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Polychlorinated biphenyls (PCBs) have been found in soil, which has typically been the result of industrial pollution in the past two decades. Although they are banned, PCBs can still be found in soils and other environmental media. For this reason, it is critical to develop an analytical method that can reliably identify and monitor their sources. This study describes a gas chromatography with mass spectrometry (GC-MS) technique, which was used to detect PCBs in soil samples by using a fast extraction method. Using the QuEChERS (quick, easy, cheap, effective, rugged, and safe) method, PCBs were more effectively extracted from soil. Different related parameters, such as time of shaking and centrifuging, type of solvent, and clean-up adsorbents, were compared and optimized. As the extraction solvent, acetonitrile/water produced the best results, and as the dispersive solid-phase extraction sorbent, diatomaceous earth produced the best results. Procedures allowed recovery values between 95.3% and 103.2%. A limit of detection of 1.9 µg/kg was determined with relative standard deviations (n = 3) of 2.1–4.0% for intra-day assays and 3.6–5.8% for inter-day assays. It was demonstrated that the method was simple, sensitive, efficient, and environmentally friendly when applied to soil samples. To our knowledge, an integrated approach based on QuEChERS for the determination of Aroclor 1254 in soil has not been published before. It is believed that this approach will eliminate the significant challenge of sample extraction in GC-MS processing, which was considered to be a procedural challenge in previous analyses. [ABSTRACT FROM AUTHOR]

The present study aimed to apply a multi-residue method for the screening and quantification of pesticide residues in ciders, low alcoholic beverages made by fermentation of apple juice. Twenty bottled craft cider samples purchased from the Czech market were analysed for pesticide residues. The residues of pesticides were extracted from samples using the QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) procedure in combination with additional solid-phase extraction (SPE) sample clean-up to achieve the lowest detection limit possible. In this study, targeted screening of pesticide residues in the samples was performed with the Q-Orbitrap mass spectrometry instrument. We identified 18 pesticides in cider samples analysed by screening method using an accurate-mass database of about 500 pesticide compounds, including their retention times, empirical formulas, and characteristic fragments. Additionally, liquid chromatography with high-resolution tandem mass spectrometer (LC-HRMS/MS) was used for re-analysis of positive findings of pesticides in samples and allowed to quantify compounds of interest at 0.2 µg·L-1 concentration level. The monitoring scheme was applied to the set of craft ciders, and the results revealed the presence of pesticide residues in most of the samples at trace levels ranging from 0.5 to 5 µg·L-1 and rarely at a level higher than 10 µg·L-1. [ABSTRACT FROM AUTHOR]

Background: Honey, the natural sweetener, obtained from Apis mellifera (honey bees) possesses many medicinal properties. Intensive use of carbamate insecticide in agricultural land not only contaminates the crop but also affects the honey and honey matrices. Hence, this study focused on the analysis of insecticide in honey. Objective: Liquid chromatography–mass spectrometry/mass spectrometry (LC-MS/MS) method development for the determination of Carbaryl insecticide in honey and Comparisons of different extraction techniques to determine the efficiency of extraction process. Materials and Methods: The LC-MS/MS method was developed by optimizing the multiple reaction monitoring (MRM) parameters. Further, the comparison study was done for the optimized extraction techniques such as quick, easy, cheap, effective, rugged, and safe (QuEChERS) method and ultrasound solid phase extraction (SPE) in the developed method. The validation was studied for the developed method as well as the extraction techniques to confirm the robustness of the developed method. Results: The validation study showed good accuracy for the developed method for the concentration from 2 to 9 ppb of the working solution. Limit of detection for the developed method was 0.08 and 0.05 ppb for the fragments 145.1 m/z and 127.1 m/z, respectively. Moreover, limit of quantification for the fragment 145.1 m/z was 0.24 ppb and for 127.1 m/z was 0.16 ppb. The average accuracies for the developed method of both the fragments (145.1 m/z and 127.1 m/z) were 98.51% and 98.15%, respectively. Recovery percentage for optimized QuEChERS ranged from 107% to 112% and for the ultrasound-SPE and from 107% to 118% of the honey samples which were spiked with three different concentrations of analyte. Conclusion: From the validation, it was confirmed that the developed method was robust and simple and provides better sensitivity and intensity and low consumption of chemicals. Thus, the developed method can be used for the routine analysis of carbaryl in honey. [ABSTRACT FROM AUTHOR]

Abstract: A quick, easy, cheap, effective, rugged, and safe procedure was designed to extract pesticide residues from fruits and vegetables with a high percentage of water. It has not been used extensively for the extraction of phthalate esters from sediments, soils, and sludges. In this work, this procedure was combined with gas chromatography with mass spectrometry to determine 16 selected phthalate esters in soil. The extraction efficiency of the samples was improved by ultrasonic extraction and dissolution of the soil samples in ultra‐pure water, which promoted the dispersion of the samples. Furthermore, we have simplified the extraction step and reduced the risk of organic solvent contamination by minimizing the use of organic solvents. Different extraction solvents and clean‐up adsorbents were compared to optimize the procedure. Dichloromethane/n‐hexane (1:1, v/v) and n‐hexane/acetone (1:1, v/v) were selected as the extractants from the six extraction solvents tested. C18/primary secondary amine (1:1, m/m) was selected as the sorbent from the five clean‐up adsorbents tested. The recoveries from the spiked soils ranged from 70.00 to 117.90% with relative standard deviation values of 0.67–4.62%. The proposed approach was satisfactorily applied for the determination of phthalate esters in 12 contaminated soil samples. [ABSTRACT FROM AUTHOR]

One of the main factors involved in entheseal changes (EC) aetiology may be related to the physiological limits of biomechanical loading fixed during bone development, such that higher load during childhood and the adolescent growth spurt leads to a lower frequency of EC during adulthood. In this sense, it is possible that ECs may be related to overloading beyond an individual's normal physiological limits as established during childhood and adolescence. This meta-analysis tested this aetiological possibility by studying the influence of terrain on the entheses of the lower extremities. The hypothesis is that individuals who inhabited rugged terrain have lower EC than those living in flat terrain. This is because biomechanical loads associated with rugged terrain will lead to a higher normal capacity (defined during skeletal development) mitigating the probability of overloading compared to those living in flat terrain who will therefore have a higher frequency of ECs. To test this, papers reporting EC frequencies in the lower limbs were analysed alongside the local terrain. Terrain was defined into two categories: flat or rugged based on altimetry profile, i.e. the average elevation gains and losses along four specific paths (North-South, East-West, Northwest-Southeast, Southwest-Northeast). Odds ratios were calculated to compare rugged and flat terrain. The overall results are consistent with the hypothesis that overloading is a factor in EC aetiology. However, when the analysis is conducted by sex and side, this general trend does not always occur. Limitations such as the lack of standardized age ranges could be affecting the outcome, i.e. older individuals have a higher frequency of ECs. The findings of this analysis suggest that the theoretical assumptions associated with the cause of ECs require further testing and evaluation. Copyright © 2017 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

A poly(lauryl methacrylate- co -methacrylic acid- co -ethylene glycol dimethacrylate) [LMA-MAA-EDMA] monolithic column was used to simultaneously determine amphenicol antibiotics (chloramphenicol/CAP, thiamphenicol/TAP, and florfenicol/FF) in milk and honey samples by capillary liquid chromatography tandem mass spectrometry (LC-MS/MS). QuEChERS (quick, easy, cheap, effective, rugged, and safe) method was optimized for sample pretreatment. Good linearity (0.1−15 ng g −1 ) and extraction recoveries (95.8−100.2% and 95.6−99.3% for milk and honey samples, respectively; n =3) with minor matrix effect (≦5% ion suppression) were obtained. Limits of detection were estimated at 0.02−0.045 ng g −1 . Good intra-day/inter-day precision (0.2−9.1%/0.3−8.7%) and accuracy (90.5−110.0%/93.4−109.3%) were achieved. With more than 200 analyses of real samples, no noticeable carry-over and deterioration of separation efficiency were observed using the monolithic column. The applicability of the developed QuEChERS-capillary LC-MS/MS method was demonstrated by determining the occurrence of CAP, TAP, and FF in various milk and honey samples. [ABSTRACT FROM AUTHOR]

A simple extraction technique has been developed for seven macrolide antibiotics in milk. The procedure involves a modified quick, easy, cheap, effective, rugged, and safe method based on acetonitrile extraction, followed by the addition of a mixture of salts (sodium sulfate, sodium chloride, and potassium carbonate) not yet reported in literature. The method was validated for tylosin and was selective, free of matrix effect, and linear in the range of 0.78-18.75 ng/mL in the final extract, corresponding to 0.125-3 times the maximum residue limit. The limit of detection, limit of quantification, decision limit, and detection capability were, respectively, 0.84, 2.79, 58.4, and 71.7 μg/kg. The overall average recovery at 25, 50, and 75 μg/kg ranged from 89-97%. Repeatability and intermediate precision expressed by relative standard deviations were below 10.5 and 12%, respectively. The extension of the validation for spiramycin, throleandomycin, oleandomycin, roxithromycin, erythromycin, and clarithromycin is under consideration since the procedure proved to be able to efficiently extract all studied macrolides, with recoveries from 74-104% at 50 μg/kg for tylosin, erythromycin, spiramycin, and oleandomycin and 20 μg/kg for throleandomycin, roxithromycin, and clarithromycin. [ABSTRACT FROM AUTHOR]

Abstract: Single domain antibodies (sdAb) are recombinantly produced variable domains derived from the heavy-chain only antibodies found in camelids. Previously, we selected sdAb that were specific for both ricin and botulinum A (BoNT A) toxin complex from phage display libraries of sdAb and evaluated the solubly expressed protein. Here, phage-displayed sdAb were used as reporter reagents and compared to soluble, unfused sdAb. We found that using phage-displayed sdAb as reporter elements in immunoassay formats gave improved detection over using unfused, soluble sdAb reporters. In enzyme-linked immunosorbent assays (ELISAs), the lowest level of toxin detected for both ricin and BoNT A toxoid complex was decreased by one to two orders of magnitude using phage-displayed sdAb as reporter reagents. Use of the phage preserved the ability to discriminate ricin and RCA120 by at least a factor of 10 fold. In an effort to reduce the number of steps in the assays, we directly labeled phage displaying sdAb with a Cy-3 fluorescent dye. Signal was greatly decreased using the dye-labeled phage compared to biotinylated phage followed by streptavidin–phycoerythrin. In these assays the use of phage-displayed sdAb gives more sensitive detection than soluble sdAb alone, however directly dye labeling the phage failed to provide responses of a similar magnitude. [Copyright &y& Elsevier]

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 (r2 > 0.99) was obtained over the range of concentration from 0.05 μ g/mL to 0.5 μ 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. [ABSTRACT FROM AUTHOR]

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 MgSO4 and 3 g NaCl was applied in the sample preparation. The clean-up was carried out by applying dispersive solid-phase with 150 mg MgSO4 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 (R2) 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. [ABSTRACT FROM AUTHOR]

Abstract: A new method for the analysis of phenoxy acid herbicide residues in rice, based on the use of liquid extraction/partition and dispersive solid phase extraction (dispersive-SPE) followed by ultra-performance liquid chromatography–electrospray ionization tandem mass spectrometry (UPLC–ESI–MS/MS), is reported. 5% (v/v) formic acid in acetonitrile as the extraction solvent and inclusion of citrate buffer helped partitioning of all the analytes into the acetonitrile phase. The extract was then cleaned up by dispersive-SPE using C18 and alumina neutral as selective sorbents. Further optimization of sample preparation and determination allowed recoveries of between 45 and 104% for all 13 phenoxy acid herbicides with RSD values lower than 13.3% at 5.0μgkg−1 concentration level. Limit of detections (LODs) of 0.5μgkg−1 or below were attained for all 13 phenoxy acids. Quantitative analysis was done in the multiple-reaction monitoring (MRM) mode using two combinations of selected precursor ion and product ion transition for each compound. This developed method produced relatively higher recoveries of the acid herbicides with a smaller range of variation and less susceptibility to matrix effects, than the original QuEChERS ( Quick, Easy, Cheap, Effective, Rugged, and Safe) method. [Copyright &y& Elsevier]

A rapid, high-throughput method employing ultra-performance liquid chromatography with tandem quadrupole mass spectrometry (UPLC-MS/MS) was developed and optimized for simultaneous quantification and confirmation of 64 pesticide residues and their toxic metabolites in fruit extracts prepared by a buffered QuEChERS procedure. The total time required for UPLC-MS/MS analysis was 8 min plus 2 min for re-equilibration to the initial UPLC conditions. Performance characteristics were determined for apple extracts spiked at 10 µg kg-1. The repeatability of measurements expressed as relative standard deviations was in the range 1.5-13% at this level for most analytes. Thanks to very low limits of quantification (<10 µg kg-1for the majority of pesticides), an optimized method allows for the reliable control of not only common maximum residue limits (MRLs) set by European Union regulation for various pesticides/fruit combinations, but also of a uniform MRL of 10 µg kg-1endorsed for baby food. [ABSTRACT FROM AUTHOR]