by the designees, academic entities, the American Indians in Science and Engineering Society, AISES, or charity. The Board requires Awardees, its students, or affiliates, to sign non-disclosure agreements. 185/1526

Stochastic Resonance and Safe Basin of Single-Walled Carbon Nanotubes with Strongly Nonlinear Stiffness under Random Magnetic Field.

PubMed

Xu, Jia; Li, Chao; Li, Yiran; Lim, Chee Wah; Zhu, Zhiwen

2018-05-04

In this paper, a kind of single-walled carbon nanotube nonlinear model is developed and the strongly nonlinear dynamic characteristics of such carbon nanotubes subjected to random magnetic field are studied. The nonlocal effect of the microstructure is considered based on Eringen’s differential constitutive model. The natural frequency of the strongly nonlinear dynamic system is obtained by the energy function method, the drift coefficient and the diffusion coefficient are verified. The stationary probability density function of the system dynamic response is given and the fractal boundary of the safe basin is provided. Theoretical analysis and numerical simulation show that stochastic resonance occurs when varying the random magnetic field intensity. The boundary of safe basin has fractal characteristics and the area of safe basin decreases when the intensity of the magnetic field permeability increases.

A Comparative Study on Bearing Capacity of Shallow Foundations in Sand from N and ϕ

NASA Astrophysics Data System (ADS)

Sakleshpur, V. A.; Satyanarayana Reddy, C. N. V.

2017-12-01

This work presents a comparative study on the bearing capacity of strip, square, circular footings and raft foundations in sand, estimated from the standard penetration resistance, N, and the angle of shearing resistance, ϕ. The net safe bearing capacity estimated directly from N using Teng's equation is compared with that obtained from ϕ as per IS:6403. Likewise, the net safe settlement pressure determined from IS:8009 (Part 1), based on N, is compared with that attained from the semi-empirical approach of Schmertmann et al. A parametric study quantifies the effects of the standard penetration resistance and the size and depth of foundation on the net safe bearing capacity and the net safe settlement pressure of strip, square, circular footings and raft foundations in sand. Interactive charts are prepared in terms of the standard penetration resistance to highlight the appropriate method for the benefit of civil engineers.

Chemical composition and aroma evaluation of volatile oils from edible mushrooms (Pleurotus salmoneostramineus and Pleurotus sajor-caju).

PubMed

Usami, Atsushi; Nakaya, Satoshi; Nakahashi, Hiroshi; Miyazawa, Mitsuo

2014-01-01

This study is focused on the volatile oils from the fruiting bodies of Pleurotus salmoneostramineus (PS) and P. sajor-caju (PSC), which was extracted by hydrodistillation (HD) and solvent-assisted flavor evaporation (SAFE) methods. The oils are analyzed by gas chromatography-mass spectrometry (GC-MS), GC-olfactometry (GC-O), and aroma extract dilution analysis (AEDA). A total of 31, 31, 45, and 15 components were identified in PS (HD and SAFE) and PSC (HD and SAFE), representing about 80.3%, 92.2%, 88.9%, and 83.0% of the oils, respectively. Regarding the aroma-active components, 13, 12, 13, and 5 components were identified in PS (HD and SAFE) and PSC (HD and SAFE), respectively, by the GC-O analyses. The results of the sniffing test, odor activity value (OAV) and flavor dilution (FD) factor indicate that 1-octen-3-ol and 3-octanone are the main aroma-active components of PS oils. On the other hands, methional and 1-octen-3-ol were estimated as the main aroma-active components of PSC oils.

Anatomical Basis for Safe and Effective Volumization of the Temple.

PubMed

Breithaupt, Andrew D; Jones, Derek H; Braz, Andre; Narins, Rhoda; Weinkle, Susan

2015-12-01

One of the earliest but often unaddressed signs of facial aging is volume loss in the temple. Treatment of the area can produce satisfying results for both patient and practitioner. Safe injection requires explicit knowledge of the anatomy to avoid complications related to the multitude of vessels that course throughout the region at various depths. The authors aim to detail the anatomy of the area and provide a safe and easy-to-follow method for injection. The authors review the relevant anatomy of the temporal region and its application to cosmetic filler injections. The authors describe an easy-to-follow approach for a safe and effective injection window based on numerous anatomical studies. Injection in this area is not without risk, including potential blindness. The authors review the potential complications and their treatments. Hollowing of the temple is an early sign of aging that, when corrected, can lead to significant patient and practitioner satisfaction. Proper anatomically knowledge is required to avoid potentially severe complications. In this study, the authors present a reliable technique to safely and effectively augment this often undertreated area of the aging face.

Incinerator technology overview

NASA Astrophysics Data System (ADS)

Santoleri, Joseph J.

1993-03-01

Many of the major chemical companies in the U.S. who regarded a safe environment as their responsibility installed waste treatment and disposal facilities on their plant sites in the last two decades. Many of these plants elected to use incinerators as the treatment process. This was not always the most economical method, but in many cases it was the only method of disposal that provided a safe and sure method of maximum destruction. Environmental concern over contamination from uncontrolled land disposal sites, and the emergence of tougher regulations for land disposal provide incentives for industry to employ a wide variety of traditional and advanced technologies for managing hazardous wastes. Incineration systems utilizing proper design, operation, and maintenance provides the safest, and in the long run, the most economical avenue to the maximum level of destruction of organic hazardous wastes.

[Experimental intervention study of safe injection in basic-level hospitals in Hunan by medical staff].

PubMed

Li, Li; Li, Yinglan; Long, Yanfang; Zhou, Yang; Lu, Jingmei; Wu, Ying

2013-07-01

To experimentally intervene safe injection by medical staff in basic-level hospitals and observe the recent and long-term effect after the intervention and to provide practical measures to improve safe injection. We used random sampling methods to set up groups in county hospitals and township hospitals of Hunan Province, and offered lectures, delivered safe injection guide, brochure and on-site guidance in the experimental group. We surveyed the 2 groups after the intervention at 1 month and 6 months to compare the effect of unsafe injection behaviors and safe injection behaviors. One month after the intervention, the unsafe injection rate in the experimental group decreased from 27.8% to 21.7%, while in the control group injection the unsafe injection rate rose from 26.0% to 27.9%, with significant difference (P<0.01). Six months after the intervention, the unsafe injection rate in the experimental group declined to 18.4% while the unsafe injection rate in the control group also dropped to 22.4%, with significant difference (P<0.01). Unsafe injection rate was decreased in the experimental group at different intervention points, with significant difference (P<0.01). The safe injection behavior scores in the experimental group were higher than those in the control group after the intervention of 1 month and 6 month intervention (P<0.01); the experimental group got higher scores after the intervention (P<0.01). Training of safe injection, distribution of safe injection guide, and comprehensive intervention model can significantly change the primary care practitioners' behaviors in unsafe injections and it is worth promoting.

Drug discovery and the impact of the safe harbor provision of the Hatch- Waxman Act.

PubMed

Goodson, Susanne H

2010-01-01

Many facets of drug discovery involve the use of patented materials and methods, subjecting the researcher to potential liability from infringement of the underlying patents. Enacted in 1984, the Hatch-Waxman Act established a “safe harbor” for activities that would otherwise constitute infringement of a patented invention, if those activities were “solely for uses reasonably related to the development and submission of information under a Federal law which regulates the manufacture, use, or sale of drugs or veterinary biological products”. This article examines the major court decisions interpreting the scope of the safe harbor and their application to various activities in drug development.

An effective method for terrestrial arthropod euthanasia.

PubMed

Bennie, Neil A C; Loaring, Christopher D; Bennie, Mikaella M G; Trim, Steven A

2012-12-15

As scientific understanding of invertebrate life increases, so does the concern for how to end that life in an effective way that minimises (potential) suffering and is also safe for those carrying out the procedure. There is increasing debate on the most appropriate euthanasia methods for invertebrates as their use in experimental research and zoological institutions grows. Their popularity as pet species has also led to an increase in the need for greater veterinary understanding. Through the use of a local injection of potassium chloride (KCl) initially developed for use in American lobsters, this paper describes a safe and effective method for euthanasia in terrestrial invertebrates. Initial work focused on empirically determining the dose for cockroaches, which was then extrapolated to other arthropod species. For this method of euthanasia, we propose the term 'targeted hyperkalosis' to describe death through terminal depolarisation of the thoracic ganglia as a result of high potassium concentration.

A Survey of Knowledge, Attitude, and Practice of Consumers at a Tertiary Care Hospital Regarding the Disposal of Unused Medicines.

PubMed

Sonowal, Supriya; Desai, Chetna; Kapadia, Jigar D; Desai, Mira K

2016-12-01

To evaluate the knowledge, attitude and practice of consumers in India about disposal of unused medicines. A questionnaire comprising 11 questions evaluating the Knowledge (2), Attitude (3) and Practice (6) of unused medicines was prepared and pre validated before administering to 200 consumers of medicines attending the outpatient department of Civil Hospital Ahmedabad, a tertiary care teaching hospital in Western India. Requisite permissions from Institutional Ethics Committee and informed consent were obtained prior to recruiting them for the study. Responses were recorded, in Microsoft Excel ® spreadsheet and evaluated for percentage response. Majority of the respondents (136, 68%) stored unused medicines at home. Analgesics (26.5%) were the most common unused medicine stored. Safe disposal of medicine was considered necessary by majority respondents (160, 80%) for different reasons like prevention of illegal/unintended use (84, 42%), prevention of environmental pollution (32, 16%) or possible ADR caused by old drugs (54, 27%). Only 78 (39%) respondents were aware of appropriate methods of disposal. Disposal in household trash (61, 30.5%) was the most common method used. Majority of respondents felt the need for a facility or programme to collect unused medicines (152, 76%) and an increased awareness among consumers regarding hazards and methods of disposal of unused medicines (154, 77%). Majority of consumers are aware about the need for safe disposal of unused medicines. But the right attitude for and practice of safe disposal of medicines is lacking. A need for increased awareness regarding safe disposal of medicines is acknowledged by majority of consumers.

From strange bedfellows to natural allies: the shifting allegiance of fire service organisations in the push for federal fire-safe cigarette legislation

PubMed Central

Barbeau, E; Kelder, G; Ahmed, S; Mantuefel, V; Balbach, E

2005-01-01

Background: Cigarettes are the leading cause of fatal fires in the USA and are associated with one in four fire deaths. Although the technology needed to make fire-safe cigarettes has been available for many years, progress has been slow on legislative and regulatory fronts to require the tobacco industry to manufacture fire-safe cigarettes. Method and results: We conducted a case study, drawing on data from tobacco industry documents, archives, and key informant interviews to investigate tobacco industry strategies for thwarting fire-safe cigarette legislation in the US Congress. We apply a theoretical framework that posits that policymaking is the product of three sets of forces: interests, institutions, and ideas, to examine tobacco industry behaviour, with a special focus on their and others' attempts to court fire service organisations, including firefighters' unions as allies. We discuss the implications of our findings for future policy efforts related to fire-safe cigarettes and other tobacco control issues. Conclusions: Tobacco control advocates ought to: continue efforts to align key interest groups, including the firefighters unions; contest tobacco industry "diversionary" science tactics; and pursue a state based legislative strategy for fire-safe cigarettes, building towards national legislation. PMID:16183985

Predicting water consumption habits for seven arsenic-safe water options in Bangladesh

PubMed Central

2013-01-01

Background In Bangladesh, 20 million people are at the risk of developing arsenicosis because of excessive arsenic intake. Despite increased awareness, many of the implemented arsenic-safe water options are not being sufficiently used by the population. This study investigated the role of social-cognitive factors in explaining the habitual use of arsenic-safe water options. Methods Eight hundred seventy-two randomly selected households in six arsenic-affected districts of rural Bangladesh, which had access to an arsenic-safe water option, were interviewed using structured face-to-face interviews in November 2009. Habitual use of arsenic-safe water options, severity, vulnerability, affective and instrumental attitudes, injunctive and descriptive norms, self-efficacy, and coping planning were measured. The data were analyzed using multiple linear regressions. Results Linear regression revealed that self-efficacy (B = 0.42, SE = .03, p < .001), the instrumental attitude towards the safe water option (B = 0.24, SE = .04, p < .001), the affective attitude towards contaminated tube wells (B = −0.04, SE = .02, p = .024), vulnerability (B = −0.20, SE = .02, p < .001), as well as injunctive (B = 0.08, SE = 0.04, p = .049) and descriptive norms (B = 0.34, SE = .03, p < .001) primarily explained the habitual use of arsenic-safe water options (R2 = 0.688). This model proved highly generalizable to all seven arsenic-safe water options investigated, even though habitual use of single options were predicted on the basis of parameters estimated without these options. Conclusions This general model for the habitual use of arsenic-safe water options may prove useful to predict other water consumption habits. Behavior-change interventions are derived from the model to promote the habitual use of arsenic-safe water options. PMID:23634950

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.

Mixed-Methods Evaluation of Real-Time Safety Reporting by Hospitalized Patients and Their Care Partners: The MySafeCare Application.

PubMed

Collins, Sarah A; Couture, Brittany; Smith, Ann DeBord; Gershanik, Esteban; Lilley, Elizabeth; Chang, Frank; Yoon, Cathy; Lipsitz, Stuart; Sheikh, Aziz; Benneyan, James; Bates, David W

2018-04-27

The aims of the study were to evaluate the amount and content of data patients and care partners reported using a real-time electronic safety tool compared with other reporting mechanisms and to understand their perspectives on safety concerns and reporting in the hospital. This study used mixed methods including 20-month preimplementation and postimplementation trial evaluating MySafeCare, a web-based application, which allows hospitalized patients/care partners to report safety concerns in real time. The study compared MySafeCare submission rates for three hospital units (oncology acute care, vascular intermediate care, medical intensive care) with submissions rates of Patient Family Relations (PFR) Department, a hospital service to address patient/family concerns. The study used triangulation of quantitative data with thematic analysis of safety concern submissions and patient/care partner interviews to understand submission content and perspectives on safety reporting. Thirty-two MySafeCare submissions were received with an average rate of 1.7 submissions per 1000 patient-days and a range of 0.3 to 4.8 submissions per 1000 patient-days across all units, indicating notable variation between units. MySafeCare submission rates were significantly higher than PFR submission rates during the postintervention period on the vascular unit (4.3 [95% confidence interval = 2.8-6.5] versus 1.5 [95% confidence interval = 0.7-3.1], Poisson) (P = 0.01). Overall trends indicated a decrease in PFR submissions after MySafeCare implementation. Triangulated data indicated patients preferred to report anonymously and did not want concerns submitted directly to their care team. MySafeCare evaluation confirmed the potential value of providing an electronic, anonymous reporting tool in the hospital to capture safety concerns in real time. Such applications should be tested further as part of patient safety programs.This is an open-access article distributed under the terms of the Creative Commons Attribution-Non Commercial-No Derivatives License 4.0 (CCBY-NC-ND), where it is permissible to download and share the work provided it is properly cited. The work cannot be changed in any way or used commercially without permission from the journal.

Arsenic-Safe Aquifers in Coastal Bangladesh: AN Investigation with Ordinary Kriging Estimation

NASA Astrophysics Data System (ADS)

Hassan, M. M.; Ahamed, R.

2017-10-01

Spatial point pattern is one of the most suitable methods for analysing groundwater arsenic concentrations. Groundwater arsenic poisoning in Bangladesh has been one of the biggest environmental health disasters in recent times. About 85 million people are exposed to arsenic more than 50 μg/L in drinking water. The paper seeks to identify the existing suitable aquifers for arsenic-safe drinking water along with "spatial arsenic discontinuity" using GIS-based spatial geostatistical analysis in a small study site (12.69 km2) in the coastal belt of southwest Bangladesh (Dhopakhali union of Bagerhat district). The relevant spatial data were collected with Geographical Positioning Systems (GPS), arsenic data with field testing kits, tubewell attributes with observation and questionnaire survey. Geostatistics with kriging methods can design water quality monitoring in different aquifers with hydrochemical evaluation by spatial mapping. The paper presents the interpolation of the regional estimates of arsenic data for spatial discontinuity mapping with Ordinary Kriging (OK) method that overcomes the areal bias problem for administrative boundary. This paper also demonstrates the suitability of isopleth maps that is easier to read than choropleth maps. The OK method investigated that around 80 percent of the study site are contaminated following the Bangladesh Drinking Water Standards (BDWS) of 50 μg/L. The study identified a very few scattered "pockets" of arsenic-safe zone at the shallow aquifer.

Guidelines and Recommendations for Developing Interactive eHealth Apps for Complex Messaging in Health Promotion

PubMed Central

Heffernan, Kayla Joanne; Maclean, Skye Tamara; Callegari, Emma Teresa; Garland, Suzanne Marie; Reavley, Nicola Jane; Varigos, George Andrew; Wark, John Dennis

2016-01-01

Background The now ubiquitous catchphrase, “There’s an app for that,” rings true owing to the growing number of mobile phone apps. In excess of 97,000 eHealth apps are available in major app stores. Yet the effectiveness of these apps varies greatly. While a minority of apps are developed grounded in theory and in conjunction with health care experts, the vast majority are not. This is concerning given the Hippocratic notion of “do no harm.” There is currently no unified formal theory for developing interactive eHealth apps, and development is especially difficult when complex messaging is required, such as in health promotion and prevention. Objective This paper aims to provide insight into the creation of interactive eHealth apps for complex messaging, by leveraging the Safe-D case study, which involved complex messaging required to guide safe but sufficient UV exposure for vitamin D synthesis in users. We aim to create recommendations for developing interactive eHealth apps for complex messages based on the lessons learned during Safe-D app development. Methods For this case study we developed an Apple and Android app, both named Safe-D, to safely improve vitamin D status in young women through encouraging safe ultraviolet radiation exposure. The app was developed through participatory action research involving medical and human computer interaction researchers, subject matter expert clinicians, external developers, and target users. The recommendations for development were created from analysis of the development process. Results By working with clinicians and implementing disparate design examples from the literature, we developed the Safe-D app. From this development process, recommendations for developing interactive eHealth apps for complex messaging were created: (1) involve a multidisciplinary team in the development process, (2) manage complex messages to engage users, and (3) design for interactivity (tailor recommendations, remove barriers to use, design for simplicity). Conclusions This research has provided principles for developing interactive eHealth apps for complex messaging as guidelines by aggregating existing design concepts and expanding these concepts and new learnings from our development process. A set of guidelines to develop interactive eHealth apps generally, and specifically those for complex messaging, was previously missing from the literature; this research has contributed these principles. Safe-D delivers complex messaging simply, to aid education, and explicitly, considering user safety. PMID:26860623

The fire-safe cigarette: a burn prevention tool.

PubMed

Barillo, D J; Brigham, P A; Kayden, D A; Heck, R T; McManus, A T

2000-01-01

Cigarettes are the most common ignition source for fatal house fires, which cause approximately 29% of the fire deaths in the United States. A common scenario is the delayed ignition of a sofa, chair, or mattress by a lit cigarette that is forgotten or dropped by a smoker whose alertness is impaired by alcohol or medication. Cigarettes are designed to continue burning when left unattended. If they are dropped on mattresses, upholstered furniture, or other combustible material while still burning, their propensity to start fires varies depending on the cigarette design and content. The term "fire-safe" has evolved to describe cigarettes designed to have a reduced propensity for igniting mattresses and upholstered furniture. Legislative interest in the development of fire-safe smoking materials has existed for more than 50 years. Studies that showed the technical and economic feasibility of commercial production of fire-safe cigarettes were completed more than 10 years ago. Despite this, commercial production of fire-safe smoking materials has not been undertaken. The current impasse relates to the lack of consensus on a uniform test method on which to base a standard for fire-safe cigarettes. Although the fire-safe cigarette is a potentially important burn prevention tool, commercial production of such cigarettes will not occur until a standard against which fire-starting performance can be measured has been mandated by law at the state or federal level. The burn care community can play a leadership role in such legislative efforts.

Health Care Ergonomics: Contributions of Thomas Waters.

PubMed

Poole Wilson, Tiffany; Davis, Kermit G

2016-08-01

The aim of this study was to assess the contributions of Thomas Waters's work in the field of health care ergonomics and beyond. Waters's research of safe patient handling with a focus on reducing musculoskeletal disorders (MSDs) in health care workers contributed to current studies and prevention strategies. He worked with several groups to share his research and assist in developing safe patient handling guidelines and curriculum for nursing students and health care workers. The citations of articles that were published by Waters in health care ergonomics were evaluated for quality and themes of conclusions. Quality was assessed using the Mixed Methods Appraisal Tool and centrality to original research rating. Themes were documented by the type of population the citing articles were investigating. In total, 266 articles that referenced the top seven cited articles were evaluated. More than 95% of them were rated either medium or high quality. The important themes of these citing articles were as follows: (a) Safe patient handling is effective in reducing MSDs in health care workers. (b) Shift work has negative impact on nurses. (c) There is no safe way to manually lift a patient. (d) Nurse curriculums should contain safe patient handling. The research of Waters has contributed significantly to the health care ergonomics and beyond. His work, in combination with other pioneers in the field, has generated multiple initiatives, such as a standard safe patient-handling curriculum and safe patient-handling programs. © 2016, Human Factors and Ergonomics Society.

Optimal design of a piezoelectric transducer for exciting guided wave ultrasound in rails

NASA Astrophysics Data System (ADS)

Ramatlo, Dineo A.; Wilke, Daniel N.; Loveday, Philip W.

2017-02-01

An existing Ultrasonic Broken Rail Detection System installed in South Africa on a heavy duty railway line is currently being upgraded to include defect detection and location. To accomplish this, an ultrasonic piezoelectric transducer to strongly excite a guided wave mode with energy concentrated in the web (web mode) of a rail is required. A previous study demonstrated that the recently developed SAFE-3D (Semi-Analytical Finite Element - 3 Dimensional) method can effectively predict the guided waves excited by a resonant piezoelectric transducer. In this study, the SAFE-3D model is used in the design optimization of a rail web transducer. A bound-constrained optimization problem was formulated to maximize the energy transmitted by the transducer in the web mode when driven by a pre-defined excitation signal. Dimensions of the transducer components were selected as the three design variables. A Latin hypercube sampled design of experiments that required a total of 500 SAFE-3D analyses in the design space was employed in a response surface-based optimization approach. The Nelder-Mead optimization algorithm was then used to find an optimal transducer design on the constructed response surface. The radial basis function response surface was first verified by comparing a number of predicted responses against the computed SAFE-3D responses. The performance of the optimal transducer predicted by the optimization algorithm on the response surface was also verified to be sufficiently accurate using SAFE-3D. The computational advantages of SAFE-3D in optimal transducer design are noteworthy as more than 500 analyses were performed. The optimal design was then manufactured and experimental measurements were used to validate the predicted performance. The adopted design method has demonstrated the capability to automate the design of transducers for a particular rail cross-section and frequency range.

Safe Maritime Autonomous Path Planning in a High Sea State

NASA Technical Reports Server (NTRS)

Ono, Masahiro; Quadrelli, Marco; Huntsberger, Terrance L.

2014-01-01

This paper presents a path planning method for sea surface vehicles that prevents capsizing and bow-diving in a high sea-state. A key idea is to use response amplitude operators (RAOs) or, in control terminology, the transfer functions from a sea state to a vessel's motion, in order to find a set of speeds and headings that results in excessive pitch and roll oscillations. This information is translated to arithmetic constraints on the ship's velocity, which are passed to a model predictive control (MPC)-based path planner to find a safe and optimal path that achieves specified goals. An obstacle avoidance capability is also added to the path planner. The proposed method is demonstrated by simulations.

Handling small arbovirus vectors safely during biosafety level 3 containment: Culicoides variipennis sonorensis (Diptera:Ceratopogonidae) and exotic bluetongue viruses.

PubMed

Hunt, G J; Tabachnick, W J

1996-05-01

Equipment and procedures are described for biosafety level 3 (BL-3) containment work with small, zoophilic arthropods. BL-3 classified pathogens always must be manipulated in biological safety cabinets. Procedures, including physical barriers and handling methods, that prevent the escape of potentially virus-infected insects are discussed, and the use of a monitoring system for insect security is explained. The inability to recover escaped minute, flying insects poses a major difference from similar work with larger insects, such as mosquitoes. Methods were developed for the safe and secure handling of Culicoides variipennis sonorensis Wirth & Jones infected with exotic bluetongue viruses during BL-3 containment.

Methods and protocol of a mixed method quasi-experiment to evaluate the effects of a structural economic and food security intervention on HIV vulnerability in rural Malawi: The SAGE4Health Study.

PubMed

Weinhardt, Lance S; Galvao, Loren W; Mwenyekonde, Thokozani; Grande, Katarina M; Stevens, Patricia; Yan, Alice F; Mkandawire-Valhmu, Lucy; Masanjala, Winford; Kibicho, Jennifer; Ngui, Emmanuel; Emer, Lindsay; Watkins, Susan C

2014-01-01

Poverty and lack of a predictable, stable source of food are two fundamental determinants of ill health, including HIV/AIDS. Conversely, episodes of poor health and death from HIV can disrupt the ability to maintain economic stability in affected households, especially those that rely on subsistence farming. However, little empirical research has examined if, and how, improvements in people's economic status and food security translate into changes in HIV vulnerability. In this paper, we describe in detail the methods and protocol of an academic-NGO collaboration on a quasi-experimental, longitudinal study of the mechanisms and magnitude of the impact of a multilevel economic and food security program (Support to Able-Bodied Vulnerable Groups to Achieve Food Security; SAFE), as implemented by CARE. Primary outcomes include HIV vulnerability (i.e., HIV risk behaviors, HIV infection), economic status (i.e., income, household assets) and food security (including anthropometric measures). We recruited participants from two types of areas of rural central Malawi: traditional authorities (TA) selected by CARE to receive the SAFE program (intervention group) and TAs receiving other unrelated CARE programming (controls). In the intervention TAs, we recruited 598 program participants (398 women, 200 men) and interviewed them at baseline and 18- and 36-month follow-ups; we interviewed 301 control households. In addition, we conducted random surveys (n = 1002) in the intervention and control areas with a 36-month assessment interval, prior to and after implementation of SAFE. Thus, we are examining intervention outcomes both in direct SAFE program participants and their larger communities. We are using multilevel modeling to examine mediators and moderators of the effects of SAFE on HIV outcomes at the individual and community levels and determine the ways in which changes in HIV outcomes feed back into economic outcomes and food security at later interviews. Finally, we are conducting a qualitative end-of-program evaluation consisting of in-depth interviews with 90 SAFE participants. In addition to examining pathways linking structural factors to HIV vulnerability, this research will yield important information for understanding the impact of a multilevel environmental/structural intervention on HIV, with the potential for other sustainable long-term public health benefits.

REVISITING THE SAFE PLACE:Method and Regulatory Aspects in Psychotherapy when Easing Allostatic Overload in Traumatized Patients.

PubMed

Gerge, Anna

2018-01-01

Safe-place inductions are considered important altered states of consciousness (ASC) to be (re)installed during trauma-informed psychotherapy. Coregulation aimed at changing implicit relational knowing and increasing integration and coherence through relational work and hypnotic techniques is crucial, as clients' abilities to self-soothe and regulate have become seriously impaired. Thus, resource-oriented metaphors as inner strength imagery is advocated. Also, methods such as creative-arts therapy and neurofeedback will induce ASCs, as most methods used with complex traumatized clients, due to their high hypnotizability. When positive or soothing imagery or relationally held suggestions for changed attentional focus are added to both psychodynamic psychotherapy and CBT, a hetero-hypnosis will be induced-a prerequisite for phase-specific trauma therapy aimed at changing inner schemas and scripts.

METHODS FOR EMERGING CONTAMINANT GROUPS: EXPLOSIVES AND NITROSAMINES

EPA Science Inventory

Background
In support of requirements in the Safe Drinking Water Act, the National Exposure Research Laboratory (NERL), has been developing analytical methods for chemicals on the 1998 contaminant candidate list (CCL) and for other chemicals of emerging interest. The purpose ...

Manufacturing Methods and Technology Program Accomplishments

DTIC Science & Technology

1980-10-01

573,74,77.78,4139 AppI of Radar to Ballistic ACC Test of Amo (ARBAT) 43 574 4162 Automated Line for Melt-Pour Process of High Explosives 44 571,72 4171 Investigation...Sensitivity Criteria 49 576 4288 Explosive Safe Separation and Sensitivity Criteria 50 577 4288 Explosive Safe Separation and Sensitivity Sriteria 51...1 ANICIPATE. BEN(EPITS ACTUAL BENE’ITS PRO3ECT NUMBER $ SAVINGS OTHER SAVINGS OTHER REMARKS 5 73 1139 REDUCED EXPLOSIVE HAZARD TWO MACHINES WERE

The Evolution of Israeli Civil-Military Relations: Domestic Enablers and the Quest for Peace

DTIC Science & Technology

2009-12-01

Israeli society, its sense of security, and its view of military institutions. It is safe to assume, however, the changing social attitudes will...It is safe to assume, however, the changing social attitudes will continue to shape the state’s often obscure civil-military dynamic, which will...2 (2005): 231. “For Israelis, armed conflict became the ultimate method of resolving the issue of their state’s disputed existence.” 5 Charles D

Physical and chemical test results of electrostatic safe flooring materials

NASA Technical Reports Server (NTRS)

Gompf, R. H.

1988-01-01

This test program was initiated because a need existed at the Kennedy Space Center (KSC) to have this information readily available to the engineer who must make the choice of which electrostatic safe floor to use in a specific application. The information, however, should be of value throughout both the government and private industry in the selection of a floor covering material. Included are the test results of 18 floor covering materials which by test evaluation at KSC are considered electrostatically safe. Tests were done and/or the data compiled in the following areas: electrostatics, flammability, hypergolic compatibility, outgassing, floor type, material thickness, and available colors. Each section contains the test method used to gather the data and the test results.

Updated Guidance for Safe and Effective Use of Contraception.

PubMed

Tepper, Naomi K; Curtis, Kathryn M; Jatlaoui, Tara C; Whiteman, Maura K

2016-11-01

Progress has been made in efforts to reduce unintended pregnancy; however, unintended pregnancy remains a public health issue in the United States. A key component of reducing unintended pregnancy is to increase correct and consistent use of contraception by reducing barriers to access and use. The CDC has recently updated its guidance for the safe and effective use of contraception. The U.S. Medical Eligibility Criteria for Contraceptive Use (US MEC), 2016, and U.S. Selected Practice Recommendations for Contraceptive Use (US SPR), 2016, are intended for healthcare providers to help patients choose a method that is safe and can be used effectively. The recommendations aim to reduce certain barriers to contraception and thus help women, men, and couples to control timing of pregnancies.

Structured Kernel Subspace Learning for Autonomous Robot Navigation.

PubMed

Kim, Eunwoo; Choi, Sungjoon; Oh, Songhwai

2018-02-14

This paper considers two important problems for autonomous robot navigation in a dynamic environment, where the goal is to predict pedestrian motion and control a robot with the prediction for safe navigation. While there are several methods for predicting the motion of a pedestrian and controlling a robot to avoid incoming pedestrians, it is still difficult to safely navigate in a dynamic environment due to challenges, such as the varying quality and complexity of training data with unwanted noises. This paper addresses these challenges simultaneously by proposing a robust kernel subspace learning algorithm based on the recent advances in nuclear-norm and l 1 -norm minimization. We model the motion of a pedestrian and the robot controller using Gaussian processes. The proposed method efficiently approximates a kernel matrix used in Gaussian process regression by learning low-rank structured matrix (with symmetric positive semi-definiteness) to find an orthogonal basis, which eliminates the effects of erroneous and inconsistent data. Based on structured kernel subspace learning, we propose a robust motion model and motion controller for safe navigation in dynamic environments. We evaluate the proposed robust kernel learning in various tasks, including regression, motion prediction, and motion control problems, and demonstrate that the proposed learning-based systems are robust against outliers and outperform existing regression and navigation methods.

Exploring Space and Place with Walking Interviews

ERIC Educational Resources Information Center

Jones, Phil; Bunce, Griff; Evans, James; Gibbs, Hannah; Hein, Jane Ricketts

2008-01-01

This article explores the use of walking interviews as a research method. In spite of a wave of interest in methods which take interviewing out of the "safe," stationary environment, there has been limited work critically examining the techniques for undertaking such work. Curiously for a method which takes an explicitly spatial approach, few…

78 FR 37463 - Expedited Approval of Alternative Test Procedures for the Analysis of Contaminants Under the Safe...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-06-21

... Total Coliform Total Coliform 9221 A, B, C..... 9221 A, B, C..... Fermentation Technique. Total Coliform... Methodology category Method SM 22nd Edition \\28\\ Total Coliforms Lactose Fermentation Standard Total 9221 B.1, B.2 Methods. Coliform Fermentation Technique. Enzyme Substrate Colilert[supreg].... 9223 B Methods...

Airway management through submental derivation: a safe and easily reproduced alternative for patients with complex facial trauma

PubMed Central

2018-01-01

Objectives Airway management in patients with panfacial trauma is complicated. In addition to involving facial lesions, such trauma compromises the airway, and the use of intermaxillary fixation makes it difficult to secure ventilation by usual approaches (nasotracheal or endotracheal intubation). Submental airway derivation is an alternative to tracheostomy and nasotracheal intubation, allowing a permeable airway with minimal complications in complex patients. Materials and Methods This is a descriptive, retrospective study based on a review of medical records of all patients with facial trauma from January 2003 to May 2015. In total, 31 patients with complex factures requiring submental airway derivation were included. No complications such as bleeding, infection, vascular, glandular, or nervous lesions were presented in any of the patients. Results The use of submental airway derivation is a simple, safe, and easy method to ensure airway management. Moreover, it allows an easier reconstruction. Conclusion Based on these results, we concluded that, if the relevant steps are followed, the use of submental intubation in the treatment of patients with complex facial trauma is a safe and effective option. PMID:29535964

Constraint-based semi-autonomy for unmanned ground vehicles using local sensing

NASA Astrophysics Data System (ADS)

Anderson, Sterling J.; Karumanchi, Sisir B.; Johnson, Bryan; Perlin, Victor; Rohde, Mitchell; Iagnemma, Karl

2012-06-01

Teleoperated vehicles are playing an increasingly important role in a variety of military functions. While advantageous in many respects over their manned counterparts, these vehicles also pose unique challenges when it comes to safely avoiding obstacles. Not only must operators cope with difficulties inherent to the manned driving task, but they must also perform many of the same functions with a restricted field of view, limited depth perception, potentially disorienting camera viewpoints, and significant time delays. In this work, a constraint-based method for enhancing operator performance by seamlessly coordinating human and controller commands is presented. This method uses onboard LIDAR sensing to identify environmental hazards, designs a collision-free path homotopy traversing that environment, and coordinates the control commands of a driver and an onboard controller to ensure that the vehicle trajectory remains within a safe homotopy. This system's performance is demonstrated via off-road teleoperation of a Kawasaki Mule in an open field among obstacles. In these tests, the system safely avoids collisions and maintains vehicle stability even in the presence of "routine" operator error, loss of operator attention, and complete loss of communications.

New digital anti-copy/scan and verification technologies

NASA Astrophysics Data System (ADS)

Phillips, George K.

2004-06-01

This white paper reviews the method for making bearer printed information indistinguishable on a non-copyable substrate when a copied attempt is made on either an analog or digital electrostatic photocopier device. In 1995 we received patent number 5,704,651 for a non-copyable technology trademarked MetallicSafe. In this patent the abstract describes the usage of a reflective layer, formed on a complex pattern region and having graphic or font size shapes and type coordinating to particular patterns in the complex pattern region. The technology used in this patent has now been improved and evolved to new methods of creating a non-copyable substrate trademarked CopySafe+. CopySafe+ is formed of a metallic specular light reflector, a white camouflaged diffused light reflector, and the content information 'light absorption' layer. The synthesizing of these layers on a substrate creates dynamic camouflaged interference patterns and the phenomena of image chaos on a copy. In short, the orientation of a plurality of spectral and diffused light reflection camouflaged layers, mixed and coordinated with light absorption printed information, inhibits the copying device from reproducing the printed content.

A discharge summary adapted to the frail elderly to ensure transfer of relevant information from the hospital to community settings: a model

PubMed Central

2010-01-01

Background Elderly patients admitted to Geriatric Assessment Units (GAU) typically have complex health problems that require multi-professional care. Considering the scope of human and technological resources solicited during hospitalization, as well as the many risks and discomforts incurred by the patient, it is important to ensure the communication of pertinent information for quality follow-up care in the community setting. Conventional discharge summaries do not adequately incorporate the elements specific to an aging clientele. Objective To develop a discharge summary adapted to the frail elderly patient (D-SAFE) in order to communicate relevant information from hospital to community services. Methods The items to be included in the D-SAFE have been determined by means of a modified Delphi method through consultation with clinical experts from GAUs (11 physicians and 5 pharmacists) and the community (10 physicians and 5 pharmacists). The consensus analysis and the level of agreement among the experts were reached using a modified version of the RAND®/University of California at Los Angeles appropriateness method. Results A consensus was reached after two rounds of consultation for all the items evaluated, where none was judged «inappropriate». Among the items proposed, four were judged to be « uncertain » and were eliminated from the final D-SAFE, which was divided into two sections: the medical discharge summary (22 main items) and the discharge prescription (14 main items). Conclusions The D-SAFE was developed as a more comprehensive tool specifically designed for GAU inpatients. Additional research to validate its acceptability and practical impact on the continuity of care is needed before it can be recommended for use on a broader scale. PMID:20863405

Flywheel Rotor Safe-Life Technology

NASA Technical Reports Server (NTRS)

Ratner, J. K. H.; Chang, J. B.; Christopher, D. A.; McLallin, Kerry L. (Technical Monitor)

2002-01-01

Since the 1960s, research has been conducted into the use of flywheels as energy storage systems. The-proposed applications include energy storage for hybrid and electric automobiles, attitude control and energy storage for satellites, and uninterruptible power supplies for hospitals and computer centers. For many years, however, the use of flywheels for space applications was restricted by the total weight of a system employing a metal rotor. With recent technological advances in the manufacturing of composite materials, however, lightweight composite rotors have begun to be proposed for such applications. Flywheels with composite rotors provide much higher power and energy storage capabilities than conventional chemical batteries. However, the failure of a high speed flywheel rotor could be a catastrophic event. For this reason, flywheel rotors are classified by the NASA Fracture Control Requirements Standard as fracture critical parts. Currently, there is no industry standard to certify a composite rotor for safe and reliable operation forth( required lifetime of the flywheel. Technical problems hindering the development of this standard include composite manufacturing inconsistencies, insufficient nondestructive evaluation (NDE) techniques for detecting defects and/or impact damage, lack of standard material test methods for characterizing composite rotor design allowables, and no unified proof (over-spin) test for flight rotors. As part of a flywheel rotor safe-life certification pro-ram funded b the government, a review of the state of the art in composite rotors is in progress. The goal of the review is to provide a clear picture of composite flywheel rotor technologies. The literature review has concentrated on the following topics concerning composites and composite rotors: durability (fatigue) and damage tolerance (safe-life) analysis/test methods, in-service NDE and health monitoring techniques, spin test methods/ procedures, and containment options. This report presents the papers selected for their relevance to this topic and summarizes them.

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.

Behaviour of mesotrione in maize and soil system and its influence on soil dehydrogenase activity.

PubMed

Kaczynski, Piotr; Lozowicka, Bozena; Hrynko, Izabela; Wolejko, Elzbieta

2016-11-15

The aim of this study was to investigate the dissipation of mesotrione and effect on dehydrogenase activity (DHA) in maize and soil system. The paper for the first time describes behaviour of this herbicide applied at various doses (separately or in mixture with other herbicide) in acidic and alkaline environment. The experiments were conducted using the method randomized blocks in four repetition cycles. Chemical application in seven variants at recommended doses of herbicide were performed. The sample preparation was performed by a modified QuEChERS method and the concentrations of mesotrione in maize and soil were determined by the liquid chromatography with tandem mass spectrometry (LC-MS/MS). The limit of detection was 0.0005mgkg(-1) and quantification 0.001mgkg(-1). The dissipation of mesotrione were described according to first-order (FO) kinetics equation with R(2) were between 0.8794 and 0.9934. The initial deposit of herbicide in soil and maize was higher in an acidic environment (0.06-0.18mgkg(-1)). A positive correlation between an alkaline pH and the rate of dissipation in soil was observed. The results showed that the time after which 50% (DT50) of substance has been degraded was different for both plant and soil. DT50 for soil was within the range 3.2-6.0days and 2.9-4.4days, for the maize 3.9-4.8days and 3.4-4.5days in an alkaline and an acidic environment, respectively. Concentration of mesotrione at applicable MRL level of 0.05mgkg(-1) in maize was achieved at 0.5-5.9days and at proposed MRL of 0.01mgkg(-1) at 8.8-15.8days. The results indicate that the application of mesotrione affected on DHA in the soil. One day after application this herbicide, concentration of DHA in soil was lower than in control plots, but after 21days was observed trend of increasing DHA. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

Using a Hazard Quotient to Evaluate Pesticide Residues Detected in Pollen Trapped from Honey Bees (Apis mellifera) in Connecticut

PubMed Central

Stoner, Kimberly A.; Eitzer, Brian D.

2013-01-01

Analysis of pollen trapped from honey bees as they return to their hives provides a method of monitoring fluctuations in one route of pesticide exposure over location and time. We collected pollen from apiaries in five locations in Connecticut, including urban, rural, and mixed agricultural sites, for periods from two to five years. Pollen was analyzed for pesticide residues using a standard extraction method widely used for pesticides (QuEChERS) and liquid chromatography/mass spectrometric analysis. Sixty pesticides or metabolites were detected. Because the dose lethal to 50% of adult worker honey bees (LD50) is the only toxicity parameter available for a wide range of pesticides, and among our pesticides there were contact LD50 values ranging from 0.006 to >1000 μg per bee (range 166,000X), and even among insecticides LD50 values ranged from 0.006 to 59.8 μg/bee (10,000X); therefore we propose that in studies of honey bee exposure to pesticides that concentrations be reported as Hazard Quotients as well as in standard concentrations such as parts per billion. We used both contact and oral LD50 values to calculate Pollen Hazard Quotients (PHQ = concentration in ppb ÷ LD50 as μg/bee) when both were available. In this study, pesticide Pollen Hazard Quotients ranged from over 75,000 to 0.01. The pesticides with the greatest Pollen Hazard Quotients at the maximum concentrations found in our study were (in descending order): phosmet, Imidacloprid, indoxacarb, chlorpyrifos, fipronil, thiamethoxam, azinphos-methyl, and fenthion, all with at least one Pollen Hazard Quotient (using contact or oral LD50) over 500. At the maximum rate of pollen consumption by nurse bees, a Pollen Hazard Quotient of 500 would be approximately equivalent to consuming 0.5% of the LD50 per day. We also present an example of a Nectar Hazard Quotient and the percentage of LD50 per day at the maximum nectar consumption rate. PMID:24143241

Using a hazard quotient to evaluate pesticide residues detected in pollen trapped from honey bees (Apis mellifera) in Connecticut.

PubMed

Stoner, Kimberly A; Eitzer, Brian D

2013-01-01

Analysis of pollen trapped from honey bees as they return to their hives provides a method of monitoring fluctuations in one route of pesticide exposure over location and time. We collected pollen from apiaries in five locations in Connecticut, including urban, rural, and mixed agricultural sites, for periods from two to five years. Pollen was analyzed for pesticide residues using a standard extraction method widely used for pesticides (QuEChERS) and liquid chromatography/mass spectrometric analysis. Sixty pesticides or metabolites were detected. Because the dose lethal to 50% of adult worker honey bees (LD50) is the only toxicity parameter available for a wide range of pesticides, and among our pesticides there were contact LD50 values ranging from 0.006 to >1000 μg per bee (range 166,000X), and even among insecticides LD50 values ranged from 0.006 to 59.8 μg/bee (10,000X); therefore we propose that in studies of honey bee exposure to pesticides that concentrations be reported as Hazard Quotients as well as in standard concentrations such as parts per billion. We used both contact and oral LD50 values to calculate Pollen Hazard Quotients (PHQ = concentration in ppb ÷ LD50 as μg/bee) when both were available. In this study, pesticide Pollen Hazard Quotients ranged from over 75,000 to 0.01. The pesticides with the greatest Pollen Hazard Quotients at the maximum concentrations found in our study were (in descending order): phosmet, Imidacloprid, indoxacarb, chlorpyrifos, fipronil, thiamethoxam, azinphos-methyl, and fenthion, all with at least one Pollen Hazard Quotient (using contact or oral LD50) over 500. At the maximum rate of pollen consumption by nurse bees, a Pollen Hazard Quotient of 500 would be approximately equivalent to consuming 0.5% of the LD50 per day. We also present an example of a Nectar Hazard Quotient and the percentage of LD50 per day at the maximum nectar consumption rate.

Syringe disposal among injection drug users in Harlem and the Bronx during the New York State Expanded Syringe Access Demonstration Program.

PubMed

Cleland, Charles M; Deren, Sherry; Fuller, Crystal M; Blaney, Shannon; McMahon, James M; Tortu, Stephanie; Des Jarlais, Don C; Vlahov, David

2007-04-01

Effective January 1, 2001, New York State enacted the Expanded Syringe Access Demonstration Program (ESAP), allowing syringes to be sold in pharmacies without a prescription or dispensed through doctors, hospitals, and clinics to adults. A concern in the assessment of ESAP is its effects on syringe disposal practices. Syringe use data regarding the last injection episode were combined from three projects (N = 1,030) recruiting injection drug users. Disposal of syringes by methods known to be safe decreased significantly over time after the implementation of ESAP. Syringes obtained either from syringe exchange programs or ESAP sources were more likely to be disposed of safely than syringes obtained from other sources. Efforts to enlist pharmacists and others involved in ESAP implementation to encourage safe disposal are needed. More detailed information on disposal practices is needed to capture the continuum from least to most safe practices and variation within individuals.

The challenge of improving boiling: lessons learned from a randomized controlled trial of water pasteurization and safe storage in Peru.

PubMed

Heitzinger, K; Rocha, C A; Quick, R E; Montano, S M; Tilley, D H; Mock, C N; Carrasco, A J; Cabrera, R M; Hawes, S E

2016-07-01

Boiling is the most common method of household water treatment in developing countries; however, it is not always effectively practised. We conducted a randomized controlled trial among 210 households to assess the effectiveness of water pasteurization and safe-storage interventions in reducing Escherichia coli contamination of household drinking water in a water-boiling population in rural Peru. Households were randomized to receive either a safe-storage container or a safe-storage container plus water pasteurization indicator or to a control group. During a 13-week follow-up period, households that received a safe-storage container and water pasteurization indicator did not have a significantly different prevalence of stored drinking-water contamination relative to the control group [prevalence ratio (PR) 1·18, 95% confidence interval (CI) 0·92-1·52]. Similarly, receipt of a safe-storage container alone had no effect on prevalence of contamination (PR 1·02, 95% CI 0·79-1·31). Although use of water pasteurization indicators and locally available storage containers did not increase the safety of household drinking water in this study, future research could illuminate factors that facilitate the effective use of these interventions to improve water quality and reduce the risk of waterborne disease in populations that boil drinking water.

Effects of Source- versus Household Contamination of Tubewell Water on Child Diarrhea in Rural Bangladesh: A Randomized Controlled Trial

PubMed Central

Unicomb, Leanne; Arnold, Benjamin F.; Colford Jr., John M.; Luby, Stephen P.

2015-01-01

Background Shallow tubewells are the primary drinking water source for most rural Bangladeshis. Fecal contamination has been detected in tubewells, at low concentrations at the source and at higher levels at the point of use. We conducted a randomized controlled trial to assess whether improving the microbiological quality of tubewell drinking water by household water treatment and safe storage would reduce diarrhea in children <2 years in rural Bangladesh. Methods We randomly assigned 1800 households with a child aged 6-18 months (index child) into one of three arms: chlorine plus safe storage, safe storage and control. We followed households with monthly visits for one year to promote the interventions, track their uptake, test participants’ source and stored water for fecal contamination, and record caregiver-reported child diarrhea prevalence (primary outcome). To assess reporting bias, we also collected data on health outcomes that are not expected to be impacted by our interventions. Findings Both interventions had high uptake. Safe storage, alone or combined with chlorination, reduced heavy contamination of stored water. Compared to controls, diarrhea in index children was reduced by 36% in the chlorine plus safe storage arm (prevalence ratio, PR = 0.64, 0.55-0.73) and 31% in the safe storage arm (PR = 0.69, 0.60-0.80), with no difference between the two intervention arms. One limitation of the study was the non-blinded design with self-reported outcomes. However, the prevalence of health outcomes not expected to be impacted by water interventions did not differ between study arms, suggesting minimal reporting bias. Conclusions Safe storage significantly improved drinking water quality at the point of use and reduced child diarrhea in rural Bangladesh. There was no added benefit from combining safe storage with chlorination. Efforts should be undertaken to implement and evaluate long-term efforts for safe water storage in Bangladesh. Trial Registration ClinicalTrials.gov NCT01350063 PMID:25816342

Fluorescence based spectral assessment of pork meat freshness

USDA-ARS?s Scientific Manuscript database

Development of sensitive, nondestructive measurement methods for meat freshness is necessary to ensure safe distribution of meat products in the continually growing meat market. Fluorescence spectral technology has been shown to be a promising measurement method for quality and safety evaluation of ...

Impacts of using salt and salt brine for roadway deicing.

DOT National Transportation Integrated Search

2014-06-01

Idaho Transportation Department (ITD) uses a variety of methods to help ensure safe travel on the state highway system : following winter storm events. These methods include plowing, use of sand to improve traction, and use of salt and chemical : com...

Production of hydrocarbons from hydrates. [DOE patent application

DOEpatents

McGuire, P.L.

1981-09-08

An economical and safe method of producing hydrocarbons (or natural gas) from in situ hydrocarbon-containing hydrates is given. Once started, the method will be self-driven and will continue producing hydrocarbons over an extended period of time (i.e., many days).

41 CFR 102-35.30 - What actions must I take or am I authorized to take regardless of the property disposition method?

Code of Federal Regulations, 2013 CFR

2013-07-01

... Public Contracts and Property Management Federal Property Management Regulations System (Continued... of the disposition method used: (a) You must maintain property in a safe, secure, and cost-effective...

A Novel Biopsy Method for Isolating Neural Stem Cells from the Subventricular Zone of the Adult Rat Brain for Autologous Transplantation in CNS Injuries.

PubMed

Aligholi, Hadi; Hassanzadeh, Gholamreza; Gorji, Ali; Azari, Hassan

2016-01-01

Despite all attempts the problem of regeneration in damaged central nervous system (CNS) has remained challenging due to its cellular complexity and highly organized and sophisticated connections. In this regard, stem cell therapy might serve as a viable therapeutic approach aiming either to support the damaged tissue and hence to reduce the subsequent neurological dysfunctions and impairments or to replace the lost cells and re-establish damaged circuitries. Adult neural stem/progenitor cells (NS/PCs) are one of the outstanding cell sources that can be isolated from the subventricular zone (SVZ) of the lateral ventricles. These cells can differentiate into neurons, astrocytes, and oligodendrocytes. Implanting autologous NS/PCs will greatly benefit the patients by avoiding immune rejection after implantation, better survival, and integration with the host tissue. Developing safe and efficient methods in small animal models will provide us with the opportunity to optimize procedures required to achieve successful human autologous NS/PC transplantation in near future. In this chapter, a highly controlled and safe biopsy method for harvesting stem cell containing tissue from the SVZ of adult rat brain is introduced. Then, isolation and expansion of NS/PCs from harvested specimen as well as the techniques to verify proliferation and differentiation capacity of the resulting NS/PCs are discussed. Finally, a method for assessing the biopsy lesion volume in the brain is described. This safe biopsy method in rat provides a unique tool to study autologous NS/PC transplantation in different CNS injury models.

Causal inference with missing exposure information: Methods and applications to an obstetric study.

PubMed

Zhang, Zhiwei; Liu, Wei; Zhang, Bo; Tang, Li; Zhang, Jun

2016-10-01

Causal inference in observational studies is frequently challenged by the occurrence of missing data, in addition to confounding. Motivated by the Consortium on Safe Labor, a large observational study of obstetric labor practice and birth outcomes, this article focuses on the problem of missing exposure information in a causal analysis of observational data. This problem can be approached from different angles (i.e. missing covariates and causal inference), and useful methods can be obtained by drawing upon the available techniques and insights in both areas. In this article, we describe and compare a collection of methods based on different modeling assumptions, under standard assumptions for missing data (i.e. missing-at-random and positivity) and for causal inference with complete data (i.e. no unmeasured confounding and another positivity assumption). These methods involve three models: one for treatment assignment, one for the dependence of outcome on treatment and covariates, and one for the missing data mechanism. In general, consistent estimation of causal quantities requires correct specification of at least two of the three models, although there may be some flexibility as to which two models need to be correct. Such flexibility is afforded by doubly robust estimators adapted from the missing covariates literature and the literature on causal inference with complete data, and by a newly developed triply robust estimator that is consistent if any two of the three models are correct. The methods are applied to the Consortium on Safe Labor data and compared in a simulation study mimicking the Consortium on Safe Labor. © The Author(s) 2013.

Access to safe abortion: progress and challenges since the 1994 International Conference on Population and Development (ICPD).

PubMed

Shah, Iqbal H; Åhman, Elisabeth; Ortayli, Nuriye

2014-12-01

The 1994 International Conference on Population and Development (ICPD) viewed access to safe abortion as imperative for public health. Globally, the number of induced abortions (safe and unsafe) per 1000 women aged 15-44 years declined from 35 in 1995 to 28 in 2008. The number of deaths due to unsafe abortion declined from 69,000 in 1990 to 47,000 in 2008, as safe and effective methods of abortion, including manual vacuum aspiration and medical abortion, became more widely available. During the same period, there was a slight increase in the number of countries where abortion is permitted on request, and 70 countries made grounds for abortion more liberal. Since ICPD, the decline in unsafe abortion was slower than that in safe abortion, and unsafe-abortion-related mortality continued to be a problem. Nearly all unsafe abortions and mortality occur in developing countries. While more must be done to ensure universal access to safe, acceptable and affordable contraception to reduce the need for abortion, this need will always exist. Information on grounds for safe abortion should be made widely available for women to access services to which they are legally entitled to. As recommended by ICPD, quality postabortion care including contraception counseling and provision should be available to all women, regardless of the legal grounds for abortion. The paper provides the evidence on unsafe abortion, a reproductive health issue that is entirely preventable but has been largely neglected or tarnished by emotional and contentious debates. Copyright © 2014 Elsevier Inc. All rights reserved.

Accounting for water quality in monitoring access to safe drinking-water as part of the Millennium Development Goals: lessons from five countries

PubMed Central

Bain, Rob ES; Wright, Jim A; Yang, Hong; Pedley, Steve; Bartram, Jamie K

2012-01-01

Abstract Objective To determine how data on water source quality affect assessments of progress towards the 2015 Millennium Development Goal (MDG) target on access to safe drinking-water. Methods Data from five countries on whether drinking-water sources complied with World Health Organization water quality guidelines on contamination with thermotolerant coliform bacteria, arsenic, fluoride and nitrates in 2004 and 2005 were obtained from the Rapid Assessment of Drinking-Water Quality project. These data were used to adjust estimates of the proportion of the population with access to safe drinking-water at the MDG baseline in 1990 and in 2008 made by the Joint Monitoring Programme for Water Supply and Sanitation, which classified all improved sources as safe. Findings Taking account of data on water source quality resulted in substantially lower estimates of the percentage of the population with access to safe drinking-water in 2008 in four of the five study countries: the absolute reduction was 11% in Ethiopia, 16% in Nicaragua, 15% in Nigeria and 7% in Tajikistan. There was only a slight reduction in Jordan. Microbial contamination was more common than chemical contamination. Conclusion The criterion used by the MDG indicator to determine whether a water source is safe can lead to substantial overestimates of the population with access to safe drinking-water and, consequently, also overestimates the progress made towards the 2015 MDG target. Monitoring drinking-water supplies by recording both access to water sources and their safety would be a substantial improvement. PMID:22461718

The challenges of simulating wake vortex encounters and assessing separation criteria

NASA Technical Reports Server (NTRS)

Dunham, R. E.; Stuever, Robert A.; Vicroy, Dan D.

1993-01-01

During landings and take-offs, the longitudinal spacing between airplanes is in part determined by the safe separation required to avoid the trailing vortex wake of the preceding aircraft. Safe exploration of the feasibility of reducing longitudinal separation standards will require use of aircraft simulators. This paper discusses the approaches to vortex modeling, methods for modeling the aircraft/vortex interaction, some of the previous attempts of defining vortex hazard criteria, and current understanding of the development of vortex hazard criteria.

Familiarization and Detection of Green Monopropellants Image

NASA Technical Reports Server (NTRS)

Coan, Mary R.

2015-01-01

Ammonium dinitramide (ADN) and hydroxyl ammonium nitrate (HAN) are green monopropellants which will be appearing at Kennedy Space Center (KSC) for processing in the next few years. These are relatively safe replacements for hydrazine as a monopropellant; however, little is known about methods of leak detection, vapor scrubbing, air emissions, or cleanup that will be required for safe and environmentally benign operations at KSC. The goal of this work is to develop leak detection and related technologies for the two new green monopropellants.